Professional Documents
Culture Documents
r4 it _I Ai
4
. C I,- 04., 4.
Catalyst Chemistry 1
Process Variables 2
Process Evaluation
(Water Chloride) 2
Procedures - Startup 3
Regeneration 3
%
,,
UOP Inc.
Des Plainrs, Illinois
United States of America
IIVITRODUCTION
This material is UOP Inc 's technical information of a conficlontial nature for use only by personnel
within your organization requiring the information. T he material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc
PLATFORMS-11
NC
COURSE SCHEDULE
Chemistry
Hydrocarbon Chemistry
Reaction Rates/Heats of Reaction
Equilibrium & Selectivity Considerations
Hydrocarbon Conversion Profiles
Catalyst Chemistry/Pressure Effects
Process Variables
Catalyst Activity Determination
Effects of Process Variables on C5 + Yield
Effects of Process Variables on Catalyst Deactivation
Calculation of Heat of Reaction
Process Flow
Variations of Commercial Flow Schemes
Selected Control Schemes
Water-Chloride Control
Typical Water/Chloride Injection Rates
Methods of Proper Water/Chloride Control
On-Stream Catalyst Sampling
Analytical Methods
Typical Sampling Schedule
Required Sample Size
Shipping Considerations
Outlines of Selected Laboratory Methods
Catalyst Handling
Catalyst Loading Considerations
Unloading Spent (Carbonized) Catalysts
Procedures
Startup
Shutdown
Emergency
Operation of Recycle Gas Drier
On-Stream Catalyst Sampling
Regeneration
Procedure
Sulfate Removal
Regeneration Piping Locations
Chemical Specifications and Properties
Calculations
Sampling Schedule
Mechanical
Corrosion/Materials of Construction
Inspection Considerations
Compressor Washing Procedure
Acidizing Procedure
General 30 Day Shutdown
Mechanical Evaluation Test
Energy Conservation
Process Changes
Mechanical Improvements
Safety
Entering a Contaminated Atmosphere
Chemical Hazards
Continuous Platforming
Need For Continuous Catalyst Regeneration
Process Description
A4
117013
HISTORY OF UOP
A-7
(17013
Merox
Molex
Udex
Sulfolane
Olex
Butamer
Penex
Isomax (Unibon) - IZCU, HUG, LPG, etc.
Detergent Alkylation
Alkar
ii yd eat
Tatoray
I LIOP RN;.
ppocESS
D‘InsioN
I I
RNAMCI SwenuelAusa lawman TicR summit IMARKSTUla PLANNING
I
I
Rom pRociEss DISTRICT
OPCRATIOKS SuSINESS
aRouPs *LS»Cis DEVELOpilitiff laiSPCCnces
I ...11. G M•
PLATPoRsusea
117013
I NTRODUCTION
A-11
uop Inc
117013
B or BZ benzene
BTX benzene, toluene, xylene
EDC ethylenedichioride
F, F - flourine, flouride
Fe iron
H2 molecular hydrogen
MCP methylcyclopentane
Mn manganese
Mo molybdenum
N naphthene (nitrogen)
N6 6 carbon number naphthene
N7 7 carbon number naphthene
" etc.
Na sodium
Na2CO3 sodium carbonate (soda ash)
NaOH sodium hydroxide (caustic)
Ni nickel
0 olefin (oxygen)
P paraffin
P1 1 carbon number paraffin (methane)
P2 2 carbon number paraffin (ethane)
P3 3 carbon number paraffin (propane)
" etc.
Pb lead
POC propylene dichloride
PONA paraffin-olefln•naphthene•aromatic
Pt platinum
Re rhenium
S sulfur
T toluene
ICE trichloroethane
TEL tetraethyl lead
TML tetramethyl lead
X xylene
A•16
GENERAL PLATFORMER TERMS
A — angstrom, 10 - Mmeter
ABD — average bulk density
activity — the temperature requirement needed by a catalyst to produce a
given octane Platformate at fixed operating conditions and feed•
stock quality
acid site — a position or function of the catalyst needed to promote certain of
the desired reactions; generally provided by flouride or chloride
ASTM — American Society for Testing and Materials
attenuation — modification or tempering of the metal function of the catalyst
DC4 — debutanizer
delta P (QP) — pressure change
delta T ( QT) — temperature change (normally across a reactor)
GC — gas chromatography
GHSV — gas hourly space velocity
GLC — gas/liquid chromatography
G/O ratio — gas/oil ratio (total moles of recycle gas divided by moles of fresh
naphtha feed)
gph — gallons per hour
A-17
IBP — initial boiling point
A•18
SG — specific gravity
shield — part of radial reactor internals (see page G-11)
skirt — same as shield
slump catalyst — extra catalyst added to the top of a radial flow reactor to com-
pensate for bed settling during operation (see page G-10)
soda ash — sodium carbonate
SOR — start of run
stability — the quality of a catalyst enabling it to run for long periods of time
with almost constant yields and temperature requirement
WABT — weighted average bed temperature (the sum of the average reactor
temperatures multiplied by the fraction of catalyst in each reactor)
WAIT — weighted average inlet temperatures (the sum of the reactor inlet
temperatures multiplied by the fraction of catalyst in the reactor)
wt, wt.% — weight, weight percent
UOP P + I DIAGRAM ABBREVIATIONS
AR Analysis Recorder
ARC Analysis Recording Controller
DR Specific Gravity Recorder
FA Flow Alarm
FE Orifice Flange Assembly
FFRC Flow (ratio) Recording Controller
Fl Flow Indicator
FIC Flow Indicator Controller
FIF Flow Indicator Float Type
FQI Flow Meter Displacement Type
FR Flow Recorder
FRA Flow Recording Alarm
FRC Flow Recording Controller
FRCF Flow Recording Controller Float Type
FRCQI Flow Recording Controller Integrator
FROI Flow Recorder Integrator
FRQIA Flow Recorder Integrator Alarm
HC Hand Control
II Current Indicator
LA Level Alarm
LC Level Controller
LG-E1 Gage Glass Boiler Type — Visible Length Shown
LG R - Gage Glass Reflex Type —Visible Length Shown
LG-RLT Gage Glass Reflex Type — Visible Length Shown — Low Temperature
LG-T Gage Glass Through View Type Visible Length Shown
—
LG-TK Gage Glass Through View Type — Visible Length Shown — KEL-F
LG - TLT Gage Glass Through View Type — Visible Length Shown — Low Tem-
perature
LI Level Indicator
LIA Level Indicating Alarm
LIC Level Indicating Controller
LR Level Recorder
LRA Level Recording Alarm
LRC Level Recording Controller
PA Pressure Alarm
PC Pressure Controller
PDC Pressure Differential Controller
PDI Pressure Differential Indicator
PDIC Pressure Differential Indicating Controller
PDR Pressure Differential Recorder
PORA Pressure Differential Recording Alarm
PDRC Pressure Differential Recording Controller
PORCA Pressure Differential Recording Controller Alarm
PI Pressure Indicator
PIA Pressure Indicating Alarm
PiC Pressure Indicating Controller
PR Pressure Recorder
PRA Pressure Recording Alarm
PRC Pressure Recording Controller
A-20
Si Speed Indicator
SR Speed Recorder
TA Temperature Alarm
TC Temperature Controller
TDR Temperature Differential Recorder
TDRA Temperature Differential Recording Alarm
TDRC Temperature Differential Recording Controller
TI Temperature Indicator
TIC Temperature Indicating Controller
TIX Temperature Indicator Skin
TR Temperature Recorder
TRA Temperature Recording Alarm
TRC Temperature Recording Controller
TRX Temperature Recorder Skin
TW Thermowell
ZI Valve Position Indicator
HYDROCARBON
CHEMISTRY
This material is UOP Inc.'s technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc
PLATFORMING 1
117013
I NTRODUCTION
D. Heats of Reaction
E. Equilibrium Considerations
C. PlatfOrming Catalysts
117013
FIGURE 1
LEAN RICH
PLATFORMATE PLATFORMATE
NAPHTHA NAPHTHA
LOSS
L O SS
P
P
P
N —N
FROM P
FROM P
N A FROM N
N A FROM N
A }FROM A A • FROM A
LEGEND
P = PARAFFINS LOSS: DUE TO BOTH CRACKING
N = NAPHTHENES AND SHRINKAGE
A ir AROMATICS
B-7
uopprbc.
117013
B. Platforming Reactions
1. Dehydrogenation of Naphthenes:
FIGURE 2
NAPHTH EN E DEHYDROGENATION
+ 3H 2
NOTE
FIGURE 3
NAPHTHENE ISOMERIZATION
II 0
117013
FIGURE 4
PARAFFIN ISOMERIZATION
C
R-C-C-C-C R-C-C-C
trOP , 0 , 11
3. Dehydrocyclization of paraffins:
FIGURE 5
PARAFFIN DEHYDROCYCLIZATION
+H
2
R-C-C-C-C 11
+ H2
.101..“8"
4. Hydrocracking:
FIGURE 6
HYDROCRACKING
C HC
R-C-C-C + H2 --as- RH C-C-C
.20P •71, .2
5. Demethylation:
FIGURE 7
DEMETHY LATION
R-C-C-C-C + H R-C-C-CH + CH 4
2
AND
R-C RH
+ H
2 Cji + CH 4
Li- 1 2
117013
6. Dealkylation of aromatics:
FIGURE 8
AROMATIC DEALKYLATION
rr
+ H2 +R
von ,Olti 14
TABLE 1
RELATIVE REACTION RATES
C 6 AND C 7 HYDROCARBONS
CARBON NO. C. C7 C6 C7 C6 C7
a
REACTION CLASS RELATIVE REACTION RATE
ISOMERIZATION
PARAFFIN 10 13
NAPHTHENE 10 13
DEHYDROCYCLIZATION 1.0 4.0
HYDROCRACKING 3.0 4.0
DECYCLIZATION
( RING OPENING) 5 3
DEHYDROGENATION 100 120
B-15
UOP Inc
117013
E. Equilibrium Considerations
K k1 = ( P ■ACP)(P112)
P
k2 (P
nC )
6
PMCP
P
nC P
EI
6 2
FIGURE 11
CYCLOMEXANE
METHYLCYCLOPENTANE
EQUILIBRIUM
0.14
0
1
17. 0.12
4
2 0.10
a.
Ca A 0.08
Ci 0.06
0.04
400 450 500 550 800
(752) (932) (1112)
TEMPERATURE, °C (°F) , t •t
▪ •
117013
FIGURE 13
Z
kil uj .40
5 kg / cm2 (71 psig)___
Z cg
O Z
0
LAI cc .10
IIJ
N
a
2 0 NU, ,17f1
uop Inc
•
117013
FIGURE 15
SELECTIVITY OF NORMAL HEPTANE
TO TOLUENE
W.80
7 kg I cm 2 1100 psig) —
> .60
> Q 14 kg/cm± 42000 prig)
0
• u 21 kg/cm 2 130(---
) psig)
w .40
w
ca
cc
I .20
• "
aL ch
Lki 0
X -1
500 550
O 450
2 (842) (932) (1022)
REACTOR TEMPERATURE, "C (°F)
1.0, and 0.5 moles per 100 moles of feed through reactors 1 through
4. Paraffin disappearance on an absolute molar level is comparable
to cyclopentane conversion (4.0, 4.0, 7.0, and 6.5 moles per 100
moles of feed) but on the basis of percent converted per mole of
specific hydrocarbon feed, the paraffin conversion is much lower.
TABLE 3
PARAFFIN AND NAPHTHENE
CONVERSION PER REACTOR
TOTAL
REACTOR NO. 1 2 3 4 CONVERSION
CONVERSION OF FEED
HYDROCARBON TYPE,
PERCENT
CYCLOPENTANES 39 35 9 4 87
PARAFFINS 7 7 13 12 39
FIGURE 17
CYCLOPENTANE CONVERSION
REACTOR PROFILE
3
MOLES PER 100 MOLES OF FEED
111111i
Rim CP
6
1
1 CPS
11114
7-CPS
CP9
CP10 j
I 01 0.25 0.5 i.
FRACTION OF TOTAL CATALYST
117013
FIGURE 16
HYDROCARBON TYPES CONVERSION
REACTOR PROFILE
2 2
A
MOLES PER 100 MOLES OF FEED
—ger
30
10
CP
CH
0_1 0.25 0.5 1
13-2
117(113
FIGURE 14
SELECTIVITY OF
METHYLCYCLOPENTANE TO
BENZENE
W
Z uji
uj 1.. .70 7 kg / cm - (100 psig) —
ITJ
ef t-
,
• r 0
fo! (ret:viAlgo
W
o .60
14 kg / cm (200 psig) _
W
.so 21 kg / cm2 (300
P-
o cz
W
I" .40
ti) faa
0
2 2
.30
400 450 500 550
(752) (842) (932) (1022)
REACTOR TEMPERATURE, °C (°F)
B-22
117013
FIGURE 12
CYCLOHEXANE - BENZENE
EQUILIBRIUM
103
15 20
5 10
Ill) (142) 1213) (295)
2
HYDROGEN PARTIAL PRESSURE, kg / cm (psig)
ii 1 t,
•
117013
FIGURE 10
NORMAL - HEXANE /
METHYLCYCLOPENTANE
EQUILIBRIUM
1.2
1.0
CI
▪ U 0.8
cea.e
▪11u
2
O.
0.6
-400 ° C (752 ° F)
▪
ca
5
E
.
0.4
0.2
. .Ai 600 °C (1112 °F) -
W 500 °C (932 °F)
0 5 10 15 20 kg / cm
(71) (1421 (213) (285) ( Psig)
HYDROGEN PARTIAL PRESSURE ono .0 , 11 irf
117013
FIGURE 18
PARAFFIN CONVERSION
REACTOR PROFILE
MOLES PER 100 MOLES OF FEED
Pg
P 10
P11
01 0_25 05 1.0
FRACTION OF TOTAL CATALYST
l3-27
uop
117013
FIGURE 19
PARAFFIN ISOMERIZATION
REACTOR PROFILE
os
4
0
r
it
-
i■
3
2
0 2 _....
O
1
FIGURE 20
AROMATIC FORMATION
REACTOR PROFILE
20
Ac
MOLES PER 100 MOLES OF FEED
16 Ag-
As
A7-
12 W
FWEL 111
MOW A9
8
VA
Aio
WA.
A 10
211111W44
Mg
4
All
/II A
ll
0 01 0.25 05 10
FIGURE 21
C5+ RESEARCH OCTANE RATING
REACTOR PROFILE
100
MICRO RESEARCH CLEAR OCTANE
90
SO
70
60
l3-30
•
117013
FIGURE 22
TEMPERATURE
REACTOR PROFILE
I NLET
U.
-20
• (-36)
▪ 40
E4
1
tiJ
CC
-80
(-108)
ce
W
E -80
(-144)
CATALYST
CHEMISTRY
This material is UOP Inc 's technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not he reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc.
PLATFORMINC
117013
The concept of a single complex site does not effect the inherent
dual functional nature of a Platforming catalyst. The surface must
still possess both acidic and metallic characters. The acidic
character is mainly responsible for the formation of carbonium ions
by either extraction of hydride ions or addition of protons to
double bonds. Carbonium ions are, in turn, the intermediates in
such reactions as isomerization and hydrocracking. The metal
function is responsible for the extraction of hydrogen from
hydrocarbons, the splitting of hydrogen molecules and subsequent
addition of hydrogen atoms to unsaturated species. Combinations
of these two functions into a single complex site allows these
reactions to occur simultaneously.
- 85
YIELD, WT - % OF CHARGE
20
% OF CHARGE
18 MIDCONTINENT NAPHTHA - 80
PRODUCT 95 RONC
12 75
a - 70
- 65 ci
+ C2 C3 + C4 C5 +
H2
117013
FIGURE 24
EFFECT OF PRESSURE ON YIELD
STRUCTURE OF R-15 CATALYST
42 kg/cm 2 1000psig) 7 kg/cm 2 (100 psig) 771
90
24
YIELDS, WT - % OF CHARGE
YIELDS, WT - % OF CHARGE
80
20 HONG
70
2
99.9
16 7 kg/cm
42 kg/cm 2 104.2 80
12
50
8
40
4
30
s\
C2 C3 C4 C5 +
1 17013
FIGURE 25
EFFECT OF PRESSURE
ON YIELD STRUCTURE
100
HYDROGEN
PRODUCT YIELD, WT -
90
+ C2 C3 +
Jr
80
C5 + PLATFOR MATE
70
0 10 20 30 40
(143) (285) (428) (570)
FIGURE 26
EFFECT OF PRESSURE ON
PARAFFIN CONVERSION
4
HYDROCRACKED
MOLE % OF FEED PARAFFINS
TO AROMATICS
35
.. 42
/
I
■
i
.........
30 //
'"
,
..
.0,04
\
25 -,1---.
,
15
10 15 20
(285)
25
J
In
(42R)
lc an
(570)
PRESSURE, kg/cm2 ipsigi
PERFORMANCE SUMMARY OF
CURRENT COMMERCIAL UOP
PLATFORMING CATALYSTS
+8
+6
R-22 n-7 0
■
.... .,
R-60, R-62
w +4 - n•50
R• 16G
c." +2
ALL PT
BASE
+60
REACTION TEMPERATURE, 'C
+50
ALL PT R-22
+40
+30 - 11•504R-70 - --
R-d0, 62
+20
+10
BASE
a 711 40 60 80 100 120 140 160 18
CATALYST LIFE, DAYS ON STREAM
117013
TABLE 4
UOP PLATFORMING CATALYSTS
SOCK
NOMINAL LOADED
DIAMETER DENSITY PLATINUM RHENIUM CHLORIDE
CATALYST mm k g/m 3 WT 4o WY% WT% STATE
I
NOTES: EX = EXTRUDATE R - II, II - 11, R - 16H, R -22 and R -32 aro also
D = DENSE LOADED BY MACHINE available as 1/6" (Ramat*catalyst Those
,
- 16H (L).
= REDUCED AND SULF1DED cater/1e are deelgdaled with (1.), i... R
R = REDUCED
PROCESS
VARIABLES
This material is UOP Inc.'s technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not he reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc
1
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r1
1-1
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now ab 1
1170136015
Rev. 2
PROCESS VARIABLES
The operating variables which are the most pertinent are shown in
Table 1. For practical purposes, these variahles are sufficient to
define a Platforming operation.
Type of Mode
Platforming Operation Descriptor
Continuous Catalyst
Regeneration CCR
1
117013F,015
Rev. 2
A. Catalyst Type
B. Reactor Temperature
The temperature at which the Plat forming reactor catalyst beds are
held is the major control parameter the refiner uses to meet
product quality requirements. Platforming catalysts are capable of
operation over a wide range of temperature with little adverse
affect on product yield and catalyst stability. However, very high
temperatures, above 543°C ( 1010°F), may cause thermal reactions
which will decrease Platformate yield and catalyst stability.
- 2 -
1 171J13&015
Rev. 2
Although both the WAIT and the WART are of practical use,
neither exactly defines the true average catalyst temperature.
Also, in the discussion to follow, the WAIT will be used
exclusively. The WART will only have to fall within bounds as a
criterion for certain calculations.
C. Space Velocity
0. Reactor Pressure
-3
117013&015
Rev. 2
E. Hydrogen/Hydrocarbon Ratio
Laboratory
Property Method
Source of Stock
-4
117013&015
Rev. 2
Suffice it to say that the reader will obtain reasonable results when
using the following charts with either the UOP Method 777 or UOP
Method 273 PONA data. The important thing to hear in mind is (as
stated in the Chemistry Section) the leaner the stock is the more
difficult it is to reform. The converse is also true.
G. Feed Additives
A. Catalyst Activity
Numbers (ii) and (iii) require some explanation, but the reader
will note that the concept is simple. The basic idea is to determine
a number (Delta WAIT) which puts the catalyst temperature
requirement on a consistent basis for comparing day-to-day
operation. This would not be necessary, of course, if the semi-
regen or CCR Plat former ran at the same conditions (Feed N and A,
RONC, LI ISV) all the time. This is seldom t he case.
-
- 6 -
117013&015
Rev. 2
Semi-regen CCR
Step Mode Mode
1. List - RONC 95
- N and A '1'13
d
a; .3 - Actual Unit Operating Data-
- N + 3.5A
21
' 3 s. 3 33.:*
- LI--ISV
- Catalyst Type 2- 62.
3. Estimate Correction
for actual LIISV Figure 3 0-
0 Figure 3
111A T
•te, a Al
4)14
i I
((An e2 e...rneA ote.1
-
14 ea.., 4 4 . 4...c,40 .( W
SEMI-REGEN CCR
APPLICATION APPLICATION
Suppose now that the semi-regen unit for the day in question was
running an actual WAI r of 970°F. The engineer would tabulate and
plot for this day the following "Delta WAIT":
I n other words, the catalyst has lost a total of 13°F activity from
fresh catalyst. Day to day calculations would allow the engineer
- -
8
117013&015
Rev. 2
B. Catalyst Selectivity
SEMI-REGEN CCR
APPLICATION APPLICATION
2. Averages: 2. Averages
RONC 94 RONC 98
N+2A 57 N+2A 57
- 10 -
1171113&015
Rev. 2
C. Catalyst Stability
The rate at which a given catalyst forms coke is set by the process
variables listed below. The appropriate figures for both semi-
regen and CCR modes are also given and the reader may wish to
examine the differences between the two sets.
SEMI REGEN
- CCR
Relative Relative
Process Variables Deactivation Rate Coking Factor
a. Case Base A
RONC 93 95
N+A, LV-$ 50 44
Feed EP °F 360 385
Avg. Rx Pressure, psig 450 330
H2/HC 7 5.2
(1.42)(1.15)(1.30)(1.51)(1.57) = 5.10
Thus, case "A" will deactivate 5.10 times faster than the base
case. If the base case had shown at 30°F deactivation in WAIT
requirement over 100 BPP catalyst life, then case "A" would show
a 30 ° F WAIT deactivation over only 19.6 BPP catalyst life.
- 12 -
117013E015
Rev. 2
The refiner should also realize that any significant periods of Plat-
forming operation without catalyst circulation will increase the
amount of carbon on the spent catalyst above the level calculated
by the estimating procedure.
17.78 lbs/hr
(0.038) (450) =
Carbon laydown =X (CCR) =
1 -X ( 0.962)
Charge: 18,500111'1)
36 N + A, LV-%
350°F EP
*Total H2HC mol ratio equals H2HC mol ratio to the reactor plus 70
percent of the net gas hydrogen produced, on a mol ratio net gas to
mol ratio feed basis.
- 13 -
117013&015
Rev. 2
or X Carbon Laydown
CCR Carbon Laydown
12.37
450 + 12.37
The total delta T over the catalyst is directly related to the total
heat of reaction. While the heat of reaction is not a function of the
H2/HC mole ratio, the total delta T is, due to the "diluent effect"
of the recycle gas. Li-6V does not materially affect of the heat of
reaction.
- 14 -
11711136015
Rev. 2
Using Figures 21A and 21B or Figures 22A and 22)3, the heat of
reaction may he determined when the following are known:
MW correction =
+8(145/100) +12
TABLE 2
Catalyst Correction
°F °C
TABLE 3
CCR APPLICATIONS
CATALYST CORRECTIONS
FIGURE 2 - SOR WAIT REQUIREMENT
Catalyst Correction
FIGURE 1
1000
, --, BASIS:
r/411 MT
980
♦ IF•
r iv/
ALL PLATINUM
RONC-
4.1
520 CATALYSTS
,,
I4
960 `'46-7,.104
1
1T- 1 1
2 200.600 PSIG
/
r
510
1 Z(1.1. 11111
AVERAGE REACTOR
fa 1
/I/ /itlitl
1/
i
WAIT REQUIREMENT
fit!
940 PRESSURE
1111-1
►
`
- 500
1;11
1, ► 1
I
I
920 AND CHLORIDE
;r.f
!
490 LEVELS
-.1■414wimummi libb.
1_;
900
Jiil
4. 100 165 'C (210 330 -TI
(rrif
480
:
95 _—
►
1
ii1
.1‘1111irNIZNII
1
lim
ON CHARGE
880
I
- 470
90 5. I WAIT - WABTI
LESS THAN 15°C
860 460 125"F)
85
840 450
1111111111 80 _
440
820
30 50 70 90 110
HYDROTREATED NAPHTHA N + 3.5A CONTENT, LV%
117013&015
Rev. 2
FIGURE 2
WAIT REQUIREMENT
CORRECTION FOR LHSV
°F °C
- 35
60
- 30
50
- 25
WAIT CORRECTION
40
- 20
30
- 15
20
-- 10
10
- 5
-10 - -5
.75 1
1170 13F,0 15
Rev. 2
FIGURE 4
4
7
WAIT °C/RONC
WAIT °F/RONC
3
5
4
2
3
75 80 85 90 95 100 u0P 15413 4
C5 + PLATFORMATE RONC
117013&015
Rev. 2
FIGURE 5
5.0
MMEMMOIMMEMMEMINIMMEMMEMMINI
4.0 MEMMEMERMINIMINIMMEMMEMMEMM
MMEMUMME2==== 30
N ().orn
111.:411111111111 k 44111. .14.416.11mAIIIII: — nM
• Imp. 114.• •.4E.Ili
3
mil . 116 op. 1 Ilk Wilk am■im■a■■s 8
m
::::::::111.44:1111 MAI' %N MI 410111101::::::: >
r
MM■■MMMM■ porn& milimm I
mommums II. um s mob. limm.immal it.11191,1114.1mgems
ansOmOm. 10.0.1011 ■ .mill mil, • m. IP E. ■ OSS ■
miggsmassommomig• - mggommn_livellsou mipsift'lig•miss.mplim r0 8 - m
9 Cl,
LI l
• ■
millaaMMOMOSOOMINIMEMSSOOMOOMIPOSIff SINO0001 qm888m888■181111.81811
mmom gmmormaimmisma om moss ge. mai MOMOOMa gOOOmaamm.vramm
liOnsOOMOOROWORMOOmmmOmmEMOOM womMOOMMUMMIUM OmMUIMMIO MO
lemsellommo rmesseeminseumegiommomummmunklimmilk Isms
O W EOM SIIMMOIOSO gimp nummorommosessui limme • • MOD
simmegonmS magillOWNIRO umum SommemooMMOOMUMMege k wommana.Imm
MOOSOrm001,400000Esomm imummemiiiiSMOMMOmm ok mourns§ en
MM ... •••• im• •••••memagmum miegg egmesommomlsommusklo
mes••••••• ■ •••• MMMMMMMMMMMMMMMM gm elp imemplimma MMMMMMM Mikes
mimmosmommemmomm101111112i rmliraill SWOO 00Ofkloo mmis
• Imps mpg liggeopm.g.lesmosim
■ 9'0
OMOSOROMOO Immall m .
mmammama ■■ mem meamaSSO Mem man momMESIOnlb OSIOMOMME
WOOMMO ■ I millmmommullmOmmigwougualeffillerrOMUMOOMMELIOEMEOMO
MOOMOSMOU4 11:111::111111:111111111101111:011:1:11111011::::
MOOMMOOMMOSOOOMMOOMBO MMOIMOOMMOMMOOMOI OOMMOSOMMMOStIMSOMM
MOOMOOMMESMIMOMMOMMEMMOMOMIEMOSMSOOMOSOROODOBOOMOLMOSO
111 MON
111 •1111•0111111111111111 MMMMMMMMMMMM 111•10•111111••••••••••11111MIN•1110111111111111•1111111111111111. MN
OassmamomaaaammaasmomearniaaMaiallaaim palMOSOSOOORI WM L'O
MOMMEMOMMORMOMOOSMOSSI MON IIII II 00111 MOMMSOOSOOSSOMIRIMM
misamsmaaMOMMaaMasaaaagaammw ol • same aamMESOMMOMOMO,Ma
meamaiThammumaimmaaaammommumaaameaaaalleaasMailaarnammana , 0
aaaaalaMmanasmasaamumaamammamaasamaammaaaallaMagaaaassaMmaiftl
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiffilliiiiiiiiiiiiiiiii
Imewww"
:106:::::::45::::::::5:0::::41::::::::::::::::::::: 8'0
C1131A %Al + 5 3 NO
IN3.1.NO3 3113A3 JO 133333
9 3EMDIA
Z •Aau
SlO MOLll
117013E015
Rev. 2
FIGURE 7
EFFECT OF REACTOR
PRESSURE ON C 5 + LV% YIELD
GOOD FOR
1. FULL BOILING RANGE STRAIGHT RUN NAPHTHA
2. AVERAGE REACTOR PRESSURE 8.5 TO 42.0 kg / cm 2
(125 TO 600 psig)
4.0
IIIIIIIIIIIIIIIIIIIIIIII1
1111111111111111111111111
InoImilmommoIErna INFA
3.5
MMEMMIIMINIMMINIM IIIMMETMEM
MOMMIIMMO MM. MOW 30
MI MOM
MI WM IMO MMOMM 1.4. 40
N + 2A, LV°/o
E 3.0 mmEMMIWAvA
MOMMOMMEMMOMMOMMINWAINV 50
MINIMMOMMEMOMMTIMITAFA
90.4
OMMINIMMOMMIMMOM rfirA, 60
cc
2.5 1111111111.1111 Lb Ad 70
1111111111 IPAIIMOVW 80
9
2.0 111111111PAIIPARAWA
1
11111M19 74511
IAA
1.5 IPAgilliaidighl
:my igimpni 'WSJ/
il
(100
iliggalginie0p11111111
IPS11050T4041mill
U)
0
Z 1.0 arimmmiddleAr 40 .4 a rum
...m..706.4 '10.A MOM OM=
Ongitre061111111111111
0.5
100 ,17.40 0P■ MINIMERIMMEMOMINE
milm■ - otagnil orrahrimommurri
:;.00t
rimdi rmim insimmi milm
'um mil
0
80 85 90 95 100 105
C 5 RONC
UOP 19IR
- 23 -
117013F.015
Rev. 2
FIGURE 8
EFFECT OF F-1 CLEAR OCTANE
NUMBER ON C5+ LV% YIELD
GOOD FOR
1. FULL BOILING RANGE STRAIGHT RUN NAPHTHA
3. R - 30 SERIES CATALYSTS
5
111111111111111111111111111111111111M11111111111
11111111111111111111111M11111111111M1111111111
IN F-1 CLEAR OCTANE NUMBER
4
1 11 11111 1111111111 1111111111 1111111111
3 II 30
11 0 40
1
N + 2A LW/0
2 11111111111111111111111 111111111111111111r 0:4
p ll' 1
50
60
1 11111 1 0 °
1111111 011 I 1111 /1 ,00:00/0 70
,.,,,,,,0,0 /
80
1oluh::::.......mvads-
1 1 0101111
:„..... Illiooroi000
..............„,,...d.,......0,‘„,
90
1
ts.i
cn
a 0.9
al I v
v
'c'c' 0.8 ummmunnor-AstgOrauni, Ari
" fradon
Z 0.7 ummumum
i i r . is
Amp or , ist,r,40 inmn
- 410
lannignitrli0P.....
- 00.0•404iMum
1 :1 1 1 1 1 1 1 1 IIIIIII"
▪ 0.6
PRI211,79;iittilePteli5d111111111
p wri i m i
cr
t
a 0.5
opliiorp oprocioti or inmpuni
9 R
•ilow_dedi .."0 0 w rg 11111m1PIII
0.4 0 o
NogNiu sitiol ilarorri
iyi
j
J 0.3
0
:::;ii iiiis ruiliii III 11 I III 1111111111
i s
tu
5
0.2
IIIIII
0.1
80 85 90 95 100 1 05
C 5 + RONC UOD 391 ?
- 2ri -
In o a
O 0 O LO 0
CO co co
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00 n CD to Q M el
VZ + N NI 3SV383N1 %Al WI. H3d CI131A %Al + 9
3 NI 3SV3U3NI
1 17013&015
Rev. 2
FIGURE 10
EFFECT OF REACTOR
PRESSURE ON C5 4- LV% YIELD
GOOD FOR
1. FULL BOILING RANGE STRAIGHT RUN NAPHTHA
2_ AVERAGE REACTOR PRESSURE 8.5 TO 42.0 kg / cm 2
1125 TO 600 psig I
4.0
INIMMEMINIMMIONEMMEMMMOMMEE
OMMEMEMMEMMEMMEMINIMMEMME
MOMMINIMMOMMIIIMMOMMIMM
MOMMIMMIMINME 11111MOMMOMM
3.5
MEMEMMOMmmommE MIMMEMMEM
MEMMIMMIIMMONIMMOMMOMMINI
MMINIMMINMEMEmmommlIMMEMINIMI 30
MMOMOMMEMMAMMIMMEMMOMMVJ
MEMEEMMOMM MO NOMMEEMPAIr 40
MIIIMMEMMEMM Mm immilIMIWAWAI
+ LV% YIELD PER 7 kg / cm 2
3.0
MMEMMEMMEMMMOMMIMMWARINV 50
OMMINIMMOMMIMMEMEMON TO4
MINIMMEMMOMMEMOMINIVA IMF
60
1100 PSI) DECREASE INPRESSURE
MMOMONOMMIMMME mrAm Ar i 70
1.5
ii
Figure 11
O a
3 6
• 5
4
3
1
0
78 80 82 84 88 88 90 92 94 96 98 100 102 104 106
C5+ RONC
def e t i„•
r Y f► t .. ha 1 1)
if eL t(fele.
E
- 27-
1170136015
Rev. 2
FIGURE 12
RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA
1.6
1.5
1.4
I
1.3
RELATIVE DEACTIVATION RATE
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
30 40 50 60 70
UOP 1539 9
N + A RV %)
o 4
I .
) fl 4 ,4 / A
- 28 -
117013&015
Rev. 2
FIGURE 13
RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA
1.6
1.5
14
RELATIVE DEACTIVATION RATE
13
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
149 160 171 182 193 204
(300) (320) (340) (360) (380) (400)
ASTM ErC ("F)
117013&015
Rev. 2
FIGURE 14
RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA
2.6
2.4
2.2
2.0
RELATIVE DEACTIVATION RATE
1.8
1.6
1.4
1.2
1.0 •
0.8
0.6
0.4
0.2
0
7.0 14.0 21.0 28.1 35.1 42.1
(100) (200) (300) (400) (500) 1600)
1,r P
.
- Z 0 t -0 ei
- 30 -
117013&015
Rev. 2
FIGURE 15
RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA
2.5
2.4
2.3
2.2
2.0
RELATIVE DEACTIVATION RATE
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1.0
0.9
0.8
0.7
4.0 5.0 6.0 7.0 8.0
H 2 / HC MOLE RATIO
J y- 19 t 1, /a ru
--1 , UOP 1S48
f•-#
S, 0 iv 'I.0 f/ )./ r. I.
IC I e-
- 31 -
117013&015
Rev.
FIGURE 16
2.4
2.0
RELATIVE COKING FACTOR
1.6
1.2
0.8
0.4
0.0
96 98 100 102 104
C5 -4- RONC
UOP 391 9
FIGURE 17
EFFECT OF N + A ON RELATIVE
COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA
1.6
1.4
RELATIVE COKING RATE
1.2
1.0
0.8
0.6
30 40 50
N -4- A, LW/0
•
117013&015
Rev. 2
FIGURE 18
1.4
O 1.2
2
O
0.8
0.6 1
BASIS: IBP 82°C (180'F)
0.4 I
RGURE 19
EFFECT OF AVERAGE REACTOR
PRESSURE ON RELATIVE COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA
0 0
inor i2or
roy. 15:54
117013&015
Rev. 2
FIGURE 20
EFFECT OF H2/HC RATIO ON
RELATIVE COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA
4.4 •
4.0
3.6
cc
• 3.2
Le
O
Ni
L4
2.0
1.5
1.2
ILI
IA
1.0 1.5 2.0 2.5 30 40 4.5 5.0
HYDROGEN HYDROCARBON
mol• ratio
H2HC RATIO = COMBINED FEED H2HC RATIO + O.T•H2 NET GAS MOL RATIO
(H2 NET GAS MOL RATIO IS BASED ON FRESH FEED)
u0P t2410-2
-36-
117013E015
Rev. 2
FIGURE 21A
TOTAL HEAT OF REACTION
FROM TOTAL DELTA T
N1111
ENGLISH UNITS
260
240
1, IL
IIq
H 2 / HC
• 220
r-
GQ 200
u
w cc 160
OC kai
Of 160
W I
X a-
(
z
140
00
H
120
co
100
-
11 0
60 70 80 90 100
MOLE % HYDROGEN IN RECYCLE GAS
,f1. r 1
FIGURE 218
MOLECULAR WEIGHT CORRECTION
TO HEAT OF REACTION
ENGLISH UNITS
+ 40
PARAMETER
g I -4
+20 HR / 100 °F QT
g!!
C0•
100
0 113,
B . 150
200
10 -20
260
100 120 140
CHARGE MOLECULAR WEIGHT
- 37 -
117013F.015
Rev. 2
FIGURE 22A
TOTAL HEAT or REACTION
FROM TOTAL DELTA T
METRIC UNITS
1100
1000
I-
!go
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300 -
81170 80 40 ¶00
MOLE "; HYDROGEN IN RECYCLE GAS
FIGURE 22R
MOLECULAR WEIGHT CORRECTION
TO HEAT OF REACTION
METRIC UNITS
100
160
1-
4E
X 120 PARAME 1F11
HR 100 C.2‘,3
Z
O 6.4. in
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1000
- 8 -
UOP Inc.
Des Plaines, Illinois
United States cA America
PROCESS FLOW
This material is UOP Inc 's technical information of a confidential nature for use only by personnel
within your organization requiring the information. The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc and
except as authorized under agreements with UOP Inc
I
PLATFORMSINII
117013
I NTRODUCTION
The reactions that take place in the UOP Plat forming Process are
mostly endothermic (require heat input), and must occur at
elevated temperatures in a hydrogen atmosphere to obtain optimum
catalyst life and product yields. If the conditions are unfavorable,
product yields and/or catalyst life will be poor. Unit designs vary
depending upon processing conditions, optimum capital invest-
ment, desired yield structure and operating costs (based on infor-
mation projected at the time of the unit's design).
FIGURE 1
BASIC PLATFORMING PROCESS
REQUIREMENTS
HEAT
HYDROGEN
AND
OTHER GASES
HYDROGEN
LEGEND
NAPHTHA
RV = REACTION VESSEL
PS = PRODUCT SEPARATOR
PLATFORMATE
D-3
uop
117013
FIGURE 2
CONVENTIONAL PLATFORMING
CH 114 IH
COMBINED
FEW-REACTOR
CHARGE EFFLUENT
EXCHANGER
RECYCLE
EFFLUENT
LEGEND COMPRESSOR
CONDENSER
CH = CHARGE HEATER
I H = INTERHEATER
R = REACTOR
SEPARATOR
NET
SEPARATOR
GAS SEPARATOR LIQUID
TO FRACTIONATION
FIGURE 3
REACTOR EFFLUENT REBOILING
LAST
REACTOR DPIC
COLUMN
REBOILER COLUMN
TO
CHARGE
HEATER
TRC
FRC
COMBINED
FEED
41P0 I
TO SEPARATOR
I) ',
UOP Inc
117013
FIGURE 4
RECYCLE
GAS
• ■tio NET
■•■ +I
SEPARATOR
GAS
RPC
LPS HPS
REACTOR EFFLUENT
FROM COMBINED
FEED EXCHANGER TO
STABILIZATION
FACILITIES
LEGEND
HPS HIGH PRESSURE SEPARATOR
LPS —IOW PRESSURE IOR INTERMEDIATE) SEPARATOR
RC RECYCLE COMPRESSOR
RPC= REACTOR PRODUCTS CONDENSER
LOOP Inc
FIGURE 5
PLATFORMING WITH CONTINUOUS
CATALYST REGENERATION
N•M•MMM.M)k ...s.
T
/ N
COMBINED
FEED-REACTOR
EFFLUENT
CH 1--
r- \ r 1 1
EXCHANGER
CHARGE
r
RECYCLE SR
COMPRESSOR 0 EFFLUENT
CONDENSER
LEGEND
CH - CHARGE HEATER
NET 1 = I NTERHEATER
SEPARATOR
SEPARATOR SR = STACKED REACTORS
LIQUID
GAS
D?
FIGURE II
CCR PLATFORMER
REACTOR DESIGN
REACTOR 2
FEED
RUNWAY
REACTOR I
EFFLUENT
CATALYST
TRANSFER
PIPES
REACTOR 2
I
CATALYST
ENACTOR WALL
CENTER
PIPE
TER BARRET
OA SCALLOP
REACTOR 2
EFFLUENT
FIGURE 7
CCR PLATFORMER
HYDROCARBON FLOW
I NTO REACTOR
D•9
FIGURE $
CCR PLATFORMER
HYDROCARBON FLOW
THROUGH CATALYST
D•10
FIGURE
CCR PLATFORMER
HYDROCARBON FLOW
OUT OF REACTOR
n 11
FIGURE 10
CCR PLATFORMER
CATALYST FLOW
0.12
1171113
FIGURE 11
_
PLATFORMING CATALYST
REGENERATION SECTION
DISENGAGING
REDUCTION HOPPER — DUST o
ZONE —N COLLECTOR-'
CATALYST
. — FLOW
LIE, LINES
CON I ROL
HOPPER
i
CATALYST
SURGE
COLLECTO
HOPPER
LOCH
LOCK HOPPER
,
/ HOPPER NO. 2 -s.
LIFT
NO. I LIFT
ENGAGER
NO. 7—E;IGAGER
NO. 2
NITROGEN
LIFT GAS — HYDROGEN
LIFT GAS
117013
Other Variations
FIGURE 12
PLATFORMER
REACTOR
SECTION
PLATFORMATE
117013
FIGURE 13
HYDRO- ST SP PLATFORMER O SP
NAPHTHA ...lir TREATER
REACTOR
REACTOR
SECTION
SECTION
CCR
LEGEND
HEAVY
P = PREFRACTIONATOR PLAT FOR MATE 4
ST = STRIPPER
SP - SPLITTER
D = DEBUTANIZER
CCR .• CONTINUOUS CATALYST
REGENERATION
FIGURE 14
OTHER PROCESS FLOW OPTIONS
UCIP Inc
117013
Control Systems
FIGURE 15
HEATER SHUTDOWN SYSTEM
r
FUEL GAS TO BURNERS
FUEL GAS
PIAL
PILOT GAS TO PILOTS
HEATER
FUEL OIL TO RURNERS
r- - 1
ATOMIZING STEAM
0
RETURN +•■■••1 TO BURNERS
11---
1
9I r• ■••
1
FUEL OIL
SUPPLY
ATOMIZING
STEAM
1)-16
117013
FIGURE 16
PRESSURE CONTROL
SCHEME I
BOOST ER PRC
PRC COMPRESSOR
LOW SIGNAL
SELECTOR
LEGEND
S SEPARATOR
H = HYDROTR EATER
117013
FIGURE 17
PRESSURE CONTROL
SCHEME II
RECYCLE ROOSTER
PRC
COMPRESSOR COMPRESSOR
* 101 TO HYDROTREATER
H PS
O \-- LOW SIGNAL
SELECTOR
'40' RECYCLE
LEGEND GAS
FIGURE 18
PRESSURE CONTROL
SCHEME III
SIGNAL
.7 SEPARATOR
(FOR THREE OR MORE STAGES,
LEGEND DUPLICATE AS REQUIRED)
S - SEPARATOR
H-HYDROTREATER
117013
FIGURE 19
REBOILER FIRING CONTROL
PDRC
TR
REBOILER
PUMP
LEGEND
FUEL
PRODUCT C = COLUMN
RH - REBOILER HEATER
ABSORBER SYSTEM
NET GAS
PRC
30
4 NET SEPARATOR GAS
LRC
DEBUTAN1ZER GAS
r-1 FR
LEGEND
A = ADSORBER
UOP 673-13
D-21
uoP Irv,
RECONTACT DRUM
- -- 1
PRC
I
I
I
I
I
NET GAS FROM I
COMPRESSORS
I1
FR
E) 1
_I
PUMPED -
SEPARATOR
LIQUID LC
I
1
NET
I GAS
1
LIQUID TO
DEBUTANIZER
U04' 673- 34
.77
CHILLED RECONTACT/ABSORBER
TO
PULL OAS
r-
FR
TO FRACTIONATION
REFRIGERATOR
UNIT
FROM 30 LC
BOOSTER
COMPRESSORS
2.) 14
HYDROGEN TO
NATITHA USERS
HYDROTREATER
1 t ( ;,
SEPARATOR
LJOIND
LEGEND
• ABSORBER
=
F = FLASH DRUM
= SEPARATOR
THE MECHANICAL
ASPECTS OF
PLATFORMING
I. CORROSION
II. INSPECTION
III. SPECIAL MAINTENANCE PROCEDURES FOR EQUIPMENT
PROTECTION AND CLEANING
I. CORROSION
Corrosion is not a serious problem in most Platforming units. However, it is im-
portant to continually check for the unsuspected elements which might cause corrosion
and shutdowns. There are recent developments in the philosophy of maintenance, equip-
ment inspection, and corrosion prevention, and these are discussed in detail.
The original Platforming units were put into operation over 25 years ago, charging
untreated naphtha. The sulfur levels in the charge to some of these units required that
recycle gas scrubbers (Girbotol scrubbers) he utilized to remove hydrogen sulfide from the
recycle gas. The recycle gas in these units was saturated with water and also contained
sulfur and nitrogen compounds, all of which promoted fouling and corrosion. The
metallurgy was upgraded to combat the corrosion, and this helped a great deal. The in-
creased demand for higher octane gasolines led to the development and use of better
catalysts, but the new catalysts required a "cleaner" feedstock to perform as desired. The
answer was feed hydrotreating. Hydrotreating not only removed essentially all of the sulfur
and nitrogen in the charge, but also the arsenic, lead, copper, sodium and other metallic
contaminants. In addition, the hydrotreater product strippers were designed to minimize
the water content in the charge. Since most of the contaminants were now being removed
from the charge, the bulk of the remaining corrosion problems were elminated.
The remaining area which is still subject to corrosion in "wet" units is the
Stabilizer overhead system. This area (both the column and the overhead receiver) is sub-
ject to hydrochloric acid corrosion, usually in the bottom half of the overhead receiver and
in the top few trays of the stabilizer. One method used to combat corrosion in this area is
to inject water into the overhead vapor line, and add ammonia (if necessary) to control the
drawoff water at 6 to 7 pH.
Table 1 shows the materials commonly specified for various services in Plat-
forming units. If a particular unit is different, a review of the unit should be made before or-
dering replacement equipment to make sure that the original specifications are still valid.
Table 1
Materials of Construction
ASTM
Material Specifications
Heater Tubes
Conventional 2 1/4 Cr-1 Mo A-335 Gr P22
A-199 Gr T22
A-213 Gr T22
Low Pressure Drop 9 Cr-1 Mo A-335 Gr P9
A-199 Gr T9
A-213 Gr T9
Reactors
Hot Wall 1 1/4 Cr- 1/2 Mo A-337 Gr 11
Combined Feed-Reactor
Effluent Exchangers
J4
SOURCES OF HCL
SEPARATOR GAS
NET GAS
TO HYDROGEN
USERS IHCL)
RECYCLE
GAS
SEPARATOR
SOURCES OF HCL
STABILIZER OVERHEAD SYSTEM
0 NET OVERHEAD
LIQUID (HCL)
J-4a
FUEL GAS CORROSION
WET
HYDROGEN H2 S
AMMINE FUEL GAS
FROM TO USERS
OTHER SOURCES AMMONIA
• HCL
• IRON SULFIDE
NET GAS TO • IRON CHLORIDE
FUEL GAS • AMMONIA SALTS
( HCL) • WATER
• PILOT CORROSION
• BURNER CORROSION
• REFRACTORY CORROSION
• SALT PLUGGING OF SHUT OFF VALVES,
CONTROL VALVES,
PILOTS,
BURNERS
SOLUTIONS:
J ab
NET GAS TO HYDROGEN USERS
OFF GAS
ONCE THRU WET, H2S
NET GAS
( HCL) HDS RX
0.1
SECTION oc
WATER •Z=,
WASH SEPARATOR
HDS RX
SECTION
J -4c
HYDROGEN (FUEL GAS)
CORROSION POSSIBILITIES
NET GAS
Ow HYDROGEN USERS
(HCL)
— NORMALLY NO CORROSION PROBLEMS
BOOSTER
COMPRESSOR(S)
NET GAS
HYDROGEN
( HCL) USERS
BOOSTER
COMPRESSORS)
J-4d
NET STABILIZER
OVERHEAD LIQUID
NET OVERHEAD LIQUID
( HCL)
► TO LPG RECOVERY
(POSSIBLE CORROSION)
SOLUTIONS
NET GAS
CONDENSER
TRIM
COOLER RECYCLE
PLATFORMER COMPRESSOR
REACTOR
EFFLUENT
SEPARATOR
RECYCLE GAS
SOLUTIONS:
WASHING OF EQUIPMENT PRIOR TO
REGENERATION OR BEFORE OPENING
EQUIPMENT FOR UNIT TURN AROUND AM SALT DEPOSITS
J.4
DEPOSITION OF AMMONIA SALTS
STABILIZER OVERHEAD SYSTEM
.• OFF GAS
b. NET OVERHEAD
LIQUID
SOLUTIONS
• WASHING OF EQUIPMENT BEFORE
OPENING FOR UNIT TURN AROUND
?4Q.1.4, SALT DEPOSITS
• ON STREAM WATER WASH
T
O RECYCLE +
NET GAS
(SEPARATOR
40•-•• FROM
REBOILER
WATER
WASH
MPS SALT
DEPOSITS PLATFORMATE 4 TO
REBOILER
• WASH WATER INJECTED IN SMALL AMOUNTS TO AVOID
COLUMN UPSETS. WATCH COLUMN tP ITOP/BOTTOMI
• WASH WATER WITHDRAWN AT OVERHEAD RECEIVER OR
TAKEN OUT IN NET LIQUID
COLUMN OVERHEAD CORROSION
PROTECTION SYSTEM
WATER
TANK
----
::-_,3
•••- AMMONIA
I NJECTION
s OFF GAS
/ \
NET
OVERHEAD
LIQUID 1 00' WATER DRAW
II. INSPECTION
Although there are many factors which contribute to long operational runs and
plant safety, preventive maintenance is probably the most important one. A proper and
thorough plant Inspection not only results In extended run lengths and maximum safety,
but also greatly reduces the probability of unscheduled shutdowns. An unanticipated
emergency shutdown can be extremely costly, particularly if accompanied by a loss of
property and prolonged Interruption to continued operations.
A well planned inspection program pays off in many other ways as well:
4. It permits stocking major renewal equipment not usually stocked, and which
normally may require a long delivery time, so that they will be on hand for prompt in-
stallation when needed.
Many refineries run various types of charge to their Platformers, and many ti mes
the charge is of an unknown quality in regard to content of corrosives. Many types of
chemicals used today for well treatment are retained in the crude, and where these
chemicals become corrosive, if they do, is not known until It Is too late. Chemicals used in
cleaning units while on stream can also become corrosive under certain conditions.
During a turnaround, normal planning usually does not include sufficient time for
preparation and inspection of piping systems. Normally, after all other equipment has
been opened, cleaned, and inspected, the inspector then finds time to start checking the
piping system, usually by ultrasonic instruments.
The proper inspection of all piping during a turnaround can be carried out only if a
full inspection crew and sufficient maintenance personnel are available. To overcome the
need for large manned groups during a turnaround, it is recommended that a thorough
piping inspection be made prior to the turnaround.
J-5
Some time prior to a scheduled turnaround, a thorough thickness check should
be made of all process piping in the unit (within temperature limitations). This will require
less personnel, both inspectors and maintenance people, than performing the inspection
during the shutdown. A program of making holes in insulation and moving ladders can be
done by only two men on a normal working day basis. Also, ladders are more readily
available and can be placed where required, and scaffolding can be erected without in-
terferring with other work which normally takes place during a turnaround.
A far larger number of check points can be made when the inspectors and main-
tenance personnel have only piping to check. During an on-stream piping Inspection, many
other important conditions can be noted, and in many cases, rectified prior to the turna-
round.
1. Thin piping can be scheduled for replacement and most of the fabrication can
be completed before the shutdown.
2. Leaking flanges and valves can be identified and scheduled for repairs.
The hot alloy piping on Platforming units with hydrotreated feedstocks has been
almost corrosion-free. In a few instances, carbon steel has been installed by mistake in
place of alloy. In each case the carbon steel failed from hydrogen attack in about twelve
months, even though the carbon steel showed no metal loss.
The cold piping downstream of the reactor products condensers and the bottom
of the products separator is vulnerable to hydrochloric acid attack in wet plants. The drains
at the low points of these lines should be watched.
In wet units, there is generally corrosion in the stabilizer overhead area (the top of
the column and the overhead receiver) from wet acid (HCI) attack. In dry plants HCI
corrosion has not been encountered, and stabilizer section piping corrosion has been
essentially nil.
J6
A. Heaters
3. Burners: Burners should be removed and cleaned, and bad burner tips
must be replaced. The burner blocks and ports must be in good condition. Burners should
be kept in alignment to prevent flame impingement on the tubes.
4. Tubes: Experience has shown that the corrosion rate is practically nil on
Platforming heater tubes processing hydrotreated feedstock; however, thickness
measurements should be taken on the tubes during each turnaround to check the rate of
metal loss. Normally, the tubes are checked at each end and at the center on the fire side
using an ultrasonic tester (this is a reliable method for checking heater tube wall
thickness).
The external tube surface should be checked closely to determine whether
vanadium and/or sulfur attack has occurred. If the tubes are covered with oxide or ash, this
should be removed before the tubes are examined. Fine pitting is often an indication of a
fuel oil having a high sulfur or vanadium level.
B. Reactors
There are two types of reactor vessels employed in Platforming service; cold-wall
and hot-wall. Although hot-wall vessels are usually preferred by our licensees, satisfactory
service may be obtained from cold-wall reactors.
J-7
In downflow reactors having internal liners, the reactor pressure drop should
not be allowed to exceed design — usually 3.5 kg/cm 2 (50 psi) to prevent liner ruptures.
When a liner ruptures, an unscheduled shutdown with possible extensive repairs is man-
datory.
Type 405 alloy steel lining has been used very successfully in Platformer
reactors where the charge stock is hydrotreated. Corrosion of Type 405 alloy lining has
been encountered in units operating on non-hydrotreated feedstocks. This material has
been replaced with Type 321 or 347 and no further corrosion has occurred to the alloy
lining.
The bottom heads in the hot - wall reactors may be lined with refractory or fire
brick. This lining is installed to serve as a filler and not as an insulator. It must be installed
in a good manner to prevent catalyst movement into the refractory and coke buildup in it.
There have been cases where poorly installed refractory allowed coke to buildup in the
refractory and force the center pipe out of the socket joint, after which the catalyst
migrated from the reactor.
In some cases, refineries are experiencing exchanger leakage between the tube
sheet and the shell. The cause may be a combination of any of the following factors.:
J8
E. Reactor Products Condensers
Air coolers are normally trouble-free on the process side. Atmospheric fouling is
sometimes experienced on the external fins. Washing with water or blowing with air has
been effective in cleaning them.
Water coolers are fabricated from mild steel if noncorrosive cooling water is
used. With brackish or salt water as a cooling medium, Admiralty brass is often used. The
process conditions on the product side are normally noncorrosive. Corrosion is possible in
wet units having stagnant traps between the tube bundle transverse baffles. This con-
dition Is avoided when drain "V" slots are provided in the baffles. Many refiners have had
unfortunate failures due to ammonium chloride attack (stress cracking) on Admiralty tube
bundles. Cracks normally occur in the U-bends but can occur anywhere on the tubes. Reac-
tor products condensers constructed of Admiralty brass tubes should be water-flushed
free of chlorides prior to hydrostatic testing with water or before opening to atmosphere.
Ammonium chloride is hygroscopic and atmospheric humidity is enough to produce a very
corrosive condition.
During regeneration, the lower than normal flow rates to air coolers sometimes
result in distribution problems. The basic water circulation used to neutralize HCI during
regeneration may not distribute evenly to all air condenser bundles, and the result is high
corrosion rates in localized areas. In order to eliminate the corrosion problem UOP recom-
mends that the basic water circulation rate be equal to the design hydrocarbon charge
rate, and that the outside bundles of the condenser be blinded off during regeneration (see
Figure 1). It may also be advantageous to turn off the fans, if there is a water trim cooler, to
prevent condensation in the air cooler; since the cooling requirement during regeneration
is only about 30 to 50 percent of the design duty, use of the trim cooler is usually satisfac-
tory.
Early Platforming units were equipped with valves having 12% chrome stainless
tri ms. Reports from these plants indicated stress corrosion and cracking of stainless
plugs and seats in the low temperature section of the plant from the condenser through
the separator and compressors. This was attributed to moisture and chlorides, present in
the charge stock or added for process reasons.
Since most of today's Platforming units normally operate at much lower recycle
gas moisture levels, 12% chrome valve trims can be reconsidered and used. Even if the
Platformer reactor section is considered dry, the stabilizer overhead may be wet and
corrosive if outside material is fed to this column, as has been done in some instances to
maximize LPG recovery from other unit gases. If this is the case, proper consideration
should be given to the choice of metallurgy in the stabilizer overhead system.
J 9
G. Condensate and Chloride Injection Points
Corrosion of the injection nozzle and the area of the pipe around the point of in-
jection can be expected to occur when both condensate and chloride are injected together
in the same nozzle. Corrosion has occurred on some units when these materials were in-
jected separately because the nozzles were too close to each other. To eliminate this
problem and a possible fire hazard if connections fail, the chloride is injected into the com-
bined feed at the combined feed-reactor effluent exchanger inlet and the condensate is in-
jected into the hot stream at the outlet of the exchanger.
I. Inspection Schedule
A thorough inspection can save valuable operating time and avoid costly
mechanical failures. Accumulated experience with many Platforming units has allowed
UOP to develop optimum inspection intervals for the equipment.
J 10
Table 2
Platforming Unit
Inspection Intervals
' From a process standpoint reactors should be inspected for cleanliness every third regeneration or every two years
FIGURE 1
1
a
4
Irk
1
_
Tina' IIIIII REGENOERRATION
1
TO TRIM COOLER
J 11
III. SPECIAL MAINTENANCE PROCEDURES FOR EQUIPMENT
PROTECTION AND CLEANING
A. Compressor Washing
During operation, a fine gray powder-like deposit may collect 011 the internals of
Platforming recycle gas compressors. This material (mostly ammonium chloride salts) is
soluble in hot water. It is non-corrosive when dry, but when exposed to the air it absorbs
moisture readily and becomes corrosive not only to iron and carbon steel but also to all
stainless chrome steels, especially if they have been hardened. For protection of the com-
pressor internals, steps must be taken to avoid contact with air when this deposit is
present. Several precautions will assist in this matter.
3. Break the suction and discharge piping and blind off the compressor.
Make reversing connections to the inlet and outlet drains under the case so that the
solution can be pumped through from either end.
4. Pump the solution slowly into the suction drain connection with the seal
oil circulating system operating as per the manufacturer's instructions, and with the rotor
turning over at approximately 60 to 250 rpm run by an air motor, a small auxiliary motor, or
by a rope wraped around the coupling. In order not to take any chance of accelerating to a
high speed with liquid in the case, do not use the main driver to turn the rotor over. Wash
for approximately ten minutes each time, observing the color and pH of the solution.
5. Drain and replace the wash solution with fresh solution; continue the
washings until there is no change in the solution. Maintain the temperature of the solution
with a steam hose, if necessary.
6. Flush out with clean hot water at 65°C (150°F) for ten minutes; drain and
repeat twice. Remove the drain plugs to the intermediate stages in order to drain all water.
Note: If any discoloration of the drain water occurs, proceed wtih an additional soda ash
treatment.
7. If the compressor does not have individual stage drains, steam it until all
of the case is up to 95''G (20(7'F), and blow with nitrogen or dry air to remove water from
case.
J-13
8. Provide about 200 liters (50 U.S. gallons) of Platformate with four liters
(one U.S. gallon) of Unicor thoroughly mixed. (For an alternate inhibitor, Gulf Agent 178 or
Kontol 77 may be used.) With the stage drains closed, introduce Platformate through the
suction drain with the rotor turning over slowly. Wash thoroughly for at least 30 minutes
and drain.
9. Remove all blinds and prepare for startup with nitrogen purges, or if an in-
spection is desired, proceed to dismantle the machine and remove the rotor in accordance
with the manufacturer's recommendations.
In order to inspect the piston and rings, it is necessary to remove the outboard
head of the cylinder, remove the rod from the crosshead, and pull the piston out far enough
to view the rings. The dust should be wiped from the internal surfaces with a lint-free cloth
when possible.
If the piston is entirely removed, the exposed cylinder bore and valve seating sur-
faces should be covered with a li ght coat of oil to avoid contact with air and thus prevent
corrosion of the honed and polished surface of the bore. All of this oil should be removed
before the piston is reinstalled. The bore can be plugged with a pump cup or other similar
plug to assist in isolating it from the atmosphere. A steam hose can be used to remove
powder and scale from the cylinder gas passages but before doing this, the valve ports
must be blocked to avoid getting steam or water on the highly finished cylinder bore sur-
face. Extreme care must be taken if such cleaning is attempted.
If the rings are stuck, a small amount of additional clearance can be obtained by
removing the rings and sanding the sides of the rings lightly on a flat surface. If carbon
piston blocks are used and these are stuck together, washing with hot water may serve to
free them and permit removal from the rod. When a compressor is assembled before the
rest of the plant is ready for operation, it should be blanketed with gas to avoid contact
with air. Close the block valves and pressure the compressor to about 0.3 kglcm 2 (5 psig)
with nitrogen after purging out all air in the system.
J 14
B. Acidizing Heater Tubes'
5. Water wash the tubes before and after neutralizing with soda ash and
detergent to remove all traces of acid and neutralizer.
6. Dry the tubes using a low fire in the heater; blow first with steam and then
with compressed air so that no moisture is left in the tubes.
7. Remove the acidizing equipment and supplies and clean the area.
General Instructions
2. Transfer cool clean fresh water into the acid addition tank, and
slowly add acid to make up the desired concentration.
3. Fill the system with warm (25°C/80°F) fresh water and circulate it to
check the system for leaks and to check the operation of the valves and the pump.
J.15
5. Start to slowly circulate the 20 wt. % acid solution through the
system drawing from the acid addition tank and discharging into the acid circulating tank.
Check the operation of the ejector to be sure that the H 2 S is being removed from the acid
circulating tank.
9. When the acid concentration curve has stabilized for one or two
hours, or when t he concentration has fallen below 1 wt.%, circulation should be stopped
and the spent acid and sludge in the bottom of the acid circulating tank sump should be
drawn off.
10. Fresh 20 wt.%, acid from the acid tank should again be charged to
the system and circulation should be resumed. When mixing is complete, as a result of cir-
culation, the temperature should again be brought up to 70`t (160°F) or the maximum tem-
perature as recommended.
12. When the acid concentration curve has, after several flow reversals,
stabilized at not lower than 5 -6 wt.% concentration for an hour or two, the acidizing can be
considered complete.
13. Drain the spent acid from the system and begin a vigorous water
flushing using clean fresh water and adding just enough steam at the inlet connection to
keep the water warm (40-50°C/100-120°F). Reverse the flow of the flushing stream several
ti mes.
14. After half an hour of water flushing, begin circulating a 2 wt.% soda
ash solution containing 0.1 wt.% detergent, previously prepared in the soda ash neu-
tralizing tank. Continue circulating, with several reversals of flow, for half an hour to neu-
tralize any acid t hat may be in the heater tubes and to remove any of the filming inhibitor.
15. Close the circulating valves and once again vigorously flush the
tubes with clean fresh water.
16. After another half hour of water flushing, shut off the water and
blow out the tubes first with steam and then with compressed air .
17. When all water possible has been blown out of the heater tubes at a
low point drain, light a few of the burners and slowly begin to heat up the tubes. Heat
slowly to approximately 200-250 (400-500°F) firebox temperature and continue to blow
compressed air through the tubes. When no more water vapor is seen emerging from the
outlet, shut off the fires and let the heater cool down.
18. Wash down the working area to remove all traces of spent acid,
soda, or sludge. When the acidizing operation is finished, all equipment should be flushed
with water before being dismantled for removal; all acids should be sent to safe storage,
and all sludges should be properly discarded.
1. Acid
2. Pump
A high capacity pump of approximately 50 m 3lhr (250 gpm), in good
working order, built or modified to handle acid solutions is required.
3. Piping
Sound pipe in good condition, not scrap or rejects, with new gaskets in
all flanges and sharp, clean threads in all screwed connections.
J 17
6. Acid Circulating Tank
A large tank of at least 10 cubic meters (2500 gallons) containing:
b. A weir to divide the tank into a settling basin, to trap the pieces
of scale and sludge carried by the circulating acid solution, and a sump for the pump suc-
tion. The tank must be made of sound material, not scrap, and must be capable of
withstanding a slight vacuum.
3. Utilities
a. Cooling Water
It will be adequate to simply shutdown the cooling water circulation
system during warm weather and start one circulating pump during freezing weather.
b. Steam
Minimum steam requirements must be maintained for insurance pur-
poses and fire protection, and also to operate turbine-driven pumps.
All steam turbines should of course be drained and all steam header
dead ends should be checked for possible freeze ups. Make sure that all steam traps con-
-
c. Fuel Gas
Fuel gas will be used to gas blanket all of the fractionators in the unit.
All process heaters will have the fuel gas blinded off at the burners or at the main header.
J-18
d. Power
The normal power supply may need to be maintained depending on the
utility pumps In the unit and emergency requirements. Lighting requirements, etc., will
have to be satisfied.
e. Instrument Air
Having dry instrument air on all idle instruments will be of a major factor
in protecting against corrosion.
f. Plant Air
There may be no need for plant air as a standby utility. If for any reason
during the shutdown, plant air is required, It can be started at that time. We therefore
recommend that the plant air system be shut down.
h. Sewer Systems
In all cases as the various units are shut down, the remaining drips and
drains from the various vessels will be drained to the sewer. Careful attention should be
given to flush the sewer with fresh water and make certain all hydrocarbons have been
swept out after the units are down.
4. Pumps
No special corrosion considerations are necessary, except for small
chemical pumps, such as the chloride injection pumps. It would be better not to drain
these pumps, but take precautions that moisture does not get into them. Block them at the
discharge and keep the suctions open so that they cannot be damaged by expansion. All
other pumps should have suction and discharge valves blocked and the drains opened.
Reciprocating pumps should have the rods lightly lubricated to prevent corrosion.
Cooling water to pump glands and base coolers should be blocked in and
the water drained.
5. Turbines
No special precautions are required tor me t uroineb,exi- epi
that all condensate has been carefully drained. Turbines and pumps can remain coupled
up and once every few days or so they can be turned by hand with lubricators in service.
6. Compressors
When compressors in the Platforming unit are of the non lubricated type,
they will require special consideration it the plant is to be down for as long as thirty days.
The suction and discharge block valves should be closed to prevent nitrogen blanketing
gas from leaking out of the reactor systems, but nitrogen must be kept in the compressor
cases to avoid corrosion due t o the ammonium chloride on the compressor valves. Simply
pressuring the compressors and blocking them would not be adequate, because over a
thirty day period the compressor cases would breathe, allowing moisture to enter and
J.19
corrosion would be the result. It is therefore recommended that a nitrogen blanket from
cylinders controlled by a small regulator be installed to continuously bleed nitrogen
through a small pipe manifold in all compressor cases. The quantity of nitrogen should be
such that just a few inches of water pressure be maintained. Keeping the pressure at a
minimum will conserve nitrogen lost due to leakage.
A very light coat of oll should be applied to the exposed part of the com-
pressor rods, taking special care not to get oil on the carbon packing. After this, do NOT
turn the compressors over or the packing will of course wipe the oil off.
8. Relief System
Since the system will be full of fuel gas the flare system should remain in
service and the flare kept lit.
10. Heaters
The best protection for heaters against corrosion and spalling of internal
heater box insulation is to keep a very small fire going at all times, such as with pilot lights.
The stack damper should be wide open during the entire shutdown period.
J-20
FIGURE 2
ACIDIZING SYSTEM PIPING
EJECTOR
SAMPLE POINTS-
H 2 S TO
FLARE OR
SAFE DISPOSAL
sPI
STEAM HIGH POINT
VENTA\ TI
PI
STEAM
AIR
I. U
LIP SPENT ACID TO
DISPOSAL
WATER
CIRCULATION HEATER COILS
PUMP
-
A r ACID CIRCULATION TAMP(
– ACID ADDITION TANK
SODA ASH NEUTRALIZING TANK
FIGURE 3
TYPICAL ACID
CONCENTRATION CURVES
20
ae I i I I
1ST ACIDIZING CYCLE 2ND ACIDIZING CYCLE
it
•
•
•
••
▪ 10
z
%
CURVE A
• 5
0
CURVE B
0
U 0
4 0 1 2 3 4
r.-4..,
5 8 0 1 2 3 4 S
TIME IHOURSI
J 21
IV. MECHANICAL EVALUATION TEST PROCEDURE
While the majority of UOP Platforming unit performance tests are conducted in
order to satisfy contractual agreements between UOP and the customer, the potential
significance of a mechanical evaluation is much greater. From the information generated
and collected during an evaluation test, the refiner has the means to assess the potential
of his unit, to plan for future debottlenecking and to optimize refinery operations.
The following description includes data necessary for contractual tests plus in-
formation required for evaluating hydraulic systems, heaters, exchangers, pumps, com-
pressors, etc. A large amount of the information would be gathered in any case (flows, tem-
peratures, pressures, samples, etc.), and much of the rest can be obtained on a one-time
basis.
However, the test information may not be of much value unless the following
criteria are met:
1. The unit must weight balance. The weight balance must be consistently be-
t ween 98 and 102 wt.%, and preferably between 99 and 101 wt.%.
4. Sufficient technical manpower must be available to gather data and take sam-
ples, in addition to those normally available for operating the unit.
The following list indicates the amount and type of information required:
1. Flows: All process flows into and out of the unit, and also intermediate
streams such as recycle gas and reflux, utility flows such as steam, BFW, instrument and
plant air, cooling water, fuel oil and gas, power consumption .
4. Levels: Particularly storage tank levels for feed and products, chemical con-
sumption (chloride, alcohol, Unicor, BFW chemicals, etc.), process levels in columns,
drums, receivers, compressor seal oil and/or cylinder oil losses, etc.
J 23
5. Samples: Samples of feed and products, intermediate streams such as reflux,
recycle gas, fuel gas and oil, flue gas, sour water, catalyst.
Why is all this data required? There are many reasons, but those used most
frequently are to enable the refiner to debottleneck the unit or to predict how much
material he can put through it without a revamp, or for the UOP Engineering Department to
review in order to evaluate actual performance. It is suggested that the data be ac-
cumulated at one time (during the performance run for contract demonstration), and that
evaluation of the equipment be made later. It is important, however, to have all the
necessary information available. To this end, the following lists and data sheets are given
to use as guides in collecting data.
General
Ambient air conditions: temperature
relative humidity
barometric pressure
wind velocity and direction
(show on rough plot plan)
Unit system used (e.g. USA, Imperial, Metric) and definition of any uncommon
units (e.g. kPa) and Standard Conditions (0 °C, 760 mm; 60 °F, 14.7 psla, etc.)
Guarantee
Exchangers
Flow through exchangers on both sides (gas and liquid), composition and mass
flow.
If air coolers; air temperature out, air velocity out, motor amps, note any belt slip-
page, variable pitch positions, louver positions, etc_
J-24
Heaters
Process flows (volume and mass, avg. mol wt., composition, etc.)
Temperature of BFW coils in and out, superheated steam pressure and temp.
Basic data on process coils (size, number, mall., layout sketch, etc.)
Basic data on steam generating coils (size, number, man., layout sketch, etc.)
Need sufficient data to calculate heat flux from process side, heat flux from fire
side, calculate steam balance, calculate total heat release, calculate heater
efficiency.
Chemical Consumption
H 20 or alcohol
BFW chemicals
Unicor
Other
Hydraulic Survey and Process Separations
Samples of LPS liquid and vapor and HPS liquid and vapor for phase separation
data
Utility consumption/production data:
Steam (all pressures)
Air (Plant and Inst.)
N2
Cooling water
BFW
Utility water
Steam condensate
Process condensate
Samples (typical)
Unit charge
LP sep. liquid
LP sep. gas
HP sep. gas
HP sep. liquid
DC, ovhd. liquid (even if only reflux) repeat for other columns as required
DC. bottoms
Catalyst - fresh
CCR Platformer, on stream catalyst sample(s) if possible.
-
Catalyst - spent
J-26
Flue gas for each cell, if divided
Fuel gas
Fuel oil
Comments:
It is not necessary to obtain all the data at one time. It is acceptable to run various
segments of the survey at different times, and one possible period would be during the
line-out period prior to the guarantee test period. Data collections for heater and air-lin ex-
changers, in particular, are lengthly processes, and may be done any time when the unit is
stable, provided all the required process data is available.
If the data are collected, it obviously is necessary to have a good weight balance
(100 + 2%) for the information to be meaningful. For most pieces of information, if the
unit is lined out, spot data will be sufficient, rather than long-term averaged data. It might
be possible, taking this into consideration, to obtain the spot data in sections spread out
during the guarantee test (one exception is column performance).
In presenting the data, some order should be kept. Probably the best method is to
keep sections by type of information, i.e., one section on the guarantee test results, one on
heaters, one on exchangers, one on hydraulics, etc. Attached are some typical summary
sheets for this purpose.
J-27
COLUMN SUMMARY page
date
Item No • by
.
Service
Type of operation-
No. of trays: Reflux ratio:
Type of trays:
Net
Off Reb. Ovhd.
Feed Reflux Gas Btms. Out Liquid Other
Mass Flow
Temperature
Pressure
Composition,
H2
N2
H 2S
H 20
C
C2
C3
iC ,
nC i
ICs
nC s
C+
Avg. Mol. Wt.
Gravity
Distillation
IBP
5
10
20
30
40
50
60
70
80
90
95
EP
(Sketch system showing flows, P, T, Q on separate page)
Weight balance , Heat balance
Deviations from UOP Specifications:
J-29
COMPRESSOR SUMMARY page
date
Item No.: by
Service:
Type:
Manufacturer
No., Size and Style (Mfgrs. Designation):
Pressure Temperature
Suction
Discharge
Other Information:
Flow (SIP)
Flow (Suction/Discharge cond.)
Sp. Gr.
Avg. Mot. Wt .
Comp. Ratio
Discharge Head
Pct. Loaded
Speed
Seal Oil Loss to Process
Seal Oil Differential
Driver type,
Motor: Mfgr. No., Size, Rating, Efficiency and Style ( Mfgrs. Designa-on)
Power
Speed
Power Factor
Turbine Driver: Mfgr. No., Size, Rating and Style (Mfgrs. Designation)
Speed
Steam Supply
Steam Exhaust
Steam Flow
Speed changer: Mfgr. No., Rating, Gear Ratio, rated gear power loss, style ( Mfgrs.
Designation)
Supply copy of Mfgrs. compressor curve and driver, and plot operating point.
Deviations from UOP Specs.:
I /I
CONTROL VALVE SUMMARY page
date
Item No.: by
Service:
Description of Valve Design CV:
Mfgr. and catalog no.:
Positioner?
Actual Design
Pressure Temperature
Inlet
Outlet
Air in
out
No. fans on Pitch control
Louver position
Air Process
Mass flow
O (calc.)
Composition
H2
H 2S
N2
C ,
C2
C3
1C 4
nC 4
1C 5
nCs
C6+
H2O
Avg. Mol. Wt.
Relative humidify
Gravity
Distillation
IBP
10
30
50
70
90
EP
Deviations from UOP Specifications:
*Include sketch of piping geometry if different from UOP standard practice types.
J-32
FIGURE 4
MANIFOLD PIPING REQUIREMENTS
FOR AIR COOLED ITEMS
=-
TYPE A
WATER
•••- ro —1 — ro— •••■
HYDROCARBON 4
TUBE
BUNDLES
TYPE B
WATER
14
HYDROCARBON ft SI
TUBE FL] I ] 1' H
1
i ELI Eli
1 1 1 1
BUNDLES 1 1
TYPE C
4
r-17
TUBE
BUNDLES
r
TYPE D
MANIFOLDING TO BE DETERMINED
BY CONTRACTOR
TYPE E
1 1 1 1
4 1 1 1 1
rUBE
[ 1 11 1 11 1 11 1 1 11 1 1[ 1 11 1 1
I
BUNDLES
I I I I I I I
4 WO' tO7J I
J-33
FLOW METER SUMMARY page
date
Item No. by
Service:
Type of fluid: Normal Units of Flow
Type of meter:
Meter reading,
Pressure,
Temperature
Sp. Gr. • •
Meter factor
Corrected flow rate
Mass flow rate
Avg. mol. wt.
Molar flow rate
J.31
HEAT EXCHANGER SURVEY page
date
Item No.: by
Service:
Type:
Manufacturer:
No. of Bundles
No. of Passes/Bundle Tubes per pass
Tube size ID x Gauge x Length
Heat exchange surface aiealbundle
Piping Geometry: (Sketch if necessary):
Length of service -
Design Heat Transfer Coefficient:
Composition, Stream A
N :
H7S
H2
C
C2
C3
iC
nC4
IC s
+
H2O
Mass flow
Avg. Mol. Wt.
Gravity
Distillation
IBP
10
30
50
70
90
EP
J-35
HEATER SURVEY Page
date
Item No. by
Service:
Type:
Manufacturer:
No. Passes:
& Tubes per Pass:
Tube size ID x Wall x Length
Geometry (Process):
Geometry (Flue Gas):
Convection I Inlet
Outlet
Convection II Inlet
Outlet
Fuel Gas
Fuel Oil
J•36
REACTOR SECTION PRESSURE SURVEY page
(delete unused equipment) date
by
Pressure Temperature
Feed pump discharge
Feed CV Inlet
Outlet
No. 1 RX Inlet
Outlet
No. 2 RX Inlet
Outlet
J-39
REACTOR SECTION PRESSURE SURVEY page 2
date
by
Pressure Temperature
No. 3 RX Inlet
Outlet
No. 4 RX Inlet
Outlet
No. 5 RX Inlet
Outlet
1
Combined Feed Exchanger Inlet
Intershell G
H
1
J
K
L
Outlet
J.40
HEATER SURVEY date by page
G, H,
Stream A 8 C P E F I, J
Mass Flow,
Composition
H2
N
02
CO
CO2
H 2S
SO2
C,
C2
C3
I C.
nC4
ICs
nCs
Cs-205°C (400°F)
205 °C (400 OF) +
Avg. Mol. Wt.
Gravity
Viscosity
Total Sulfur
Metals
(talc.) absorbed
o (calc.) released
Heater gross e(liciency
Excess air, %
Tube skin temps:
J3/
REACTOR SECTION PRESSURE SURVEY page 2
date
by
Pressure I emperalure
No. 3 RX Inlet
Outlet
No 3 Interheater Inlet
Outlet
No. 4 RX Inlet
Outlet
No. 5 AX Inlet
Outlet
J
K
L
Outlet
J-40
REACTOR SECTION PRESSURE SURVEY page 3
date
by
Pressure Temperature
E
F
Outlet
J 41
REACTOR SECTION PRESSURE SURVEY page 4
date
by
Pressure Temperature
Outlet
RX quench CV Inlet
Discharge
to Reactor
Supply sketch of the system showing flow sot eme and all equipment.
J•42
UOP Inc.
Des Plaines, Illinois
United States of America
PROCESS
EVALUATION
This material is UOP Inc.'s technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc.
PLATFORIfili
ING
WATER/CHLORIDE CONTROL
C. COMMERCIAL EVALUATION
FIGURE 1
PILOT PLANT DATA
a
UM
1 000 \ 1 170
• %II...
icier/AC.4V
ilellA 160
• e
1%
70
68
66
93 RONC--• 100 RONC —...
1 uuu _
NI
990 1.1 I
530
.6 NO
A...A
A■PAI"N"..""--
970 520
960 I 'I k
l-s• /SYMBOL R•50 CATALYST CHiOR IDE
10 ■ 1.01 Yft•% (vo. FREI 510
1.40 Yet•% (Vol. FREE)
-
•
MO ---
wialma. w/" LEAH
7 I
ED 0 2S AND
A 100 RO W
I 500
X0.0 05 10 1.5 2.0 2.5 3.0 3.'
(0.175) (0.351) (0.526) (0.701) (0.876) (1.052) 0 227)
CATALYST UFE, BPP
PUG) UC1, 1 244C- It
FIGURE 2
PILOT PLANT DATA
180 I
1 000 • ir- -
N•91-4-• „, 160
•
WO N...T .. • .. ... ....
140 9
120
.1
74
72
•
MOP II. ■
1
1. im,
ra
ft%
70 filt
w
-
■
68 I
er/1
-..-
68 I
N,
64
1020
540
1010 V
/
1000 II
II • 530
990 °
II e .
IP•ae.
so
w. Vi
980 "' 520
. Mr .•
-
1.2
1.10
I -III
1.17 —
1.1• —
1.11 —
1.14
1.13
1.12 —
1.11 —
1.1
Og riel
1.00 —
1.07
1.0•
1.00
1.04
1.0a —
1.02 —
1.01
1
0 4.
0 2 4 •
C.^7 Li re. SPP
ADJUSTED BLOCK TEMP, °F ADJUSTED C5• YIELD, LV% H2 YIELD, SCFB
...
0 ....
U3 0 4rj U3 0 U3 0 C. 0
ii3
...) Ai LA m -JP CO 0 0 --.• •■.1 •..I — 4 0
c1. 0 0 0 0 0 a a 00 Kb al a 0 0
0
0 1
.. . ...... —... ••• - _. _ 7
. ' .
• t •i a . .....' ...i.. . • •• a .— •• 7
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■ • •-•-• •
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• • •• ... ., , ...., t•
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ill
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.
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. p. .•. • • • • •! •• • •.
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. ••
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••• • . • ..... • ..... • -•••• ■ • • • . ...............,, .... -
. .... .
a • • •
$ •• ' • •• •• •
:FER_Er4c
I
t wATEIZ-
• ••••• • • • ! •.
•• : •• • •a . • • • •!i•
:
.. . . .-
7 7 •
••••••••...... ••••11••••.• .. ••• . •••••• -...... . .... • ••••••• • •!••••• • •7••• •••
- r air
t
a • • •• •• • is 4
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i
...-.
1
I 40 6 a• • • • •
•! • • !'
•a , •* P II. , 4 • • • 4 P• -• •. •. . • • !
• • • .. ' •• •- • • • • . 7 • ' I -
..........•-• ...... ................ --la L... ••••••••• .6... • ■■•••• -. •••••• ••■■•••• ••••• •••••••••••••■ — -
, •••• •-• •••••••• .
- • • . .... •: ' . •• -'• !1
•
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• •• . . 7 , - .... ' ! i.
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. - . .'
. -... •••.
. "
..• .. • ..,.
• a_ . . .
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D . . •• . • •-• - . .
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. .. • • •• • •1-• • •, .... •• !. t !' • ! •!• • ' i I ' '' ! " 1"' '. ?I
. . ■ - 1!-+
.
.•••••••••••• •-••••• 4......1 •4., , 4•1
, 1 ,. •
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... . .-
- ''' ".I' ' ' " "'' ''' 1! '' '
• , i 7 I
• •. .
ft 90° v) A
b/ a 0
S 6Z := J. / /.
FIGURE 5
UOP PLATFORMING PROCESS
WATER—CHLORIDE EQUILIBRIUM CURVE
( 950 *F AVG. CATALYST TEMP.)
o
T
.
1A)T /. . 4= )
J (!
1( 4. (
) /44 rt 0‘
S 0/6 0 0( e t/ *
- 4,s v (0 0 t)1,1 ) 0 - T)
r11 I: AP A T3
If r. r e 4 1) (
12 1- ■ 0 1,A1
. ( I,I .' -I e
MUMS
HYDROGEN CHLORIDE
D,
• . ,
1now
1 1
11111iNall„ • IIi •It
/
Nutta lvt/ ir ma
04 ill
,
,••
„ • 1
101
/
r #
;'• #
o o
illiftfiwi/grami
FINa Iii Amp
o :•
I
to
1 • /
••
win INIFI o
noun 7
EQUILIBRIUM RECYCLE
GAS HCL CONTENT
* COMBINED FEED
WATER/CHLORIDE RATIO, R = 1.8 *WPPM WATER IN FEED
WPPM CHLORIDE IN FEED
0.6
0.5
1 I 1
1 r 1 I I I r 4
1100 IMO 900 920 940 990 990
FIGURE 4
.4
WATER AND CHLORIDE RATIO VERIFICATION
(
mol
4 =MI
O r ' T i l t
1.41 2 2.11
0.4 1.2
CHLORIDE RATIO. tom and ppavi/feed Irt ppm
C
117015
Rev. 2
Process symptoms
Methods of detection
A. Sulfur
1
117015
Rev. 2
B. Nitrogen
2. Possible sources:
C. Metals
2. Possible sources:
c. Corrosion of products:
5
117015
Rev. 2
7
117015
Rev. 2
2. Possible sources:
3. Process symptoms:
5. Methods of detection:
Measure the ASTM D-86 end point of each feed stream to the Plat-
forming unit or hydrotreating unit.
Analyze each feed stream for ASTM D - 86 end point once per shift
and adjust the fractionation to maintain each streams end point
below 204°C (400°F). Maintain sufficient reflux to minimize
'sloppy' end points on all appropriate columns.
E. Water
8
117015
Rev. 2
3. Process symptoms:
6 _
117015
Rev. 2
4
117015
Rev. 2
2. Possible Sources:
3. Process symptoms:
d. Reduced delta T I s;
S. Methods of detection:
2
COMMERCIAL EVALUATION
"COLLECT AS MUCH DATA AS POSSIBLE PERTAINING TO
H20/CL BALANCE"
0.7
0.3 i 1 r r 1 1 T II I I T T
0.4
540 BOO MO 900 $20 140
111It EN
i411120
l
II
I •
, • 1 I •
1,1 I I I
11
rill
' I
ig
f4:11 110 LO • I
41 ri
I it I
I P
III I I ,A
,
I I
tsq 100 II 1 I
I
,
•
,
•
,
I rm •
/ /MI
'
f, , , ,
IN
134 N
11i I N • • •
•:
LO
1
T f1
4 I ,•
•
•I
#
•
,
I f ISM, 8 ,/ i
4
I
i
II/ If / ' / '
70 I i ill A ! 4 1
1
RI
50 100 130 200 250 300 330 400 450 500 550 SOO
P) 171 (14 ) (21 ) rzs) PSI
saupaRaTon •Kessums. POW
WargyLli
4.101.
,
101g.
FIGURE
EQUILIBRIUM RECYCLE
GAS MOISTURE CONTENT
41
(1) THE VALUE NORMALLY USED IS THE WT. ppm WATER INJECTED INTO THE
FRESH FEED PLUS AN ADDITIONAL 0.5 TO 1.0 WM ppm ASSUMED TO BE IN
THE FRESH CHARGE.
(2) THE HCL CONTENT OF THE RECYCLE GAS CAN BE ESTIMATED FROM
FIGURES 6 & 7.
(3) THE WATER CONTENT OF THE RECYCLE GAS CAN BE ESTIMATED USING THE
VALUE OF Ypr TIMES THE MULTIPUER OBTAINED FROM FIGURES 8 &
Si
EQUOUBRIUM RECYCLE OAS MOISTURE CONTENT.
CALCULATION
MVO
R fa Y G + iYr
*RR +(Xp MWF
) I
ADJUSTED BLOCK TEMP, 'F ADJUSTED C5* YIELD, LV% H2 YIELD, SCFB
••••
w o In 43
m0 S 0 .4 -4
0
0
Or'
1.3 0 -J
0 O Co o 0 0 0
m
117015
Rev. 2
1. Possible sources:
3. Process Symptoms:
The excessively high HCI in the net gas from the Plat forming unit
may be corrosive to downstream users.
9
117015
Rev. 2
5. Methods of detection:
10
UOP Inc.
Des Plaines, Illinois
United States of America
ANALYTICAL
This material is UOP Inc 's technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc
117013
ANALYTICAL METHODS
PONA
I n the event that the material is high in endpoint, the UOP Method
777 is most preferred. Any time the PONA is questionable, the
UOP 777 PONA should be run as a check. This method's P/N/A
data will also give reasonable results when used with the UOP
correlations.
Sulfur
The Raney nickel (nickel reduction) method for sulfur (UOP 357)
is the one which is recommended for Platformer charge sulfur
analysis. A new method which also is acceptable is UOP 727 (micro-
coulometric sulfur). The Lamp Sulfur method (ASTM U - 1266) is
not acceptable because it does not allow accuracy at the lower
levels required.
Chloride
Composition (C5 - 1
11 25 and HCI
F-3
uop I ne.
117013
Aromatics
Catalyst Analyses
Many refinery laboratories have neither the time nor the budget to
run catalyst analyses. UOP's laboratory will run samples for a
refiner at the refiner's request.
3. Send a copy of the request for analysis with the samples; send
the original to:
Mr. R. W. Bennett
UOP Process Division
20 UOP Plaza
Des Plaines, Illinois 60016
Central Receiving
UOP, Inc.
Ten UOP Plaza
Des Plaines, Illinois 60016
117013
1. Quantity of sample.
2. Complete identification/description of sample.
3. Statement of value of sample for customs purposes only.
( cm 3 )
Platformer Fed
API 100
Distillation 210( 1)
Gross PONA by UOP 273 5 0 (2)
Detailed Hydrocarbon Types by UOP 273 200( 2)
PONA by UOP 777 50
Sulfur, Microcoulometric 10
Nickel Reduction IOU
Nitrogen, Kjeldahl SUM
Micr OCOLI lometric 10
Chloride 100
Arsenic 400
Lead 100
Platformate
API 100
Distillation 210( 1 )
Hydrocarbon types by GC 150( 2 )
G5 - by GLC 50
BTX by GLC 50( 2)
Catalyst
Sampling
Method Frequency
Platformer Charge
(Stripper Bottoms)
LP Separator Gas
HP Separator Gas
Stabilizer Gas
Sampling
Method Frequency
Stabilizer Bottoms
(Platformate)
Regeneration Circulating
Liquid (Every Cat Regen)
Spent Catalyst
Carbon (oven
dried sample) UOP 703 3/W
Chloride UOP 291 3/W
Regenerated Catalyst
Sampling
Method Frequency
On Stream Catalyst
Samples (Non—CCR)
Carbon (oven
dried sample) UOP 703 Occas
Chloride UOP 291 Occas
Sulfur UOP 439 Occas
Surface Area,
Pore Volume,
Pore Diameter UOP 425 Occas
117013
Subject Index
Distillation ASTN11.) 86
Doctor Test UOP 41
Octane Rating
Research ASTM U 2699
Motor ASTM D 2700
Or sat UOP 172
Numerical Index
1.1 0P 9 H 2 S (Tutweiler)
UUP 41 Doctor Test
UOP 79 Laboratory Fractionation, Ti3P
ASTM D 86 ASTM Distillation
UOP 114 Schilling Gas Gravity
UOP 144 Copper in Gasolines
UOP 155 Weathering Test (Boalaway)
ASTM D 156 Saybolt Color
UOP 172 Orsat
UOP 212 H 2 S, Mercap tans and Carbonyl Sulfides
UOP 213 Karl Fischer Water
UOP 273 PONA
UOP 275 Loss on Ignition at 900 ° C
UOP 277 Steam Jet Gum
AS TM D 287 API Gravity
UOP 290 Fluoride in Catalysts
UOP 291 Chloride in Catalysts
UOP 296 Arsenic in Naphtha
UOP 303 Emission Spectrometry on Catalysts
UUP 314 pH, Iron, Copper in Water
UOP 317 Chlorine in Hydrogen
ASTM U 323 Reid Vapor Pressure
UOP 350 Lead in Gasoline
UUP 357 Raney Nickel Sulfur
UOP 384 Nitrogen in Hydrocarbons
UOP 387 Arsenic in Catalysts and Hydrocarbons
UOP 394 Aromatics by CC
UOP 395 Chloride in Distillates
UOP 1425 Surface Area, Pore Volume,
Pore Diameter of Catalysts
UOP 439 Sulfur in Catalysts
UOP 516 Sampling of Liquids
UOP 539 Gas Analysis (GC)
UOP 581 C B Aromatic Isomer (GC)
UOP 588 Chloride in Distillates
UUP 690 Saturates thru C8 (GC)
UOP 703 Carbon on Catalysts (Leco)
UOP 727 Sulfur in Distillates (micro-coulometric)
UOP 741 Saturates thru C11 ( GC)
UOP 777 PONA (GC)
ASTM I) 1159 Bromine Number
ASTM 0 1266 Lamp Sulfur
ASTM D 2699 Research Octane
HYDROGEN SULFIDE IN GASES
BY THE TUTWILER METHOD
UOP METHOD 9.59
Scope
This method is for the determination of hydrogen sulfide in gas mixtures. Mer-
captan sulfur, if present, is determined as hydrogen sulfide. The accuracy of this method
Is not sufficient to obtain reliable results below 5 grains of H 2 S per 100 cu. ft.•
Outline of Method
Precautions
Do not confuse the blue color of the iodine-starch complex with the opalescent
milky appearance resulting from the separation of free sulfur.
Precision
Duplicate results by the same operator should be considered suspect if they dif-
fer by more than the following amounts, depending on the iodine solution used:
F-15
DOCTOR TEST
FOR PETROLEUM DISTILLATES
UOP METHOD 41.74
Scope
This is a qualitative test for the presence of hydrogen sulfide and mercaptans in
gasoline, jet fuel, kerosine and similar petroleum products.
Outline of Method
The sample is shaken with a sodium plumbite solution in a test tube. if hydrogen
sulfide is present the following reaction occurs:
NazPbO2 + H 2S + 2NaOH
The lead sulfide is black and readily visible. If this reaction does not appear,
sulfur is added to the test tube and the mixture shaken again. If mercaptans are present, on
shaking they undergo a series of reactions, coloring the hydrocarbon layer first orange,
then red and brown, and finally a black precipitate of lead sulfide appears. The overall reac•
tion may be written:
Report
(a) Hydrogen sulfide present.
If a brown or black precipitate forms, the sample contains a relatively high con-
centration of mercaptans and is reported "sour".
If the mercaptan content of the sample is low, observe the sulfur layer and judge
as follows:
Precaution
Use only sufficient sulfur to form a thin film floating on the interface between the
sample and the doctor solution.
F-16
FRACTIONATION OF PETROLEUM
DISTILLATES AND CRUDE OILS
UOP METHOD 79.68T
Scope
This method describes laboratory fractionation equipment and procedures used
in obtaining true boiling point data for petroleum distillates and crude oils. Procedures are
also given for obtaining specific boiling range fractions for further analysis.
Outline of Method
A known volume of a petroleum distillate or a crude oil sample is fractionated in a
high efficiency laboratory column. The distillation may consist of: (1) the precision frac-
tionation of normally liquid hydrocarbons to collect fractions for further identification: (2)
the quantitative separation of normally gaseous hydrocarbons, such as C3 and/or C.
hydrocarbons from Cs and heavier gasoline or crude oil fractions, and/or (3) the deter-
mination of true boiling point (TBP) distillation curves at atmospheric and reduced
pressures.
F-17
DISTILLATION OF PETROLEUM PRODUCTS
ASTM D-86
Scope
Definitions:
2: End point (E.P.) — maximum thermometer reading obtained during the test.
F•18
SPECIFIC GRAVITY OF GAS BY
SCHILLING EFFUSION METHOD
UOP METHOD 114-59
Scope
This method describes the procedure for the determination of the specific gravity
of hydrocarbon and other gases whose specific gravities do not exceed 1.3 with respect to
r
air.
This method is based on the kinetic theory of gases, i.e. the speed with which a
gas will pass through a small opening must be proportional to the average speed of the
molecules. Since the molecular speed of a gas is inversely proportional to the square root
of its specific gravity, the rate of effusion is inversely proportional to the same quantity.
The respective effusion times for the sample and air to pass through the same
orifice under identical conditions are measured. Since effusion time is directly propor-
tional to the same square root of specific gravity and the specified gravity of air Is 1.0 by
definition, the specific gravity of the gas sample may be calculated readily. The loss of
energy through friction in the orifice is assumed negligible.
Precision
Values obtained by this method for the specific gravity of gases below 1.3 are
repeatable to within ± 1%.
F•19
I
COPPER IN GASOLINE AND NAPHTHA
UOP METHOD 144-70
Scope
This Is a method for determining small concentration of copper present in a
hydrocarbon•soluabie form in gasoline, kerosine and similar distillates. It is particularly
useful on products that have been copper sweetened and its lower limit of detection is
0.002 mg of copper per liter of oil sample.
Precautions
This method is for the detection of extremely small concentrations of copper.
Therefore, keep all glassware scrupulously clean in order to avoid contamination. The best
results are obtained when the glassware is reversed only for these analyses.
Precision
Based on the arithmetic mean range for 7 pairs of duplicates, the estimated stan•
dard deviation is 0.0005 at the 0.0040 mg Cu/I concentration. Duplicate results by the same
operator should not be considered suspect unless th ;y differ by more than 0.002 at the
0.004 mg Cu/I concentration.
F.20
WEATHERING TEST FOR GASES
UOP METHOD 155.59
Scope
This is a rapid procedure for the estimation of iso- and normal butane in liquefied
butane samples. Propane does not interfere with the analysis and is determined if present
In concentrations not exceeding 25%. Pentanes and olefins will Interfere in the analysis, if
present. The test is sufficiently accurate for routine control of plant operations, the ap-
paratus is inexpensive and the technique involved requires little experience.
Precision
Duplicate results by the same operator should be considered suspect if they dif-
fer by more than the following amounts:
Maximum
Hydrocarbon Deviation, *A
Propane ± 2.5
i- butane ± 1.5
n-butane ± 10
F-21
SAYBOLT COLOR OF PETROLEUM PRODUCTS
(SAYBOLT CHROMOMETER METHOD)
ASTM D-156
Scope
This method covers the determination of the color of refined oils Such as undyed
motor and aviation gasoline, jet fuels, naphthas and kerosine. A sample of the liquid is ad-
ded to a tubular column through which a light source is seen. The color Is compared with
specified glass standards: The height of the liquid sample is decreased by levels until the
color of the sample is lighter than that of the standard. The color number above this level is
reported. The range of number is + 30 (lightest) to 1 8 (darkest color). Color standards
-
Precision
Duplicate results by the same operator should be considered suspect if they dif-
fer by more than 1 color unit.
F-22
FLUE GAS ANALYSIS (ORSAT)
UOP METHOD 172-59
Scope
This is a method for the quantitative determination of carbon dioxide, oxygen and
carbon monoxide in flue gases.
Outline of Method
Systematically, the gas sample is admitted Into a series of pipets, each con-
taining a reagent for the removal of an individual component. After contact with each
reagent, the gas is returned to the buret. The difference in residual volume indicates the
amount of component absorbed. In this manner, percentages of carbon dioxide, oxygen
and carbon monoxide are determined.
Precision
Duplicate results by the same operator should be considered suspect if they dif-
fer by more than the following amounts:
F-23
HYDROGEN SULFIDE, MERCAPTAN SULFUR
AND CARBONYL SULFIDE IN HYDROCARBON
GASES BY POTENTIOMETRIC TITRATION
UOP METHOD 212.72
Scope
This method Is for determining hydrogen sulfide, mercaptan sulfur and carbonyl
sulfide in gaseous hydrocarbons and in liquefied petroleum gas (LPG) of ordinary proper-
ties. Also covered is the determination of mercaptan in non-ordinary LPG which may con-
tain a wide range of hydrocarbon types from ethane to such gasoline boiling range
hydrocarbons as pentane and hexane. The hydrogen sulfide concentration range which
can be determined is from 0.3 to several thousand wt•ppm. The method is also applicable
to LPG samples containing as little as 1.0 ppm mercaptan sulfur.
The sample, taken either from a sample bomb or directly from a refinery stream,
is scrubbed first through a potassium hydroxide solution and then through a
monoethanolamine solution. A potentiometric titration of the absorbed hydrogen sulfide
and mercaptan sulfur follows. The monoethanolamine solution, which contains the ab-
sorbed carbonyl sufide, is titrated potentiometrically with alcoholic silver nitrate in an
acidic titration solvent. The concentration of each item sought is estimated' from the
titration curve.
Precision
F-24
MOISTURE IN GASES FISCHER REAGENT
UOP METHOD 213.59
Scope
Outline of Method
The method depends upon the fact that iodine does not oxidize sulfur dioxide ex-
cept in the presence of water. On reaction with water the dark brown Karl Fischer reagent
(brown color due to the presence of free iodine) becomes light yellow. A small excess of
the reagent will change the color back to brown. This is taken as the end point of the reac-
tion.
Precision
The sample is depentanized and the Cs - minus fraction is analyzed for total paraf-
finic and total olefinic hydrocarbons. The depentanized sample is subjected to
Fluorescent Indicator Adsorption (FIA) analysis to determine olefins, aromatics and total
saturates. A breakdown of the total saturates to determine the proportions of paraffins and
naphthenes is accomplished by processing a depentanized sample through silica gel to
Isolate a total saturates portion and analyzing this by means of a density-refractivity in-
tercept relationship. More detailed determinations of specific aromatics and naphthenes.
Including methylcyclopentane and cyclohexane, are obtained by fractionations of the
depentanized sample and total saturates portion, followed by analysis of the individual
fractions.
Repeatability
Duplicate results should be considered suspect if they differ from the mean by
more than the following amounts:
Aromatics 1%
Olef ins 1%
Paraffins 2%
Naphthenes 2%
Data for the standard deviation for the FIA part of the procedure are not available.
F•25
LOSS ON IGNITION OF CATALYSTS AT 900°C
UOP METHOD 275.64
Scope
This is a method for determining the loss on ignition of fresh or used catalysts or
catalyst bases of the various commercial shapes and sizes, when an ignition temperature
of 900°C is specified. It is also applicable to other sample types, such as catalyst fines.
Precision
Duplicate determinations should not differ by more than 0.2% absolute for
values below 3.0%, or more than 0.3% to 10.0%.
F-27
1
EXISTENT GUM IN DIOLEFIN-CONTAINING
GASOLINES AND NAPHTHAS BY THE
STEAM JET METHOD
UOP METHOD 277.73
Scope
Some gasolines and naphthas contain appreciable concentrations of diolefins or
other materials which are sensitive to oxidation. Examples are: (1) pyrolysis naphtha
(ethylene coproduct gasoline), (2) certain catalytically cracked gasolines, and (3) certain
thermally cracked gasolines. This method is used to determine the existent gum in these
types of materials. An inert gas, steam in this case, is used in the evaporation step in order
to prevent gum from forming in the test beaker during the evaporation. It has been ob-
served that the ASTM air-jet Method D 381, when used on oxidation-sensitive samples,
tends to give falsely high gum values because of gum formation during the evaporation.
Outline of Method
The steam jet method is similar to ASTM Method D 381 for "Existent Gum in
Fuels by Jet Evaporation". The sample in a tared beaker is placed in a heated metal block
apparatus maintained at 330 °F and evaporated to dryness by a jet of steam which has been
superheated to 350°F. The residue is weighed and reported as milligrams of gum per 100 ml
of sample.
Precautions
The types of gasolines and naphthas for which this method is intended must be
sampled and handled carefully in order to prevent oxidation. For best results it is recom-
mended that: (1) the sample containers be purged with inert gas such as nitrogen, carbon
dioxide, or sweet refinery gas prior to taking the samples. (2) any storage between time of
sampling and analysis be in the dark (preferably refrigerated storage). (3) the time lapse
between smapling and analysis be as short as possible.
Precision
Duplicate results by the same operator should not be considered suspect unless
they differ by more than approximately 25% of the result.
F• 28
API GRAVITY OF CRUDE PETROLEUM
AND PETROLEUM PRODUCTS
(HYDROMETER METHOD)
ASTM D-287
Scope
Using a glass hydrometer the API gravity of crude petroleum and petroleum
products which have Reid Vapor Pressures under 26 lbs. can be determined. Gravities are
determined at 60°F, or converted to 60°F, by means of standard tables. Conversion tables
are not applicable to nonhydrocarbons or essentially pure hydrocarbons such as the
aromatics. Of interest: the ID of the sample cylinder must be at least 25mm greater than
the OD of the hydrometer. The height of the cylinder shall be such that the sample height
is 25mm more than the submerged portion of the hydrometer.
Precision
Repeatability: Duplicates should not differ by more than 0.2 degrees API.
Reproducibility: Results should not differ by more than 0.5 degrees API when
done by different labs.
The above judgements are valid providing API gravities were obtained at a tem-
. perature not differing from 60°F by more than 18°F.
FLUORIDE IN CATALYSTS
UOP METHOD 290-64
Scope
Repeatability
F•30
TOTAL CHLORINE IN PLATFORMING
CATALYSTS BY DIGESTION AND
POTENTIOMETRIC TITRATION
UOP METHOD 291-65
Scope
This is a procedure for the determination of total chlorine and bromine in Plat-
forming catalysts.
The catalyst is leached with hot dilute sulfuric acid. Chloroplatinic acid, if
present, Is reduced. The chloride is titrated potentiometrically with silver nitrate solution.
Precision
Duplicate determinations on catalyst samples should not differ by more than
0.02% for the 0.02 to 1 wt•% chloride levels.
F-31
I
ARSENIC IN PETROLEUM NAPHTHAS
UOP METHOD 296.58
Scope
This is a method for determining total arsenic in petroleum naphthas. The limit of
detection is approximately 0.5y (1y . = - 0.001 mg). For a 500 g naphtha sample, this
corresponds to a limit of detection of one part per billion (1 ppb).
Precautions
Samples must not be stored in the light In clear bottles prior to analysis since ar-
senic may be lost. Wrap sample bottles in dark paper or otherwise protect from light.
Precision
The quantitative estimation of the amount of arsenic will be most precise in the
range of 5 to 10 micrograms. In this range the accuracy and repeatability should be ± 10%.
F-32
I MPURITIES IN ALUMINA-BASE
CATALYSTS BY SPECTROGRAPHY
UOP METHOD 303.63
Scope
This method is designed for the determination of 22 trace elements in fresh and
used alumina-base catalyst. Fe, Si, Mg, Ca and As are determined quantitatively. Cu, Pb,
Ga, Mn, Zn, Ni, Mo, Cr, V, Ti, Na, Sn, P, Sb, Co, Zr and Ba are determined semi-
quantitatively, but they may be determined quantitatively with proper standardization. The
sensitivity is as follows for a large 3.4 — m grating spectrograph: Cu, Ga, Mn, Mo, CO-
0.001%; Fe, Si, Ca, Mg, Pb, V, Ti, Zr — 0.002%; Ni, Cr, Sn-0.003%, As-0.004%; Sb-0.01%;
Zn-0.03%; Ba•0.05%; Na, P-0.1%.
Catalyst samples are mixed with spectrographic grade graphite in a ratio of 1 part
sample to 2 parts graphite. A weighed portion of the mixture is burned to completion using
a 8-amp do arc. Aluminum is used as the internal standard. A microphotometer is used to
measure the densitites of selected iron, silicon, magnesium, calcium and aluminum lines.
Concentrations of these metals are then determined from calibration curves prepared from
spectra of synthetic standard mixtures. The remaining elements are determined by visual
comparison of the sample spectra to the spectra of standard powders whose com•
positions bracket the elemental concentrations in the catalyst.
Precision
Duplicate determinations should not differ from the mean by more than 0.002%
at the 0.010% level and below based on 5 replicate samples.
F.33
ANALYSIS OF REFINERY WATERS FOR
pH, IRON, AND COPPER
UOP METHOD 314.68T
Scope
This method is designed for measuring the extent of corrosion caused by refinery
waters. Copper and iron are determined at a level of 0.1 ppm and higher. The metals may be
present as simple dissolved ions, as complex ions with cyanide or other complexing
agents, or as part of the suspended solids that often are present. Ammonia, hydrogen
Sulfide, hydrogen cyanide and organic matter do not interfere.
The pH of the water Is determined because it usually correlates with the extent of
corrosion.
The water sample, including any suspended solids, is concentrated in the presen-
ce of sulfuric acid until sulfur trioxide fumes appear and then treated successively with
nitric acid and aqua regla.
Iron is determined calorimetrically. The lower limit of detection is 0.1 ppm iron.
The pH of the original water sample is determined with a pH meter using a glass-
calomel electrode system. Samples drawn for determination of pH at the refinery should
be taken in glass bottles, leaving little or no air space above the liquid, and should be stop-
pered immediately with rubber or neoprene. The pH should be measured as soon thereaf-
ter as possible as it is often subject to fairly rapid change with ti me. Draw samples to be
sent out of the refinery in polyethylene bottles to avoid breakage.
Precision
F-34
CHLORINE IN HYDROGEN GAS BY
A COLORIMETRIC PROCEDURE
UOP METHOD 317.66T
Scope
The gas sample is scrubbed with a dilute hydrogen peroxide solution to collect
the chlorine and convert it to ionic chloride. The solution from the scrubber is made basic,
heated to destroy excess peroxide and concentrated to a smaller volume. The resulting
Concentrate is acidified and the chloride content determined by a colorimetric method.
This is based on the liberation of thiocyanate ions from mercuric thiocyanate by chloride
ion and measurement of the colored ferric thiocyanate complex:
Precision
Based on a limited amount of data it is believed that duplicate results should not
differ from the mean by more than 10% for the 0.1 to 1 mol•ppm range.
This method determines the absolute vapor pressure of volatile crude oil and
volatile nonviscous petroleum products, except LPG. The gasoline chamber of the testing
apparatus is filled with a chilled sample and connected to the air chamber section which
should be at 100°F. The container Is then Immersed in a constant-tem mature bath and
shaken periodically until equilibrium Is reached. A manometer attached at the end of the
cylinder-like apparatus is read and corrected It the air chamber temperature is initially at
Something other than 100°F.
Precision
Repeatability: duplicate results by the same operators should be considered
suspect if they differ by more than the following:
Range Repeatability
0- 5 psi 0.1
5-16 psi 0.2
16 - 26 psi 0.3
Range Repeatability
0- 5 psi 0.35
5.16 psi 0.3
16 - 26 psi 0.4
F-3t5
TRACE CONCENTRATIONS OF LEAD IN
GASOLINE OR PETROLEUM NAPHTHAS
UOP METHOD 350-72T
Scope
This is a rapid method for determining trace concentrations (10 to 400 ppb) of
lead in gasolines and petroleum naphthas.
The sample is brominated and the lead present is extracted with a dilute nitric
acid solution. The total lead present is measured colorimetrically after conversion to lead
dithizonate.
Precision
F-37
TRACES OF SULFUR IN
PETROLEUM DISTILLATES BY THE
NICKEL REDUCTION METHOD
UOP METHOD 357.64
Scope
Precision
Duplicate results should be considered suspect if they differ from the mean by
more than the following amounts:
Allowable Deviation
Level of from Mean,
S, ppm ppm, S
1 0.2
10 0.4
50
250 3
F-111
NITROGEN IN PETROLEUM DISTILLATES AND
HEAVY OILS BY ACID EXTRACTION OR DIRECT
KJELDAHL PROCEDURE
UOP METHOD 384-64
Scope
The types of nitrogen compounds which can be determined are those which
usually are determined by a macro Kjeldahl procedure and include amines, amides,
-
pyridines, pyrroles and quinolines. The method does not apply to organic nitro - compounds
nor to those containing a -N = N- linkage.
Precision
Duplicate determinations run in the same laboratory by the same operator on the
same equipment should not differ from the mean by more than the percent relative in the
table below:
Total Percent,
Nitrogen, ppm Relative
0.5 20
5 11
45 5
500 2
The estimated standard deviation was calculated to be 0.35 at the 16-ppm level,
based on 5 replicate samples; 1.38 at the 54-ppm level, based on 6 replicates.
F-39
ARSENIC IN PETROLEUM STOCKS AND
CATALYSTS BY SPECTROPHOTOMETRY
UOP METHOD 387.62
Scope
Arsenic Is extracted from the liquid petroleum stock by boiling with a sulfuric
acid-hydrogen peroxide mixture and Is then converted to arsine. The evolved arsine is reac•
ted with a solution of silver diethyldithlocarbarnate in pyridine and the red coloration
produced by this reaction is measured spectrophotometrically.
Precision
Sample Type
Liquid Petroleum Stocks Repeatability
5 20 ppb As
- ± 10%
Over 20 ppb As ± 5%
Catalysts + 3%
AROMATICS IN HYDROCARBONS
BY GAS CHROMATOGRAPHY
UOP METHOD 394.71
Scope
Outline of Method
boiling points.
I mmediately after the Ce aromatics have eluted, the flow through the non-polar
column is reversed to backflush the Co and heavier aromatics from the column through the
detector. Quantitative results are obtained from the measured areas of the recorded
aromatic peaks by utilizing factors obtained from the analysis of a blend of known
aromatic content.
Precision
Based on 5 pairs of analyses the estimated standard deviation (esd) In Table 3
was calculated for the components listed at the 10 liquid volume-percent level.
Table 3
Allowable
esd, Difference,
Component LV-% LV•%
Benzene 0.08 0.3
Toluene 0.07 0.3
F-41
TOTAL CHLORIDES IN LOW-SULFUR
DISTILLATES BY SODIUM BIPHENYL
REDUCTION WITH COLORIMETRIC FINISH
UOP METHOD 395-66 (Procedure A and B)
Scope
This method is for the rapid determination of low concentrations of chloride In
li quid hydrocarbons low in sulfur. This method can be used only on H I S-free samples con-
taining less than 100 ppm total sulfur. Otherwise, erratic chloride results are obtained and
UOP Method 588 should be used instead.
Both organic and inorganic chlorides, as well as bromides and iodides, will be
determined by this method. Since bromides and iodides are rarely, if ever, present in
petroleum samples, the method treats all halogens as chlorides.
This method cannot be used on samples, such as styrene, that are polymerized
by sodium biphenyl.
Precision
F-42
SURFACE AREA, PORE VOLUME AND
PORE DIAMETER OF POROUS SUBSTANCES
BY NITROGEN ADSORPTION
UOP METHOD 425-63
Scope
Precision
Surface Area
Duplicate determination should not differ by more than 8% from the mean.
Pore Volume
F-43
Pore Diameter
Duplicate determinations should not differ by more than 5% from the mean.
F-44
SULFUR IN CATALYSTS BY HIGH
TEMPERATURE FURNACE METHOD
UOP METHOD 439-75
Scope
This method Is a modification of ASTM Method D1552 to permit the deter-
mination of total sulfur In various catalysts. Halogens and nitrogen compounds, in the con-
centrations normally found present, do not Interfere. Molybdenum, boron and tungsten are
Interferences and catalysts containing these elements cannot be analyzed by this method.
Sulfur concentrations as low as 0.005% can be determined by this procedure.
The sample is weighed into a combustion boat and is inserted into a ceramic
tube contained in a high temperature resistance furnace. The products of decomposition
are swept from the tube by a stream of oxygen into an absorber containing hydrogen
peroxide. The sulfuric acid formed is titrated with barium perchlorate using Thorin as the
indicator.
Precision
Based on 6 pairs of catalyst samples which had been finely ground, and con-
tained 0.02 to 0.06% sulfur, the estimated standard deviation was found to be 0.002%
sulfur.
Duplicate analyses should not differ by more than 0.007% sulfur on finely-ground
samples (95% probability). The precision is poorer on non-uniform or unground catalysts.
Outline
Proper sampling techniques are specified to obtain an uncontaminated, air-free
sample in a suitable container; viz., a double-valved, stainless steel cyclinder. The cylinder
is mounted vertically near the sampling point and connected to the plant sample line by
steel tubing or pipe. The connecting lines are flushed with the sample, which is then
allowed to flow upward through the cylinder. Several volumes of sample are discarded
before closing the sample cylinder valves of the cylinder.
F-46
GAS ANALYSIS BY GAS CHROMATOGRAPHY
UOP METHOD 539-73
Scope
This method Is for determining the composition of a wide variety of gaseous
hydrocarbon mixtures obtained from refining processes or from natural sources, including
minor concentrations of the composite of CS olefins and Ce + hydrocarbons. 1•Butene is
not resolved from isobutylene and argon is determined as a composite with oxygen. The
lower limit of detection for a single component is 0.1 mol-%.
Outline of Method
All the constituents of a total gas sample cannot be resolved by a single
chromatographic column. Therefore in this procedure, 3 columns are connected In series
with appropriate coupling valves. Each column is used to separate a specific portion of the
total sample. The first column is able to resolve gases in the C3 - Cs boiling range. The
second column separates the components in the intermediate boiling range — carbon
dioxide, ethylene, and ethane — while the third resolves the light gases — hydrogen,
oxygen + argon (composite), nitrogen, methane, and carbon monoxide.
Precision
Based on 7 replicate determinations, the estimated standard deviations (esd) In
Table 2 were calculated for the components listed.
Table 2
Allowable
Level, esd, Difference,
Component mol•% mol•% mol•%
Hydrogen 10 0.10 0.36
Nitrogen 20 0.02 0.07
Methane 10 0.03 0.09
Carbon monoxide 10 0.14 0.49
r 47
1
Ca AROMATIC ISOMER DISTRIBUTION
BY GAS CHROMATOGRAPHY
UOP METHOD 581.651
Scope
This method is for the determination of the relative distribution of isomers in C e
aromatic concentrates. It is limited to fractions which contain no C 10 non•aromatic
hydrocarbons, because certain C to components have the same retention times as the C e
aromatic isomers. C• aromatics, including isopropyibenzene and n-propylbenzene, are
resolved from Ce aromatics. Total non-aromatics, benzene, toluene and total CA aromatics
can be determined by UOP Method 394.
Outline of Method
Precision
Based on 6 pairs of analyses, the estimated standard deviations (esd) have been
calculated for the components at the concentrations listed in Table III.
Table HI
Concentra- Allowable
Component tion, wt-% esd Difference
p-Xylene 83 0-09 0.2
F 46
-
TOTAL CHLORIDE IN PETROLEUM OILS
BY SODIUM BIPHENYL REDUCTION WITH
POTENTIOMETRIC FINISH
UOP METHOD 588.65
Scope
This method is for the determination of total chloride in hydrocarbons containing
more than - 100 ppm sulfur. Both organic and inorganic chlorides, as well as bromides and
iodides, will be determined. Since bromides and iodides are rarely, if ever, present in
petroleum samples, the method treats all halogens as chlorides. This method is similar to
UOP Method 395 but has an additional step for removal of titratable sulfur and a poten.
tiometric finish.
This method works well on most samples. However, on samples with very poor
endpoints a potentiographic titrator must be used.
Precision
The estimated standard deviation (esd) is 0.44 ppm in the 1.0- to 20.0-ppm range
based on the mean range for 5 duplicate determinations on heavy oil samples.
F.49
INDIVIDUAL SATURATED HYDROCARBONS
THROUGH Co IN PETROLEUM DISTILLATES
BY GAS CHROMATOGRAPHY
UOP METHOD 690-73
Scope
Outline of Method
The olefin-free sample is injected into the first column of a 2-column, 2-detector
system connected in series through a pressure backflushing system. The first column is
employed as a fractionator to separate the sample into light and heavy cuts of desired
boiling range. The light fraction is allowed to enter the analytical column while the heavy
cut is backflushed out of the fractionator column. Thus the boiling range of the fraction
taken for analysis may be limited to those compounds of analytical interest, when desired,
such as Ce - minus, Cy -minus or Ce -minus_ Samples having endpoints below 135°C may be
injected without backflushing If an analysis of the total sample is desired. The con-
centration of each component is obtained on an absolute basis by comparing the peak
area obtained for an internal standard to the areas obtained for the components in the frac-
tion analyzed.
Precision
Concentra- Allowable
Component lion, wt-% sad, wt-% Difference, wt-%
n-Pentane 7 0.05 0.15
n-Hexane 6 0.04 0.13
Cyclohexane 3 0.04 0.14
n-Heptane 7 0.06 0.21
Methylcyclohexane 6 0.04 0.15
n-Octane 6 0.10 0.35
F-50
CARBON ON CATALYST BY "LECO"
WR-12 WIDE RANGE CARBON DETERMINATOR
UOP METHOD 703-71
Scope
It is necessary that the analyst be provided with the history of the sample so that
the proper sample preparation can be applied.
The sample is weighed In a ceramic crucible, mixed with accelerators and burned
in an induction furnace using oxygen carrier gas. The products of combustion pass
through a purifying train consisting of a dust trap, antimony metal for chloride removal,
manganese dioxide for sulfur removal, and a heated catalyst tube for conversiton of car-
bon monoxide to carbon dioxide and hydrogen to water. The carbon dioxide is adsorbed on
molecular sieves at ambient temperature. After the adsorption period is ended, the
molecular sieve column is rapidly heated to 600°F and the carbon dioxide eluted and
carried through the measuring thermistor by an auxiliary flow of oxygen. The output of the
thermistor bridge is integrated and read on a digital voltmeter and converted to percent
carbon by calculation.
Precision
For the 95% probability level, duplicate results by the same operator should not
be considered suspect unless they differ by more than the amounts shown in the
"allowable difference" column.
Allowable
Carbon Level Number of Number of esd, Difference,
°/• C Pairs Used Replicates % C %C
0.01 - 0.6 5 8 0.005 0.02
0.6 - 2 7 0.015 0.05
2-5 7 — 0.022 0.07
20 5 — 0.334 1.25
F. 51
TOTAL SULFUR IN NAPHTHAS AND PETROLEUM
DISTILLATES BY OXIDATIVE PYROLYSIS AND
MICROCOULOMETRIC TITRATION
UOP METHOD 727-72
Scope
This method is for determining total sulfur in hydrocarbons at the 0.1 to 1-ppm
level and the 1•ppm or higher level. Samples may be analyzed directly If viscosity permits
injection by syringe. Samples having a high content of sulfur may be analyzed after
dilution with a suitable solvent. Halides in excess of 10 times the sulfur level, nitrogen con-
tent greater than 10% and heavy metals interfere with the analysis.
Precision
Allowable
Sulfur Level, No. of esd, Difference
Type of Sample wt•ppm S Replicates wt•ppm S wt.ppm S
Hydrotreated
Naphtha 0.27 5 0.034 0.131
0.50 5 0.039 0.154
0.54 5 0.041 0.159
0.65 5 0.047 0.185
1.86 5 0.087 0.340
5.18 5 0.040 0.155
II
Outline of Method
The saturated hydrocarbon sample is injected into a gas chromatograph em-
ploying a column packed with molecular sieves_ The column temperature is li nearly in•
creased from 250 to 450°C. The weight- or liquid volume•percent concentration of each
saturated hydrocarbon type, by carbon number. is obtained from the measured areas of the
recorded peak groups, adjusted for deviation in response by the use of factors.
Precision
Scope
Outline of Method
Definition: Bromine No. is the number of grams of bromine which will react
with 100 g of sample.
Bromine Index is the number of milligrams which will react with 100
g of the sample.
Precision
Repeatability and reproducibility charts should be consulted in an ASTM book of
standards when laboratory results are in question. These numbers depend on type of
distillate and their physical properties.
F•55
SULFUR IN PETROLEUM PRODUCTS
(LAMP METHOD)
ASTM D-1266
Scope
This method determines the total sulfur in liquid petroleum products in con-
centrations above 0.002 weight percent. The procedure involves burning the sample in a
closed system using a suitable lamp apparatus. An artificial atmosphere composed of
70% CO2 and 30% 0 2 Is used to burn the sample to prevent formation of nitrogen oxides.
The oxides of sulfur are then oxidized to sulfuric acid. Sulfur as sulfate is determined
acidimetrically by titration or gravimetrically by precipitation as barium sulfate.
Precision
Repeatability: duplicate results by same operator should not differ by more than
0.005%.
Reproducibility: results by two laboratories should not differ by more than 0.010
+ 0.025S where S = the total sulfur content, weight percent, of the sample.
KNOCK CHARACTERISTICS OF MOTOR FUELS
BY THE RESEARCH METHOD
ASTM D 2699
Scope
Summary of Method
Repeatability
Data for limits on duplicate results by the same operator have not been de-
veloped.
Reproducibility
F•57
SAMPLE CONTAINERS
OCTANE LOSS
It has been found that sample collection in clear bottles, which are left exposed
to sun light (or ultra violet li ghting) either direct or Indirect, and whether or not the sample
-
has been treated with oxidation inhibitors, will result in a severe loss of octane rating
within a very short time. Every effort must therefore be made to see that only the brown or
amber sample bottles are used for daily samples and more important that all samples ship-
ped to UOP for analysis are taken in amber bottles, are kept in a cool dark place until
packaged for shipment, and are shipped as soon as possible after sampling.
F 58
SUNLIGHT AND OCTANE RATINGS
I. Effect of Fuel Type
Peroxide No. Octane No., F-1 Clear
Hours exposure (a) 0 6 54 121 169 217 0 6 54 121 169 217
Platformate, 0.21 11.1 1 3.2 12.6 15.5 22.1 88.3 84.7 84.1 83.7 - 82.0
Polymer, (Inhib.1 0.26 12.3 1 4.4 17.4 28.0 30.6 96.7 94.8 94,4 94.2 - 92.0
Cat. Crackea,TInfilb.) 0.29 3.54 5.30 4.60 5.82 8.72 98.8 91.4 91.4 - - 90.6
Thermal Cracked, (Inhib.) 3.49 5.41 8.40 12.0 11.9 13.2 72.4 72.0 72.2 - - 70.3
Reference Fuel (b) 0.02 0.73 0.85 0.83 1.90 2.02 130.7 78.7 - - - 79.2