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DEVELOPMENT AND IMPROVEMENT OF PROCESSES FOR LIQUID

PARAFFIN PRODUCTION

A. S. Leont'ev, A. N. Pereverzev, UDC 665.637.7


Ya. V. Mirskii, R. A. Martirosov,
A. G. Martynenko, Yu. I. Lipert,
Yu. Z. Votlokhin, L. T. Bolotov,
L. V. Borisova, V. P. Prokof'evD
and M. M. Remova

In the decisions of the 25th Congress of the Communist Party of the Soviet Union (CPSU),
a goal was set "...to organize large-scale production of liquid paraffins for the needs of
the microbiological industry and the production of synthetic detergents" [I].
In the Soviet Union, paraffins are currently obtained mainly by urea dewaxing of diesel
fuel cuts. Three methods of urea dewaxlng have been used commercially:
l) Dewaxing of diesel fuel cuts with water/alcohol solution of urea; method developed
at INP AzSSR [Institute of Petrochemical Processes of the Azerbaidzhan SSR], cor~nercial unit
designed by VNIPlneft' [All-Union Scientific-Research and Design Institute of the Petroleum
Refining and Petrochemical Industry].
2) Dewaxing of diesel fuel cuts with saturated aqueous urea solution.
3) Dewaxing of diesel fuel cuts with crystalline urea in the presence of methanol as an
activator; commercial unit design developed by Grozgiproneftekhim [Groznyi State Design In-
stitute of the Petroleum Refining and Petrochemical Industry] on the basis of data from
GrozNll [Groznyi Petroleum Scientific-Research Institute].
Small amounts of liquid paraffins are also being produced in a commercial crystalliza-
tion unit with selective solvents, and in a semicommereial unit using a fluidized bed of
zeolite.
In the 10th and llth Five-Year Plans, construction is scheduled for units to cover
liquid paraffins on zeolites, in either a fixed or fluidized bed.
In other countries, liquid paraffins are obtained mainly by adsorptive recovery on zeo-
lites.
The present article is aimed at an analysis of commercial experience and improvements
in processes for obtaining liquid paraffins.
Urea Dewaxing with Water/Alcohol Solution of Urea (64-1 and 64-2M Units)
Several large-scale commercial units are presently operating in this version of the
process.
The urea adduct formation with the hydrocarbons is effected in tubular reactors of the
heat-exchanger type; the separation of the adduct from the filtrate and the washing of the
adduct are performed in settlers. The equipment used in these units is distinguished by a
high degree of reliability and stability. The liquid paraffin produced in these units con-
tains a minimum of 97% n-alkanes and 0.4-1.2% aromatic hydrocarbons. When the units are
operating on feedstocks from high-wax Mangyshlak crude, the yield of liquid paraffins is
higher by a factor of 1.8-2. By means of certain proposals that have been developed and are
being implemented at the present time for improvements in the reactor section and in the
adduct settling and washing section, the capacity of the units can be increased by 20-25%.

Groznyi Petroleum Scientific-Research Institute (GrozNll). Translated from Khimiya


i Tekhnologiya Topliv i Masel, No. i0, pp. 7-11, October, 1978.

0009-3092/78/0910-0711507.50 9 1979 Plenum Publishing Corporation 711


TABLE i. Operating Indices of Individual
Units in 1977 (actual data)

i Un~
Indices 64-1 64-1 9 64-2M

Production capacity, thou-


sand metric tom per year 471,7 420,7
Feedstock
Distillation, "C
IBP 185 193
90% 307 307
IBP 325 324
Solidpoint,"C --13 --12
Finished paraffin
Distillation, "C
IBP . 245 247
50% 271 278
EP 336 343
Content of n--alkane~, % 97,2 97,2
Content of aromatic
hydrocarbons, ~ 0,47 0,47

The basic operating indices of the type 64 units during 1977 are listed in Table i.
Diesel Fuel Dewaxing Process with Crystalline Urea (G-64)
The characteristic feature of this process, which was developed by Grozgiproneftekhim
on the basis of GrozNII data in 1962j is the use of urea in crystalline form in the presence
of methanol as an activator, An 85-120~ naphtha cut is used to dilute the feedstock; cen-
trifuges are used to separate the slurries of the adduct and urea into solid and liquid
phases.
In the currently operating commercial units of the G-64 type, liquid paraffins and die-
sel fuel are being produced.
A G-64 unit includes the following main sections:
Diesel Fuel Dewaxing Section. The dewaxing and washing are performed at 25-35~ in
stirred-vessel contactors; the adduct is decomposed by heating to 90~ in decomposition
mixer s 9
Section for Extraction of Methanol from Centrifuged Diesel Fuel and Paraffin. The ex-
traction is accomplished by means of a circulating aqueous solution of methanol. The centri-
fuged diesel fuel and paraffin are separated from the aqueous methanol solution in electro-
separators; the methanol is recovered from the aqueous solution in a stripping tower.
Section for Recovery of Naphtha from Solutions of Diesel Fuel and Paraffin..... The re-
cvery of the naphtha from the centrifuged diesel fuel is performed in three stages, and the
recovery of the naphtha from the centrifuge paraffin is carried out in two stages.
Paraffin Treating Section. The paraffin is treated with oleum, with subsequent separa-
tion of the paraffin and the acid tar in electroseparators.
The basic operating indices of the G-64 units in 1977 are shown in Table 2.
In the period during which these runs were made, the basic design indices were achieved
in all units with respect to quality and quantity of product output. During this same period,
however, a number of serious shortcomings were revealed, these shortcomings representing the
main reason why extended periods were required to bring the units of this type into full ser-
vice.
Through operating tests on the units, it became possible to develop and implement the
following measures aimed at stabilization of the operation of the units:
a) In cooperation with Grozgiproneftekhim, a method was developed for removing excess
water from the system in the dewaxing section, by stripping out the water in the existing
adduct decomposition unit.

712
TABLE 2. Operating Indices of Existing G-
64 Units
G-64 units
Indices Design I"
ind ices Ir I N~2 N.o3

Production
capaeity,
metrictons/day 780
avera~ 68O
maximum 700
Feedstock
Disti .I~ation,~
9 m)c 208
50%" 256
317
Solid~oint,
--35 --35
Content of
n-alkanes, % 10--12
Liquid
Paraffin
Distillation,*C
IBP Mill. 246
365 340
Content ot
n- alkanes, % Min. 97--99
Content of
aromatic
hydrocarbons
alter treat-
ing, % Maxo 0,4

b) Settler tanks were installed for the naphtha.


c) The piping layout was improved in the dewaxing section.
d) The screw conveyors for the solid phase were replaced by individual hydrotransporters
from each centrifuge to the corresponding mixer.
e) Work was performed to improve and adjust the centrifuges, so that their operating
stability would be better.
In the interest of further improvements of the process, a search is being made for in-
ternal reserves available in the units, hydrocyclones are being introduced to replace the
centrifuges, and a pressurized filter is being built.
In the commercial G-64 units, the output of paraffin tends to be low, in connection
with the low content of n-alkanes in the feedstock (10-14%) and the low recovery of the
paraffin (35-45%) relative to the potential content in the feedstock.
In order to increase the yield of paraffin, a number of plant tests have been performed
on existing units; the following recommendations have been made:
a) A second stage of urea washing should be installed in order to reduce the amount of
urea returned to the adduct formation stage.
b) The overhead product from the drying section in the decomposition stage should be
fed to the centrifuged paraffin stream, in order to utilize the paraffin taken overhead.
The sharpness of fractionation should be improved in separating the naphtha from the
centrifuged paraffin, thereby curtailing losses of paraffins with the naphtha distilled over-
head.
d) A third stage of adduct washing should be installed, so as to reduce the content of
aromatic hydrocarbons in the paraffin.
Preliminary calculations indicate that the implementation of these measures will lead
to an increase in Paraffin output in existing units by a factor of 1.7-2.0, with a simul-
taneous improvement in paraffin quality.

713
TABLE 3. Quality of Feedstock and Products in Urea Dewaxing Units Using
Dichloromethanes (year-average data for 1977)

Feedstock Paraffin Dewaxed diesel fuel


indices
accoMingto ac-
according to ac- according to ac-
design tual design tual d~sign tual

Distillation ~
IBP Mill. 180 1'80 Mira : 265 217
5o% Max. 280 249 Max. 280 246
~P Max. 340 322 334 Max. 340 315
n-Alkane content, mass % 44 33,5 Min. 97 95
Aromatic hydrocarbon coment,
mas~ % . - Max. .17 13 Max. 0,3 0,5*
ViScosity at 20 C, cSt 4--6 3,33 4,5--8

Solid point, ~ +3--+8 --13 +13 Max. --15 --26


Flash point, "C Min. 60 70 Min. 90 70
Chlorine content,. % Max. 0,0025 0,00c Max. 0,0025 0,013
Urea conm_nt,~ Max. 0,007 0,00( Max. 0,003 0,008
*After oleum treatment

Diesel Fuel Dewaxing with Aqueous Solution of Urea


In 1973, in the Sheripov Groznyi Petroleum Refinery, a unit was constructed by assem-
bling imported equipment for diesel fuel dewaxing with an aqueous solution of urea in an
activator medium, the solvent dichloromethane (DCM), the refrigerant in the adduct formation
stage.
The design called for the production of liquid paraffins with an aromatic hydrocarbon
content below 0.5%, along with low-pour diesel fuels.
Data on the feedstock and product quality are listed in Table 3. The urea adduct for-
mation with the n-alkanes is accomplished in vertical reactors with mixing devices, under
vacuum. Used in this process is an aqueous saturated urea solution, with a concentration of
76%. The adduct formation reaction is carried out at 25-35~ maintained by vaporization of
dichloromethane at an absolute pressure of 0.6 kgf/cm 2. The mass ratio of components (feed-
stock/urea/dichloromethane) fed to the adduct formation reactor is 1/1.66/6.2. The solid
phase that is formed is separated from the dewaxed diesel fuel and solvent in pressurized
filters. The diesel fuel filtrate is washed with water to remove the urea and then directed
to solvent recovery, obtaining a finished dewaxed dSesel fuel and solvent that is returned
to the process. The adduct, in order to remove entrained diesel fuel, is washed with solvent
in two stages on filters, slurrying the adduct between stages. The washed adduct is decom-
posed to give paraffin and an aqueous urea solution at a temperature no higher than 85~
feeding water to the decomposition reactor. The mixture of paraffin and aqueous urea solu-
tion is separat@d in a settler. The urea solution is directed to a stripping tower where,
at a temperature of 85~ and an absolute pressure of 0.2 kgf/cm 2, the solution concentration
is built back up by means of vaporization of the water. The paraffin is washed with water
to remove urea and then directed for recovery of the DCM from the paraffin, after which the
paraffin is distilled into the desired fractions. The solvent recovery from the diesel fuel
and paraffin filtrates is performed at a temperature no higher than 135~ since higher tem-
peratures may give hydrolysis of the DCM.
During the course of shakedown runs on the unit, a number of serious shortcomings were
revealed, so that it was not possible to achieve the indices specified in the design for
product quality and yield.
An investigation of the conditions and character of operation of the unit, performed by
specialists of the industry association Groznefteorgsintez, Grozgiproneftekhim, and the
Lower Volga Branch of GrozNII, has made it possible to curtail the losses of solvent and to
increase the output and improve the quality of the paraffin product. "The following measures
were recommended and put into practice:
a) The gland seals on the reactor stirrer shafts were replaced with face seals.
b) A new high-capacity tower was installed for distillation of the DCM from the filtrate
solution, this tower having valve trays with four downcomers.

714
TABLE 4. Characteristics of Feedstock, n-Paraffins, and "Denormalized" (dewaxed)
Fractions in Process of Liquid Paraffin Recovery in a Fluidized Zeolite Bed (AVP)
" Romashkino crude West Siberian crude
Indices .180-350
I vC cut paraf
in
"denor- 00-300 deno~
=
~araf- mal~,
produr
~ cut
!(feed- tin
"donor-.
n' ~.arat mal~r
)roduct
product
g/c -, ,820 ~,762 0,808 0,88' 0,817 0,846
D~tillafion, "C
IBP 170 175 175 210 205 207 195 210 2O5
EP 347 345 342 315 310 315 346 342 343
Content of hydrocarbons, %
n-paraffins t9,0 98,0 19,1 t7,7 12,9 ~8,0 --
aromatics 32,0 1,2 26,0 ,3 26,0 1,3 --
Sulfur content, %
Solidpoint., *C
~,13 ~OS o_,o81 oi~2 0,02 o,m
4"~6 58 "48 --}-6 --55
Cetane number 45

c) Two-stage washing of the diesel fuel filtrate was introduced to remove urea, with an
increase in capacity of the section for recovery of the DCM from the water.
d) An absorber was installed for absorption of the DCM, using the diesel-fuel feed to
the unit as the wash liquid.
e) A system was installed for feeding DCM to the superheated vapor line from the adduct
formation reactors.
Recovery of Liquid Paraffins in a Fixed Bed of Zeolite
This process is carried out in four stages: feedstock distillation and hydrotreating;
recovery of liquid paraffins in a fixed bed of zeolite; oleum treatment of resulting paraffin
concentrate; and regeneration of acid tar.
In producing liquid paraffins, the feedstocks are 190-260~ diesel fuel cuts with n-
alkane contents no lower than 21%, and 200-320~ cuts with n-alkane contents of 18-24%; the
paraffin products have minimum n-alkane contents of 98.5 and 99% respectively, and aromatic
hydrocarbon contents no greater than 0.4 and 0.01%.
Adsorptive Recovery of Liquid Paraffins in Fluidized Bed of Zeolite (AVP process)
All stages of this process (adsorption, desorption, and regeneration) are performed in
a fluidized bed of NaA and MgA microbead zeolite, circulating through two loops, i.e., an
adsorber/desorber loop and a desorber/regenerator/adsorber loop. Displacement desorption
by means of steam is used in this process. A special steam-resistant zeolite was developed
for this purpose [2].
The AVP process was introduced in a semicommercial unit at the V. I. Lenin Groznyi
Petroleum Refinery [3]. The feedstock is a 200-320~ straight-run diesel fuel cut from
Stavropol' crude, with an n-paraffin content ranging from 32 to 36%. The principal operating
parameters of the unit are as follows: feedstock charging capacity 5-7 metric tons/h; ad~
sorption temperature 395-410*C; regeneration temperature 430-470=C; feed of displacing agent
3-4 tons per ton of n-paraffins obtained. The yield of n-paraffins relative to the potential
content in the feedstock is 60-70%; the purity of the n-paraffins is 98%, with a content of
aromatic hydrocarbons below 0.1% (after oleum treatment).
The semicommercial unit operates in a stable manner and gives long run8 between shut-
downs for maintenance (more than 330 days), during the course of which the paraffin output
and purity remain stable. The consumption of zeolite amounts to 3-3.5 kg per metric ton of
feedstock.
It is planned to increase the yield of n-paraffins and to reduce the zeolite consumption
by setting up a loop for the circulation of purge gas, and also by concentrating the sludge
and returning it to the system.
The next stage in commercialization of ~he AVP process was the start of construction of
a G-70-2 unit at Groznyi for the recovery of n-paraffins from 200-320~ diesel fuel cuts from
Stavropol' crude.
In designing this unit, use was made of the operating experience with the semicommercial
and pilot units, as well as developments in the area of design improvements for the adsorp-

715
tion section. In the G-70-2 unit, provision is made for effective contact of vapor and
solid phases, and maximum utilization of heat from the purge gas and the steam condensate
circulating in the system. A zeolite consumption no greater than 2 kg per metric ton of
feedstock is ensured through the use of improved-design cyclones and a system for concentra-
tion and return of sludge.
Currently, a technical directive is being worked out for the design of a commercial
unit of the AVP-200 type for the recovery of n-paraffins in a fluidized zeolite bed from
diesel fuel cuts obtained from crude oils of the Romashkino and West Siberian types, contain-
ing 18-22% and 12-14Zn-paraffins, respectively. Simultaneously, work is going forward on
the synthesis and testing of new modifications of synthetic zeolites with good service prop-
erties.
The AVP-200 unit can handle feedstocks with sulfur contents reduced to 0.05-0~18% by
hydrotreating including both light feedstocks (with end points up to 320~ and heavier feed-
stocks (with end points up to 350~
Studies performed in the pilot unit of GrozNII have shown that, when such feedstocks
are processed, the liquid paraffins will have n-alkane contents of 97-98% (without treating).
The characteristics of the feedstock and products obtained in the pilot unit are shown
inTable 4 .
For the simultaneous production of "denormalized" (dewaxed) products with octane num-
bers meeting the GOST standard requirements (no lower than 45), the yield of n-paraffins in
relation to the potential content in the feedstock must not exceed 80% for the 180-350~ cut
or 85% for the 200-320eC cut.

LITERATURE CITED

i. Material from 25th Congress of the CPSU [in Russian], Politizdat, Moscow (1976), p. 178.
2. Ya. V. Mirskii, I. L. Aleksandrova, et el., Khim. Tekhnol. Topl. Masel, No. 12, 17
(197!).
3. Ya. V. Mirskii, Yu. Z. Votlokhin, et el., Neftepererab. Neftekhim. (Moscow), No. 2, 32
(1978).

PROBLEMS AND TRENDS IN DEVELOPMENT OF PARAFFIN WAX PRODUCTION

R. A. Martirosov, A. N. Leonidov, UDC 665.637.7.002


and A. N. Pereverzev

In the USSR, most of the paraffin wax output is used in petrochemical production, in the
manufacture of synthetic fatty acids (SFA), secondary alcohols, ~-olefins, chloroparaffins,
specialty oils, additives, and other products. Paraffin waxes are also used in the produc-
tion of paper and packaging materials, electrotechnical goods, automotive tires, polishing
compositions, artificial leather, textiles, and many other items. Other applications are
found in the manufacture of matches, milk cartons, candles, shoe polish, cosmetics, etc.
Studies of the demand for paraffin wax have shown that its fields of applicationwill
be extended and that the volumes consumed will increase. The demands for the different grades
of wax will not all increase to the same degree. For example, the relative fraction of waxes
to be used as feedstocks for the petrochemical industry is expected to remain at the present
level; i.e., these uses will account for 75% of the entire paraffin wax output.
In connection with the increasing production of various containers and packaging items
impregnated with paraffin wax, there is a sharp increase in demand for food~grade paraffin.
According to forecasts, there will be a particularly sharp increase in demand for high-melt-
ing, highly treated wax.

Groznyi Petroleum Scientific-Research Institute (GrozNll). Translated from Khimiya i


Tekhnologlya Topliv i Masel, No. 10, pp. 11-13, October, 1978.

716 0009-3092/78/0910-0716507.50 9 1979 Plenum Publishing Corporation

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