Professional Documents
Culture Documents
PARAFFIN PRODUCTION
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%.
i Un~
Indices 64-1 64-1 9 64-2M
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
713
TABLE 3. Quality of Feedstock and Products in Urea Dewaxing Units Using
Dichloromethanes (year-average data for 1977)
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
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).
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.