United States Patent (19) 11 4,247,729

Takahashi et al. 45 Jan. 27, 1981

54, PROCESS FOR PRODUCING HIGH PURITY (56) References Cited

BENZENE U.S. PATENT DOCUMENTS
75) Inventors: Hideyuki Takahashi; Yoshiyuki 3,310,592 3/1967 Fukuda et al. ....................... 585/259
Matsuoka; Susumu Hamanishi, all of 3,835,037 9/1974 Fairweather et al. ... ... 208/260
Yokkaichi, Japan 4,024,026 5/1977 Gewartowski ....................... 585/488
4,053,388 10/1977 Bailey ................................... 585/483
73 Assignee: Mitsubishi Petrochemical Company, 4,058,452 11/1977 Loboda ................................ 585/489
Limited, Tokyo, Japan Primary Examiner-Curtis R. Davis
Attorney, Agent, or Firm-Oblon, Fisher, Spivak,
21) Appl. No.: 27,305 McClelland & Maier
22 Filed: Apr. 5, 1979 57 ABSTRACT
30 Foreign Application Priority Data A liquid product obtained by hydrodealkylation of
hydrocarbon oil containing aromatic hydrocarbons is
Apr. 10, 1978 JP, Japan .................................. 53-41 170 firstly subjected to rectification, then thus obtained
51) Int. Cl............................ C07C 4/12; CO7C 7/00 substantially pure benzene is treated with clay substance
52 U.S.C. .................................... 585/483; 585/804; under a temperature below 120° C. A highly purified
585/823 benzene especially good in color is obtained.
58 Field of Search ............... 585/483, 486, 488, 489, 7 Claims, 1 Drawing Figure
585/804, 823

15
12 14
PURIFICATION
18
DEALKYLATION DSTILLATION
16
U.S. Patent Jan. 27, 1981 4,247,729

15

DEALKYLATION
 4,247,729 2
to clay treatment, and then pure benzene is obtained by
PROCESS FOR PRODUCING HGH PURTY rectification (for example, HYDROCARBON PRO
BENZENE CESSING, November (1977),132). However, the
heavier oil in the crude benzene is also brought into
BACKGROUND OF THE INVENTION 5 contact with the clay, thereby promoting the deteriora
The present invention relates to a process for produc tion of the clay and shortening the life of clay.
ing high purity benzene by purifying crude benzene In the production of pure benzene according to the
obtained by dealkylation of hydrocarbon fraction con extraction process, no such problem appears. The crude
taining aromatic hydrocarbon, and more particularly to aromatics obtained according to the extraction process
a process for producing high purity benzene by subject O are freed from the light components and the heavy
ing the crude benzene fraction obtained in the dealkyla components by distillation, and then resulting mixed
tion step to a combination of distillation and treatment aromatics are subjected to clay treatment. Then, rectifi
with an active material. cations of benzene, toluene and xylenes are carried out
Various processes are available for obtaining benzene and thus the heavy components formed by clay treat
from hydrocarbon fractions containing aromatic hydro 5 ment are removed by the successive fractionation as
carbons as a raw material. One of the typical process is bottoms. In other words, even in the production of pure
the so-called extraction process comprising extracting benzene by extraction process, there exist a distillation
the mixed aromatic hydrocarbons, particularly of ben step after the clay treatment.
zene, toluene and xylenes by a selective organic solvent, 20 SUMMARY OF THE INVENTION
removing the solvent therefrom and fractionating to
benzene, toluene and xylenes. Another typical process The present invention provides a process for produc
is the so-called hydrodealkylation process comprising ing high purity benzene, which comprises a first step in
thermally or catalytically hydrodealkylating the similar which a hydrocarbon fraction containing aromatic hy
raw material and increasing a benzene yield, hydro 25
drocarbons is subjected to a hydrodealkylation and
cracking other hydrocarbon than the aromatics to light resulting product is then stabilized by separating a light
hydrocarbons, thereby obtaining a liquid phase rich in fraction having a boiling point less than that of benzene,
benzene, and obtaining pure benzene therefrom by dis a second step in which the stabilized product is sub
tillation. The present invention concerns the latter pro jected to distillation to obtain a substantially pure ben
30 zene containing a very small amount of olefins and
CeSS.
The light hydrocarbons are removed from the reac thiophenes, and a third step in which the substantially
tion product obtained by the hydrodealkylation process pure benzene is treated with an active material so as to
by a stabilizer to obtain a crude benzene fraction. The obtain a pure benzene.
crude benzene fraction contains aromatic hydrocarbons
such as toluene, xylenes, etc. besides benzene, heavier BRIEF DESCRIPTION OF THE DRAWINGS
oil, and a very small amount of olefins and thiophenes. 35 The FIGURE shows the three essential steps of the
Though the olefins and thiophenes are in a very small present invention in which a hydrocarbon raw material
amount, they remain in the pure benzene even after the is subjected to hydrodealkylation followed by distilla
distillation, deteriorating the quality of benzene. Thus, tion and purification by clay treatment.
it is necessary to remove the olefins and thiophenes by
clay treatment. DETALED DESCRIPTION OF THE
It is well known that it is desirable to conduct the INVENTION
clay treatment to remove the very small amount of the Any hydrocarbon containing aromatics can be used
olefins and thiophenes remaining in the pure benzene as a raw material in this invention. They are, for exam
freed from the heavier components, thereby obtaining ple, by-product cracked gasoline in the naphtha crack
benzene with a higher purity (for example, PETRO 45 ing, reformate, a crude toluene fraction for producing
LEUM REFINER, 42(1963)161). In such a clay treat benzene by Adealkylation of toluene, other by-product
ment, activated clay is chiefly used at a temperature of oil containing aromatics produced from various petro
150-230 C. under a pressure of 15-30 kg/cm2. The chemical processes, etc. A boiling range of the raw
pressure is applied to keep the benzene in a liquid phase
at the treating temperature. The clay treatment has a 50 material is usually from 40 C. to 300 C. The BTXcon
substantial effect; reduction in the thiophenes and con tent of the raw material of higher than 50% by weight
siderable improvements in acid wash color and bromine is preferable from the viewpoint of benzene production
index of product benzene can be obtained thereby. efficiency. However, the raw material having lower
However, it causes sometimes a development of unde content of aromatics is also applicable for the hydrode
sired color in the product benzene. It is a serious prob 55 alkylation to produce benzene according to the present
lem for the product to meet the standard requirements invention.
as a high purity benzene. This is because some heavier The active materials used in this invention include
oil is formed by the clay treatment, probably due to the clay substances (natural clay, acid clay, etc.), deriva
polymerization of olefins contained in the benzene. tives from the clay substances (activated clay, etc.),
Though the deterioration of color of the high purity 60 silica-alumina-containing substances (natural or syn
benzene by the clay treatment does not always appear, thetic zeolite, etc.), or any solid acid substances having
it is actually indispensable to conduct redistillation after similar acid properties.
the clay treatment to assure the quality in the industrial FIGURE shows the steps of the present invention.
production. In some processes the clay treatment is Hydrocarbon containing aromatic hydrocarbon is fed
carried out before the rectification of benzene, because 65 to a hydrodealkylation step 12 through 11. In the hy
the redistillation is required after the clay treatment. drodealkylation step 12, hydrodealkylation reactions of
That is, the crude benzene freed from the light compo aromatic hydrocarbons such as toluene, Zylenes, etc.
nents by a stabilizer in the dealkylation step is subjected take place in the presence of hydrogen. Conditions for
 3 4,247,729 4.
the dealkylation reaction are such that, for example, ing product was a substantially pure benzene and passed
when the raw material oil is a by-product oil (cracked through the layer of activated clay, Nikkanite G-36
gasoline) of naphtha cracking, it is appropriate that the made by Nippon Kasseihakudo Co., Ltd., under the
reaction temperature is 500-850 C., reaction pressure following two conditions. Benzene before the clay
10-60 kg/cm2G, and a molar ratio of hydrogen to oil is treatment shows a bromine index of about 13 and an
2-10. The resulting dealkylated product is such that, in acid wash color of 4. . .. .
the above case, the benzene content is more than 85%
by weight, and further about 0.5% by weight of light
Average temperatures of layer: 80° C. and 100° C.
Operating pressure: 20 kg/cm2G
gas, about 5% by weight of toluene, xylenes, etc. and Liquid hourly, space velocity of benzene stream: 1.0
5-6% by weight of tars are contained. The product oil 10 hr-i
is supplied to a distillation step 14 after the light hydro Purified benzene resulting from the clay treatment
carbons has been removed by a stabilizer as a part of the shows a bromine index of less than 1, and an acid wash
dealkylation step. In the distillation step 14, a benzene color of less than 1. All other properties including the
fraction is withdrawn through 15, and other aromatic color satisfied the ASTM standard requirements. The
hydrocarbons than benzene are discharged from 16. 15 results are given in Table.
The distillation step 14 may be comprised of a single
distillation column, or may be of such a system as to COMPARATIVE EXAMPLE
separate the heavy oil at first, and then separate benzene The clay treatment was carried out in the same man
from other aromatic hydrocarbons. Benzene withdrawn ner as in Example, except that the average temperature
into 15 generally has a purity of higher than 99.99% by 20 of layer was 170° C. The resulting benzene had a deteri
weight, but still contains less than about 100 wt. ppm of orated color, which did not satisfy the ASTM standard
olefins and a very small amount of thiophenes, and requirements. The results are given together in Table.
TABLE
Quality of Purified Benzene after Clay Treatment
Example Comp. Example
Feed oil Purified benzene Purified benzene
(line 15) (line 18) (line 18)
Operating Temperature (°C) 100 80 170
conditions Pressure (kg/cm2G) 20 20 20
LHSV (hr) l 1
Color good good good not good
Specific gravity (15/4. C.) 0.8853 0.8845 0.8847 0.8848
Acid wash color No.4, less than No.1 less than No. 1 less than No.1
Solidification point (C.) 5.5 5.5 5.5 5.5
Thiophene (mg/l). 1.5 0.7 0.7 0.9
Bromine index 12.9 less than less than 1 less than 1
Distillation IBP (C.) 80.0 . . 79.8 79.8 79.9
range 5% 80.1 . 80.0 79.9 80.1
10% 80.2 80.0 79.9 80.1
90% 80.2 80.1 80. 80.1
97% 80.2 80.2 80.2 80.2
EP 80.2 80.2 80.2 80.2
Total distillate (%) 98.5 98.5 98.5 98.5

shows a bromine index of about 10, and acid wash color

test of No. 4. The bromine index represents the number
of milligrams of bromine consumed by 100 g of sample
according to ASTM D1491. The benzene is fed to a 45 we claim:
purification step 17 using an active material. The step 17 1. A process for producing high purity benzene, com
is a type of an adsorping column usually packed with prising:
active materials shaped in granular forms. The operat (a) hydrodealkylating a hydrocarbon fraction con
ing conditions of such column are such that a tempera taining aromatic hydrocarbons and stabilizing said
ture is in a range of the room temperature to 120° C., 50 hydrodealkylated fraction by separating a light
and any pressure can be applied so long as benzene can fraction having a boiling point, less than that of
be kept in a liquid phase at that temperature, but usually benzene therefrom;
the pressure is 5-20 kg/cm2. A liquid hourly space (b) distilling said stabilized fraction thereby obtaining
velocity is not critical, either, but usually is 0.1 to 10 a substantially pure benzene fraction which con
vol./vol. hour. These conditions are appropriately se 55 tains a very small amount of olefins and thiophene;
lected, depending upon the kind of the active material. and
Purified benzene substantially freed from the impurities (c) treating said substantially pure benzene with an
such as olefins, thiophenes, etc, in the purification step active clay substance at a temperature from room
17 is obtained from 18. The product benzene shows the temperature to 120° C. thereby obtaining said high
color, solidification point, acid wash color, etc. which purity benzene product.
each satisfy the ATSM standard requirements of pure 2. The process according to claim 1, wherein the
benzene.
active material is a clay substance, a derivative of a clay
EXAMPLE substance, a silica-alumina containing substance or a
Crude benzene obtained by hydrodealkylation of the 65, solid acid material having a similar acid property.
by-product cracked gasoline from naphtha cracking operatingprocess
3. The according to claim 1 or 2, wherein the
temperature of step (c) is from room tempera
was freed from other aromatic hydrocarbon fractions ture to 120° C., and wherein the pressure is sufficient to
such as toluene, xylenes, etc. by distillation. The result maintain benzene in the liquid phase. .
 4,247,729 6
5
4. The process according to claim 1, wherein said ylated hydrocarbon fraction contains more than 85%
hydrocarbon fraction is a by-product cracked gasoline by weight benzene.
7. The process of claim 1, wherein said substantially
from naphtha cracking, a reformate or a crude toluene pure benzene fraction has a purity greater than 99.99%
fraction. by wt., contains less than about 100 wt. ppm of olefins,
5. The process of claim 2, wherein said silica-alumina has a bromine index of about 10 and an acid wash color
containing substance is a natural or synthetic zeolite. test of No. 4.
s sis r
6. The process of claim 1, wherein said hydrodealk
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