USOO61776OOB1

(12) United States Patent (10) Patent No.: US 6, 177,600 B1

Netzer (45) Date of Patent: *Jan. 23, 2001

(54) COMBINATION PROCESS FOR 4,107,224 * 8/1978 Dwyer .............................. 260/671 R

MANUFACTURING ETHYLENE, BENZENE 4,150,061 4/1979 Feinstein et al. ................ 260/672 T
AND ALKYLATED BENZENE 4,167,533 * 9/1979 Raymont .............................. 585/251
4,496.784 * 1/1985 Moorehead .. ... 85/486
(76) Inventor: David Netzer, 1138 Hacienda Ct., Los 4,499.316 2/1985 Garska et al. 585/415
Angeles, CA (US) 90069 4,560,820 12/1985 Field .................................... 585/489
s 4,720,293 1/1988 Rolles et al. ............................. 62/24
4,891.458 1/1990 I tal. ...... 585/323
(*) Notice: This patent issued on a continued pros- 5.176883 o SN, et al. ................... 53.
ecution application filed under 37 CFR 5,463,154 * 10/1995 Slimetal... 585/261
1.53(d), and is subject to the twenty year 5,675,054 * 10/1997 Manley et al........................ 585/809
patent term provisions of 35 U.S.C. 5,750,814 * 5/1998 Grootjans et al. 585/323
154(a)(2). 5,880,320 3/1999 Netzer .................................. 585/448
Under 35 U.S.C. 154(b), the term of this FOREIGN PATENT DOCUMENTS
patent shall be extended for 0 days. WO9809928 3/1998 (WO).
This patent is Subject to a terminal dis- OTHER PUBLICATIONS
claimer. Netzer, D., “Economically Recover Olefins From FCC Off
(21) Appl. No.:
ppl. No.:
09/209,638
9
gases.” Hydrocarbon Processing, pp. 83-91, Apr. 1997.
* cited by examiner
(22) Filed: Dec. 10, 1998
Primary Examiner Walter D. Griffin
Related U.S. Application Data Assistant Examiner Thuan D. Dang
74) Attorney, Agent, or Firm-Christie, Parker & Hale,
(63) Continuation-in-part of application No. 08/957,252, filed on E. y, Ag
Oct. 24, 1997, now Pat. No. 5,880,320, which is a continu
ation-in-part of application No. 08/906,381, filed on Aug. 5,
1997, now abandoned. (57) ABSTRACT
(51) Int. Cl. ............................... C07C 1/00; CO7C2/00; Gas and liquid products of an ethylene plant, Steam cracking
CO7C 4/00; CO7C 5/00; CO7C 6/00; CO7C 2/64; Zone, are used for the coproduction of alkylated benzene.
CO7C 15/067 Dilute ethylene in typical concentrations of 7–20 mol per
(52) 585/323; 585/446; 585/448 cent IS coproduced along with pure ethylene product. Impure
(58) 585/446, 448 benzene containing typically less than 8 wt % C6 and C7
---- --- --- ---------- --- 585/323 non-aromatics is formed by hydratreating and fractionation

of pyrolysis gasoline, rich in benzene and toluene, and also

(56) References Cited by hydrodealkylation of the toluene. The impure benzene
reacts with dilute ethylene to form ethylbenzene and hydro
U.S. PATENT DOCUMENTS gen rich vent gas. The impure benzene can be also a Source
3,966,833 * 6/1976 Cosyns et al 207 R or production
for of cumene, by reaction
production of reactOn With Drop Vene.
with propyl
4.000217 2/1977 Uitti. ... 260/669 R
4,022,847 5/1977 McClure ......................... 260/683.68 12 Claims, 5 Drawing Sheets

re
CYCLOHEXANEBENIENE
214 HYDROGENAION /? 2. 1
21 O
2 11- a She ( cloitant
; >< A - 208 CYCLOHEXANE PURGE
12, w
BENZENE RECYCLE w
;
118
-
R. E.
tly H S.U H.E.H.S
many SCRUBBER
13 O
C6H6 126 128
\20s S-134
b- -----
1- - -
132 ---
ETHYLBENZENE
HYDROGEN TO HYDROTREATING
77
TO FUEL CRACKER H2
RECOVERY
U.S. Patent Jan. 23, 2001 Sheet 1 of 5 US 6,177,600 B1

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U.S. Patent Jan. 23, 2001 Sheet 2 of 5 US 6,177,600 B1

BENZENE RICH LOUIDS

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U.S. Patent Jan. 23, 2001 Sheet 3 of 5 US 6,177,600 B1

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U.S. Patent US 6,177,600 B1
 US 6,177,600 B1
1 2
COMBINATION PROCESS FOR outlet, other than fuel gas, is found for the 5% more of the
MANUFACTURING ETHYLENE, BENZENE unrecovered gaseous ethylene. Normally the unrecovered
AND ALKYLATED BENZENE ethylene 0.1-0.3% is routed with the methane to the fuel gas
system. However, the value of ethylene as fuel is only about
CROSS REFERENCE TO RELATED 15-20% of its equivalent value as downstream product. The
APPLICATIONS ethylene product is commonly used as a feedstock to many
downstream processing including ethylbenzene. Production
This application is a continuation-in-part of U.S. appli of ethylbenzene from pure ethylene against dilute ethylene
cation Ser. No. 08/957,252, filed Oct. 24, 1997, now U.S. feed, although Somewhat advantageous from a Stand point of
Pat. No. 5,880,320, which is a continuation-in-part of U.S. the ethylbenzene plant alone, is not an absolute requirement
application Ser. No. 08/906,381, filed Aug. 5, 1997, now and its relative cost impact is rather marginal as compared
abandoned. with the estimated Saving in the ethylene plant.
SUMMARY OF THE INVENTION
FIELD OF INVENTION
If ethylbenzene is produced at an adjacent facility, dilute
The present invention is directed to an improved proceSS 15 ethylene at concentrations of about 3 to about 40 vol% and
for the production of ethylene and benzene for use in an Substantially free of propylene can be extracted from a
adjacent or remote production of alkylated benzene. cryogenic demethanizer as an overhead gas. The bulk of the
dilute ethylene Stream comprises methane and hydrogen.
BACKGROUND OF THE INVENTION The dilute ethylene stream at a typical pressure of about 330
to about 500 psig and after cold recovery and acetylene
Conventional ethylene production consists of the follow removal is the feed, along with common Specification
ing key process operation: benzene, 99.9% wt % purity, or impure benzene, 95 to 98 wt
(a) Thermal cracking of hydrocarbons in presence of % purity, to an ethylbenzene plant. The ethylbenzene is
dilution Steam, of C+ hydrocarbon at about 15-25 psig normally converted to Styrene.
and 1,500-1,600 F. to form cracked gas containing 25 When naphtha or heavier feeds are used, a pyrolysis
ethylene in an amount of 25-40 wt % (with the excep gasoline product which is rich in benzene is used as a Source
tion of ethane feed), and other by products Such as of benzene for the ethylbenzene plant. Toluene is fraction
propylene, acetylene, hydrogen, methane and C+ ated and converted by hydrodealkylation to benzene and
products. The thermal Section includes cracked gas methane. Thermal hydrodealkylation in the Steam cracking
cooling, Steam generation and Co- hydrocarbon con furnace along with co-production of ethylene is a part of the
densation. Traces of CO, CO and HS are formed in invention. The benzene and co-boilers, cyclohexane and
the cracking. dimethylpentanes, are used as a feed to the ethylbenzene
(b) Cracked gas compression to 400–600 psig, traces of plant. The Saturated C-C co-boilers are purged from the
CO and H2S removal, drying, and bulk C+ product ethylbenzene plant, alkylation reaction loop.
recovery by condensation at about 100 F., using cool 35 The benzene, along with the co-boilers, can be used also
ing Water. for the production of iso-propylbenzene (cumene) by reac
(c) Acetylene conversion to ethylene via Selective tion with propylene. The Saturated C-C, co-boilers would
hydrogenation, chill down and cryogenic recovery of be purged from the cumene plant alkylation loop in a similar
ethylene by fractionation at below -30 F. fashion.
(d) Recovery of propylene, propane and C+ hydrocar 40 The invention is applicable to Situations where the alky
bons by warm distillation at above 80 F. lated benzene plant is remote to ethylene production, and
(e) Cascade refrigeration of ethylene and propylene ethylene feed via pipeline is the mode of operation. In this
refrigerants, to Support the above, down to a tempera case, no practical option exists for using dilute ethylene
ture of below -100 F. feed.
45
(f) Methane refrigeration and or turbo expander to reach DESCRIPTION OF DRAWINGS
refrigeration below -180° F. FIG. 1 illustrates the cracking section of the ethylene plant
(g) In case of Naphtha feed, and to a lesser extent with and heat recovery with high pressure Steam generation and
propane/butane feed, residual liquid products from Superheating.
cracking Such as pyrolysis fuel oil and pyrolysis 50 FIG. 2 illustrates the quench oil and quench water pyroly
gasoline, which are rich in aromatics, are Selectively sis gasoline and pyrolysis fuel oil recovery, cracked gas
hydrotreated for di-olefin and olefin Saturation. compression, CO and H2S removal, cracked gas drying,
(h) Benzene/toluene and xylene (BTX) are extracted from pyrolysis gasoline hydrotreating, deheXanizer, benzene
the hydrotreated pyrolysis gasoline, and toluene is recovery, toluene conversion to benzene as a feed to the
fractionated and converted to benzene by hydrodealky 55 ethylbenzene plant or cumene plant (not shown).
lation. FIG.3 illustrates the dilute ethylene recovery for use in an
Efficient cryogenic recovery of the ethylene is a key adjacent ethylbenzene plant.
element in design of ethylene plants. The motive power for FIG. 4 illustrates the ethylene recovery, acetylene reactor
compression and refrigeration, and consequently the capital and off Specification ethylene diversion to the ethylbenzene
cost escalates rapidly as the rate of ethylene recovery 60 plant.
increases. For example, the typical ethylene recovery of FIG. 5 illustrate ethylbenzene production along with
99.7-99.9% requires much higher investment and 50% more hydrogen recovery.
refrigeration energy in the demethanizer as compared with
95% rate of ethylene recovery. Thus, reduction of the DETAILED DESCRIPTION OF THE
marginal refrigeration required for ethylene recovery by 65 INVENTION
using 95% or lower recovery could substantially improve For illustration and process consistency, the invention will
the Overall economics of the ethylene plant, if a down Stream be described for an ethylene plant when naphtha is the sole
 US 6,177,600 B1
3 4
feedstock followed by ethylbenzene production. This
enables demonstration of all the elements of the invention. TABLE 1-continued
This is reasonable since more than 60% of the world’s
ethylene production capacity originates from naphtha and Component Wt%. Destination
heavier feeds. C. Olefins + 9.5 Hydrotreated and recycled to
The assumed capacity of the ethylene plant for consis Paraffins cracking
tency purposes is 1,000,000,000 lb/year, along with Cs Olefins + 4.5 Hydrotreated and recycled to
Paraffins cracking
co-production of 400,000,000 lb/year of propylene, 280,000, Benzene 6.5 Light gasoline product, feed
000 lb/year of impure benzene (95 wt % benzene) and by Toluene 2.3
to ethylbenzene.
Light gasoline product, a
products Such as hydrogen, pyrolysis gasoline and pyrolysis
fuel oil. About 8,300 hours per year of operation are source of benzene by
hydrodealkylation
assumed. Pyrolysis products Such as ethane, propane, C and Xylene + 0.4 Heavy gasoline product to
Cs are internally recycled and converted to ethylene and Ethylbenzene battery limits
propylene. Acetylene is Selectively hydrogenated to Balance of Pyrolysis 8.1 Product to battery limit
ethylene, and methylacetylene and ropadiene are Selectively 15 Fuel oil and pyrolysis
gasoline (C5-Clio)
hydrogenated to propylene. H.S and CO, Traces waste to battery limits
According to the invention, for illustrative purposes about as sodium salts
CO Trace To fuel
15% of the crude ethylene originated in the cracking, is
recovered as a dilute ethylene product at a concentration of
about 10.0 vol. 9% and serves as a feed for production of The net ethylene make is about 5.5 wt % of the naphtha
550,000,000 lb/year of ethylbenzene at an adjacent facility. feed in dilute form and about 29.0 wt % of the naphtha feed
The cracking yield is based on of molecular weight of 92, in concentrated pure form. The net propylene recovery is
a specific gravity of about 0.69, paraffin content of about 80 about 14.5 wt % (before consumption to cumene).
wt % (50% normal, 50% iso), naphthene content of about 10 25 In the heat recovery section 18 of the cracker, hot com
wt % and aromatic content of 10 wt %. The naphtha contains bustion gas from the pyrolysis Section undergoes heat recov
less than 0.1 wt % olefins and traces of Sulfur. ery providing preheating boiler feed water 28 and Super
With reference now to FIG. 1, Naphtha net feed, 10 about heating saturated steam 9 at about 1,900 psig and about 650
33,000 bpsd (331,000 lb/hr) and about 65,000 lb/hr of F. to about 1,800 psig and 980 F. Stream 30. The cracked gas
combined recycles 12 of C H and CHs gas feed and 32 is cooled in transfer line exchangers 34 to about 800 to
CH, C, H2 and C.H. liquids after hydrogenation, are about 840 F. by generating Saturated steam at about 1,900
vaporized in vaporizer 14 and mixed with steam in line 16, psig and about 650 F. The overall steam production is
at a typical weight ratio of about 0.5 steam to hydrocarbons typically in balance as a motive power Source for the cracked
feeds. gas compression and refrigeration compression drivers of
The Steam helps reduce coking in the tubes of the 35 the ethylene plant.
furnaces, and also reduce the partial pressure of the With reference to FIG. 2, the cracked gas at about 800 to
hydrocarbons, thus increasing ethylene yield. about 840 F. and 10 psig in line 42 after steam generation
is quenched with pyrolysis fuel oil in quench Zone 44 using
This hydrocarbon steam mixture is further preheated in oil recycle and heat absorption by generating Saturated
heater 18 and proceeds, line 20 prior to the cracking Section 40 steam at 110-130 psig
of the pyrolysis furnace 22. The furnace is fired by fuel gas The net product made after Stripping of light pyrolysis
principally CH product 24 as recovered from the down products is C+, pyrolysis fuel oil. The steam at 110-130
stream process. The source of the CH with reference to psig is ultimately used as a dilution Steam for the naphtha
FIG.3, is the cryogenic separation Zone (80) in the ethylene and recycle feeds 16. Overhead gas 46 from the quench oil
plant. However, its final recovery is from the vent gas 121 45 system at about 220-250F. proceeds to the quench water
in the ethylbenzene plant FIG. 5. For the above naphtha net system 48, and preheat quench water at 110 F. in 50 to 180
feed and the recycles, the following typical yield, in weight F. in line 52 and recovery of aromatic rich Co-Co pyrolysis
percent per pass, is shown in Table 1. Hydrodealkylation of gasoline 54. The 180° F. water 52 serves as a low level heat
toluene in the cracking furnace would further increase Source to a number of reboiling Services in the plant facility.
benzene and methane production, but will consume hydro 50 After utilization of the low level heat, water at about 110 F.
gen
is recycled back to the quench water System 48.
TABLE 1. Quenched gas is further cooled to about 100 F. with
about 88 F. cooling water (depending on ambient
Component Wt %. Destination conditions) and the bulk of the water vapors and the C+
Hydrogen 1.05 Product to battery limit.
55 products are condensed and Separated. The cracked gas at
(After satisfy internal usage) about 5.0 psig proceeds by line 56 to compression. The gas
Methane 15.8 Fuel gas product to cracking is compressed to about 400-600 psig in four to five stages.
furnaces For illustration purposes five Stages of compression to about
Acetylene O.9 Converted to ethylene product 520 psig are assumed. After three stages of compression (58,
Ethylene 29.6 Main product to battery limits
Ethane 6.2 Recycled and converted to 60 60, and 62) to about 140 psig, the gas 64 proceeds to caustic
ethylene product scrubber (66) for CO and HS removal and further com
Propadeine O.6 Converted to propylene product pressed at 68 and 70 to about 520 psig in line 72 and after
Propylene 14.O Main product to battery cooled to about 100 F. The gas is further cooled in
limits, or for cumene exchanger 74 to about so F. by refrigeration or cold recov
production
Propane 0.4 Recycled and converted to 65 ery prior to water/hydrocarbon Separation. The gas proceeds
products. to molecular Sieve dryer 26 as needed for downstream
cryogenic product recovery. At this point about 99% of the
 US 6,177,600 B1
S 6
benzene and C, 85% of the Cs hydrocarbon and 65% of the In the primary design, as well as alternate designs, the dry
C. hydrocarbons are condensed and separated in lines at 15, cracked gas at about 500 psig and about 60° F in line 78 is
17, 19, 19a and 19b and send to raw pyrolysis gasoline 34. chilled down to about -200F. using propylene and ethylene
Water and hydrocarbon liquids, mostly C, Cs, and C are refrigeration, followed by an expander or methane refrig
condensed in the interStage and after Stage cooling of the eration (not shown). At this point essentially all the ethylene
cracked gas compression FIG. 2, stream 15, 17, 19, 19a and (99.9%) is condensed in several stages along with the bulk
also from dryer prechilling (74) and water is separated (not of the methane, and hydrogen rich gas (75% H) is separated
shown). The combined hydrocarbon liquid 19c combines from the crude ethylene liquids which are fed to a demetha
with aromatic rich stream 34 to feed stream 200 to selective nizer 80, operating at about 300 to about 500 psig and, for
olefin and di-olefin Saturation unit 202. The hydrotreated this illustration, preferably about 460 psig. In a conventional
design, the overhead product of the demethanizer overhead
stream 36 free of sulfur, proceed to dehexanizer (201) where is essentially methane, Some residual hydrogen with very
all C, Cs, and all C. except cyclohexane and benzene are minimal quantity, say 100 vol. ppm, of ethylene. The bottom
Separated overhead, at an atmospheric cut point of 167 F. product 54 is essentially ethylene, ethane, propylene and
This light saturated liquid 200 A recycles back to cracking C+ hydrocarbons. Methane content is under 100 ppm and
15
section 14, (FIG. 1). hydrogen content is essentially nil. In a conventional design,
Bottom product from 201 fractionation, proceeds to the ethylene in the overhead of the demethanizer at 48
de-cyclohexanizer 205 where benzene, cyclohexane and represents a net ethylene product loss to the fuel gas System,
dimethylpentanes are Separated, at an atmospheric cut point thus a good economical design should minimize its content
of 183 F. The overhead product, stream 206 is impure by appropriate reflux of liquid methane Stream 47 at typi
benzene containing typically 2-8 wt % of cyclohexane and cally about -145 F. The cold for the reflux is provided by
dimethylpentanes and traces of methylcyclopentane and ethylene refrigeration at about -150 F. which corresponds
methylcyclohexane. This impure benzene is used as a feed to slightly above its atmospheric pressure. Typically 99.8%
for the ethylbenzene 120 (FIG. 5) or alternately as a feed to of the ethylene, and essentially 100% of the ethane and
a cumene plant, where liquid phase or mixed phase alkyla 25 acetylene from the charge gas are recovered as a bottom
tion reactions are employed. Toluene rich Stream 207, can product for further processing and Separation. The same is
proceed to battery limits or alternately to toluene fraction essentially true for the alternate designs except that essen
ation 220. Overhead toluene proceeds to hydro-dealkylation tially no C+ and acetylene are present in the bottom of the
221 where hydrogen as formed reacts with toluene to form demethanizer.
benzene and methane. As an alternate method, thermal mode In the conventional design stream 48 the CH/H over
of hydrodealkylation will take place in the cracker at about head from the demethanizer at about 460 psig is typically
1600 F. where toluene stream 301 recycles to the naphthe expanding to fuel gas pressure of about 50 psig in a
feed stream 10. Over 30% of the toluene per pass is turbo-expander, (not shown) generating motive power as
converted to benzene, with an ultimate conversion of over well as refrigeration (needed for the low temperature ethyl
90%. ene condensation and hydrogen Separation). The cold is
35
With reference to new FIG. 3, about 12710 lb-mol/hr of recovered from the H/CH rich gas prior to diversion to the
dry cracked gas at about 500 psig and about 60 F. in line 78 fuel System for Subsequent combustion in the cracking
with the molecular composition shown in Table 2, proceeds furnaces.
to a chill down train for cryogenic product recovery. In the instant invention all hydrogen Separation occurs in
40 the demethanizer, unless the invention is applied toward
TABLE 2 revamp of an existing plant. The bottom liquid product 54 of
Component Mol% the demethanizer 80 at about 50 F. proceeds is let down to
deethanizer 100 operating at about 280 psig. The ethylene,
Hydrogen 16.9 acetylene and ethane are separated as overhead product 102
Methane 31.8 and propylene and C+ hydrocarbons as bottom products 39.
45
Acetylene O.85
Ethylene 33.O The overhead product 102 with about 1.9 wt % acetylene is
Ethane 5.65 reheated to 130 F. and to passed acetylene hydrogenator
CO O.25 104 with outside hydrogen source 106. The acetylene free,
Propadiene/ O.35 C. vapor is condensed by preheating the feed in exchange
Methyl Acetylene
Propylene 8.90 50 108 and proceeds to ethylene fractionator 112 at about 240
Propane O.45 psig, or lower pressure depending on final disposition of the
Colefins 140 ethylene product, and the refrigeration System. The above
Butanes O.15 acetylene removal Step is not required for the alternate
Cs+ O.25
designs, Since acetylene is converted upstream of the
55 demethanizer.
In an alternate design (not shown) cracked gas after the 4 The overhead product 114 from the ethylene fractionator
Stages of compression, at about 270 psig, will go through 112 is off specification ethylene product. The side draw 79
H2O/CO removal, molecular Sieve drying and than a chill typically drawn about 8-10 trays below the top in the
down for C/C Separation in a front end deethanizer. The C. ethylene fractionator. Residual methane originated from the
and lighter fractions are warmed up undergo acetylene 60 demethanizer and excess hydrogen from the acetylene
hydrogenation to form ethylene and the C and heavier converter, are vented (if necessary) from the overhead as off
hydrocarbon liquids proceed to propylene and C+ recovery. specification ethylene 114.
The acetylene free light gas at about 260 psig is further The off specification ethylene is suitable as a feed to the
compressed through the 5th Stage to about 520 psig. In yet ethylbenzene plant. The amount of flow after cold recovery
another alternate design (not shown) the front end separation 65 in 116 is small. The ethylene is mixed in an ejector 94 with
of the CO. and lighter hydrocarbons will be carried out at the bulk of the dilute ethylene feed 53 containing about 10%
about 500 psig using double fractionation System. ethylene and about 5 ppm acetylene and propylene, and Send
 US 6,177,600 B1
7 8
to ethylbenzene plant 120. The bottom product 122, essen benzene (PEB). In a separate trans alkylation reactor 126 the
tially ethane is revaporize via cold recovery and Sent to the polyethylated benzene reacts with benzene to form ethyl
cracking Section 14. In the alternate design (not shown), benzene. After Series of products fractionation and purifi
demethanizer bottom proceeds directly to the ethylene frac cations (128-130), the final products are: (1) Ethylbenzene
tionator 112. The C+ hydrocarbon product undergoes Sepa with purity above 99.5%; (2) Vent gas 132 depleted of
ration of C and Ca+ hydrocarbon (not shown). The C. 95-99% of the ethylene feed and containing 34.5 mol % of
product is undergoes hydrogenation of the methyl acetylene hydrogen; and (3) A small amount, about 0.5-2.0%, of the
and propadiene and proceeds to propylene fractionation (not benzene remains converted to polyethylated product com
shown). The overhead product is propylene, the bottom monly referred to as flux oil (134). The flux oil is routed to
product is propane which is recycled to the cracking Section pyrolysis fuel oil. The cyclohexane and dimethylpentanes
14. are close boilers to benzene and purged 208 from the
In the demonstrated case of the invention, the demetha benzene recycle loop with 75 wt % benzene. The purge will
nizer is operating in a "sloppy cut” mode, for ethylene and go to battery limits or to conventional extraction of benzene
also separate all the hydrogen at the Overhead. For illustra 212 and benzene 211 will recycle to the feed. The cyclo
tive purposes the demethanizer overhead rather than oper 15 hexane residue 210 will go to battery limits. Additional
ating with full ethylene recovery at the bottom and essen benzene can be made by separation of toluene. FIG. 2, 220
tially no ethylene at the top, has 10 mol % or more ethylene and conversion of toluene to benzene by hydrodelakylation
in the Overhead and typical propylene content of below 5 221 which is a conventional and known process. However,
ppm by volume. The methane specification for the bottom the conversion by thermal Steam cracking in the furnace
will be about 100 to about 2,000 mol-ppm. By allowing with co-production of ethylene is an element of the inven
ethylene to escape from the top, at 10 mol % concentration, tion. After toluene conversion, the benzene, will be used as
about 15% of the ethylene, about 2% of the ethane, and make up about 60% of the requirement for the ethylbenzene
about 8% of the acetylene feeds to the demethanizer, will go or cumene production. Without toluene conversion, the
overhead. The overhead product gas about 6,890 lb-mol/hr benzene will provide about 40% of the alkylated benzene
at about -115 F. and about 450 psig will have the approxi 25 requirement. As an alternative, cyclohexane rich purge 213
mate molecular composition shown in Table 3: will go to benzene hydrogenation for cyclohexane produc
tion 214.
TABLE 3 If high benzene conversion yield is desired, the cyclo
Component Lb-molfhr Mol%
hexane rich purge 208 can be ethylated in a purge reactor
(not shown). The benzene reacts with ethylene to form
Hydrogen 2147 31.1 ethylbenzene and polyethylated benzene. The reaction prod
CO
Methane
31
4041
0.44
58.6
ucts will go through a fractionation (not shown). Benzene
Acetylene 9 O.13
cyclohexane and other co-boilers will be separated at an
Ethylene 650 9.5 atmospheric cut point of about 183 F. Ethylbenzene and
Ethane 13 O.19 35 polyethylated benzene will be recycled to the trans alkyla
Propylene O.O3 5 ppm tion reaction 126 (FIG. 5).
What is claimed is:
With the reference to FIG. 3, the gas is preheated via cold 1. A process for the Simultaneous coproduction of ethyl
recovery 122 and 124 to about 92 F. and further preheated benzene and ethylene comprising:
40
in exchanger 86 to 130 F. prior to acetylene reactor 88 and (1) producing ethylene and a dilute ethylene mixture
then introduced into carbon beds 90. If the acetylene reactor containing ethylene and methane and no more than 200
is avoided, the acetylene would react with benzene to form mol-ppm propylene Via conventional Steam cracking in
di-phenyl ethane. For the alternate case, these acetylene a Steam cracker and downstream propylene Separation;
removal Steps are not required. AS further optimization, not 45 (2) producing an impure benzene mixture by hydrogena
shown, Side reboiler and Side condensers can be used for tion and fractionation of pyrolysis gasoline during the
increasing refrigeration economy. Dilute ethylene can be ethylene production, the impure benzene mixture con
made as a Side draw product. taining benzene and a total of 1.0 to 20.0 wt % of one
Propylene and acetylene free gas at about 415 psig in line or more impurities Selected from the group consisting
53 combines with off specification ethylene from ethylene 50
of cyclohexane, dimethylpentanes, methylcyclopen
fractionator in ejector 94 and the combined gas 118 proceeds tanes and methylcyclohexane,
as feed to the ethylation reactor section 120 of the ethyl (3) feeding impure benzene mixture to an integrated
benzene plant. ethylbenzene production Zone;
Liquids, mostly C, Cs, and C as condensed in the gas (4) feeding at least a portion of the dilute ethylene mixture
compression inter and after coolers FIG. 2. 19.c combines 55 produced during the Steam cracking and downstream
with 34 to a C-C raw pyrolysis gasoline 200. The raw propylene Separation to the ethylbenzene production
pyrolysis gasoline is undergoing Selective di-olefins and Zone, wherein the ethylene is present in the dilute
olefins saturation qt. 201. Hydrotreated liquid 36 and C. ethylene mixture in a concentration of about 3 to 40 vol
boilers below benzene (170 F) are separated at 202, and %; and
sent at 203 for cracking at 14. C+ stream at 204, is sent to 60 (5) reacting the ethylene in the dilute ethylene mixture
decyclohexanizer 205 where benzene and cyclohexane are with the benzene in the impure benzene mixture to
separated. The benzene cyclohexane 206, containing over 90 form ethylbenzene.
wt % benzene, is used as impure benzene feed to the 2. A process as claimed in claim 1 in which the impure
ethylbenzene plant 120, or to a cumene plant (not shown). benzene mixture contains a total of 3.0 to 8.0 wt % of one
In the ethylbenzene plant 120, ethylene reacts with ben 65 or more impurities Selected from the group consisting of
Zene feed 206 and stoichiometric excess of benzene. The cyclohexane, dimethylpentanes, methylcyclopentanes, and
exothermic reaction forms ethylbenzene and poly ethylated methylcyclohexane.
 US 6,177,600 B1
9 10
3. A proceSS as claimed in claim 1, further comprising c) reheating the dilute ethylene mixture; and
purging from the ethylbenzene production Zone a purged d) further purifying the bottoms for ethylene product
mixture comprising unreacted benzene and a total of 7.0 to recovery.
60 wt % of one or more impurities selected from the group 6. A proceSS as claimed in claim 5 in which the demetha
consisting of cyclohexane and dimethylpentanes. 5 nization Zone is operated at a pressure from 330 to about 550
4. A proceSS as claimed in claim 1, further comprising pS1g.
purging from the ethylbenzene production Zone a purged 7. A process as claimed in claim 5 in which essentially all
mixture comprising unreacted benzene and a total of 15.0 to of the hydrogen in the cracked gas is separated with the
40.0 wt % of one or more impurities selected from the group dilute ethylene fluid mixture at a temperature above about
consisting of cyclohexane and dimethylpentanes. -150 F. and at pressures of about 300 to about 550 psig.
5. A proceSS as claimed in claim 1 further comprising: 8. A process according to claim 1 further comprising:
a) forming in one or more hydrocarbon cracking Zones a (a) providing pyrolysis gasoline produced during the
cracked gas comprising hydrogen, carbon monoxide, Steam cracking containing benzene and toluene, and
methane, acetylene, ethylene, ethane and propylene and (b) converting the toluene to benzene by hydrodealkyla
a cracked liquid which includes the pyrolysis gasoline, 15
tion.
wherein the pyrolysis gasoline comprises benzene, 9. A proceSS according to claim 1, further comprising
toluene and cyclohexane, converting the ethylbenzene to Styrene.
b) fractionating said cracked gas in a demethanization 10. A proceSS according to claim 5, further comprising
Zone to form (1) the dilute ethylene mixture wherein converting the ethylbenzene to Styrene.
the dilute ethylene mixture contains hydrogen, carbon 11. A proceSS according to claim 1, further comprising
monoxide, methane, and no more than 200 mol-ppm purifying the ethylbenzene formed in the ethylbenzene pro
propylene, and ethylene present in an amount of from duction Zone to have a purity of at least about 99.5 wt %.
about 3 to about 35 percent of the ethylene fed to said 12. A proceSS according to claim 5, further comprising
demethanization Zone at a pressure of from about 70 to 25
purifying the ethylbenzene formed in the ethylbenzene pro
about 550 psig, whereby the dilute ethylene mixture duction Zone to have a purity of at least about 99.5 wt %.
undergoes no further phase change, and (2) bottoms
comprising ethylene and ethane; k k k k k