BACKGROUND OF THE INVENTION Conventional ethylene production consists of the following key process operation: (a) Thermal cracking, in presence of dilution steam, of hydrocarbon at about 15-25 psig and 1,500-1,600° F to form cracked gas containing ethylene in an amount of 25-40 wt % (and up to 80 wt% for net ethane feed), and other by products such as propylene, acetylene, hydrogen, methane and C3+ products. The thermal section includes cracked gas cooling, steam generation and C9+ hydrocarbon condensation. Traces of CO, CO2 and H2S are formed in the cracking.

(b) Cracked gas compression to 400-600 psig, traces of C02 and H2S removal, drying, and bulk C4+ product recovery by condensation at about 100 ° F, using cooling water.

(c) Acetylene conversion to ethylene via selective hydrogenation, chill down and cryogenic recovery of ethylene by fractionation at below-30° F.

(d) Recovery of propylene, propane and C4+ hydrocarbons by warm distillation at above 80 ° F.

(e) Cascade refrigeration of ethylene and propylene refrigerants, to support the above, down to a temperature of below-100 °F.

(f) Methane refrigeration and or expander to reach refrigeration below-180 ° F.

(g) In case of Naphtha feed, residual liquid products from cracking such as pyrolysis fuel oil and pyrolysis gasoline, which are rich in aromatics, are selectively hydrotreated for di-olefin and olefin saturation.

Efficient cryogenic recovery of the ethylene is a key element in design of ethylene plants.

The motive power for compression and refrigeration, and consequently the capital cost escalates rapidly as the rate of ethylene recovery increases. For example, the typical ethylene recovery of 99.7-99.9% requires much higher investment and 50% more refrigeration energy in the demethanizer as compared with 95% rate of ethylene recovery. Thus, reduction of the marginal refrigeration required for ethylene recovery by using 95% or lower recovery could substantially improve the overall economics of the ethylene plant, if a down stream outlet, other than fuel gas, is found for the 5 % more of the unrecovered gaseous ethylene. Normally the unrecovered 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 15-20 % of its equivalent value as downstream product. The ethylene product is commonly used as a feedstock to many downstream processing including ethylbenzene. Production of ethylbenzene from pure ethylene against dilute ethylene feed, although somewhat advantageous from a stand point of the ethylbenzene plant alone, is not an absolute requirement and its relative cost impact is rather marginal as compared with the estimated saving in the ethylene plant.

In recent years, processes for producing ethylbenzene from dilute ethylene feed streams have been developed by Badger, a subsidiary of Raytheon, ABB Lummus Global/CDTech, Sinopec and others. The key driving forces behind these new developments are the objectives of using offgases from fluid catalytic crackings (FCC) in petroleum refining. These offgases are at 150-250 psig and typically contain 8-18 vol% of ethylene, 3-9 vol%, of propylene and 12-20% hydrogen.

Limited integration of ethylbenzene and ethylene production was experienced in a number of locations including El Paso Products (Now Huntsman Chemical) in Odessa, Texas, where rich ethylene rich stream at 40 psig is compressed to 550 psig and feeds an ethylbenzene plant.

This invention combines the known technologies as developed for producing ethylbenzene from refinery FCC offgases, and for producing ethylene by conventional cracking of hydrocarbon feeds.

SUMMARY OF THE INVENTION More particularly dilute ethylene at concentrations of about 3 to about 40 vol% and substantially free of propylene is extracted from a cryogenic demethanizer as an overhead gas.

The bulk of the dilute ethylene stream comprises methane and hydrogen. The dilute ethylene stream at a typical pressure of about 330 to about 500 psig and after cold recovery and acetylene removal is the feed, along with common specification benzene, 99.9% wt% purity, or impure benzene, 95 to 98 wt% purity, to an ethylbenzene plant. The ethylbenzene is converted to styrene. If styrene is produced on site along with the ethylbenzene, it normally is produced by thermal dehydrogenation of ethylbenzene. Steam at about 30 psig and 1,500 F is used as a source of energy and also reduces the partial pressure of ethylbenzene, is directly premixed with ethylbenzene in a typical weight ratio of about 1.1 to about 1.8. Superheating of steam at about 30 to about 40 psig to about 1,500 F in the cracking furnace of the ethylene plant becomes a second element of this invention. Low pressure saturated steam from the ethylbenzene and styrene plants and extraction steam from turbine drivers of the ethylene plant are superheated at the convection section of the cracker in the ethylene plant. The superheated steam is routed to the styrene plant, eliminating a specially dedicated superheater at the styrene plant.

If naphtha or heavier feeds are used, a pyrolysis gasoline product which is rich in benzene, is used as a source of benzene for the ethylbenzene plant. The benzene and co-boilers, cyclohexane and dimethylpentanes, are used as a feed to the ethylbenzene plant. The saturated C6 co-boilers are purged from the ethylbenzene plant, ethylatian reaction loop.

DESCRIPTION OF DRAWINGS FIG. 1 illustrates the cracking section of the ethylene plant and heat recovery with high pressure steam generation and superheating and includes low pressure steam superheating for a styrene plant which is an element of the invention.

FIG. 2 illustrates the quench oil and quench water pyrolysis gasoline and pyrolysis fuel oil recovery, cracked gas compression, CO2 and H2S removal, cracked gas drying, pyrolysis gasoline hydrotreating, dehexanizer, benzene recovery, toluene conversion to benzene as a feed to the ethylbenzene plant.

FIG. 3 illustrates the dilute ethylene recovery which is the key element of the invention.

FIG. 4 illustrates the ethylene recovery, acetylene reactor and off specification ethylene diversion to the ethylbenzene plant, which is an element of the invention.

FIG. 5 illustrate ethylbenzene and styrene production along with hydrogen recovery.

DETAILED DESCRIPTION OF THE INVENTION For illustration and process consistency, the invention will be described for an ethylene plant when naphtha is the sole feedstock followed by ethylbenzene production and subsequent production of styrene monomer. This enables demonstration of all the elements of the invention.

This is reasonable since more than 50% of world ethylene production capacity originates from naphtha. The principles of this mode will be very similar for all other feedstocks.

The assumed capacity of the ethylene plant for consistency purposes is 1,000,000,000 lb/year, along with co-production of 400,000,000 lb/year of propylene and by products such as hydrogen, pyrolysis gasoline and pyrolysis fuel oil. About 8,300 hours per year of operation are assumed. Pyrolysis products such as ethane, propane, C4 and C5 are internally recycled and converted to ethylene and propylene. Acetylene is selectively hydrogenated to ethylene, and methylacetylene and propadiene are selectively hydrogenated to propylene.

According to the invention, for illustrative purposes about 15% of the crude ethylene originated in the cracking, is recovered as a dilute ethylene product at a concentration of about 10.0 vol. % and serves as a feed for production of 550,000,000 lb/year of ethylbenzene. The ethylbenzene is converted to 500,000,000 lb/year of styrene monomer, along with hydrogen and small amounts of other by products.

The cracking yield is based on of molecular weight of 92, a specific gravity of about 0.69, paraffin content of about 80 wt % (50% normal, 50% iso), naphtene content of about 10 wt % and aromatic content of 10 wt%. The naphtha contains less than 0.1 wt% olefins and traces of sulfur.

With reference now to FIG. 1, Naphtha net feed, 10 about 33,000 bpsd (331,000 lb/hr) and about 65,000 lb/hr of combined recycles 12 of C2 H6 and C3H8 gas feed and C4HIo, C5H12 and C6H14 liquids after hydrogenation, are vaporized in vaporizer 14 and mixed with steam in line 16, at a typical weight ratio of about 0.5 steam to hydrocarbons feeds.

The steam helps reduce coking in the tubes of the furnaces, and also reduce the partial pressure of the hydrocarbons, thus increasing ethylene yield.

This hydrocarbon steam mixture is further preheated in heater 18 and proceeds, line 20 prior to the cracking section of the pyrolysis furnace 22. The furnace is fired by fuel gas principally CH4 product 24 as recovered from the down stream process. The source of the CH4 with reference to FIG. 3, is the cryogenic separation zone (80) in the ethylene plant. However, its final recovery is from the vent gas 121 in the ethylbenzene plant FIG. 5. For the above naphtha net feed and the recycles, the following typical yield, in weight percent per pass, is shown in Table 1.

TABLE 1 Component Wt% Destination Hydrogen 1.05 Product to battery limit.

Methane 15.8 Fuel gas product to cracking furnaces Acetylene 0.9 Converted to ethylene product Ethylene 29.6 Main product to battery limits Ethane 6.2 Recycled and converted to ethylene Propadeine 0.6 Converted to propylene product Propylene 14.0 Main product to battery limits Propane 0.4 Recycled and converted to products.

C4 Olefins + Paraffins 9.5 Hydrotreated and recycled to cracking C5 Olefins + Paraffins 4.5 Hydrotreated and recycled to cracking Benzene 6.5 Light gasoline product, feed to ethylbenzene.

Toluene 2.3 Light gasoline product to battery limits or as a source of benzene Xylene + Ethlybenzene 0.4 Heavy gasoline product to battery limits Balance of Pyrolysis Fuel 8.1 Product to battery oil and pyrolysis gasoline limit (C6-C9) H2S and CO2 Traces waste to battery limits as sodium salts CO Trace To fuel The net ethylene make is about 5.5 wt% of the naphtha feed in dilute form and about 29.0 wt% of the naphtha feed in concentrated pure form. The net propylene recovery is about 14.5 wt %.

In the heat recovery section 18 of the cracker, hot combustion gas from the pyrolysis section undergoes heat recovery providing preheating boiler feed water 28 and superheating saturated steam 9 at about 1,900 psig and about 650 F to about 1,800 psig and 980 F stream 30.

The cracked gas 32 is cooled in transfer line exchangers 34 to about 800 to about 840 F by generating saturated steam at about 1,900 psig and about 650 F. The overall steam production is typically in balance as a motive power source for the cracked gas compression and refrigeration compression drivers of the ethylene plant.

Due to the process integration concept of the invention, an additional steam coil 36 is used to convert stream at a pressure of about 40 psig and below 450°F 38 to provide steam at 1,500 F for the styrene plant 40. For a styrene production rate of 500,000,000 lb/year, the thermal load of the 40 psig steam coils is estimated to be about 6% of the overall conventional fired duty in the cracking furnace (22).

With reference to FIG. 2 The cracked gas at about 800 to about 840 °F and 10 psig in line 42 after steam generation is quenched with pyrolysis fuel oil in quench zone 44 using oil recycle and heat absorption by generating saturated steam at 110-130 psig.

The net product made after stripping of light pyrolysis products is Cg+, pyrolysis fuel oil. The steam at 110-130 psig is ultimately used as a dilution steam for the naphtha and recycle feeds 16. Overhead gas 46 from the quench oil system at about 220-250F proceeds to the quench water system 48, and preheat quench water at 110°F in 50 to 180°F in line 52 and recovery of aromatic rich C6-C9 pyrolysis gasoline 54. The 180 F water 52 serves as a low level heat source to a number of reboiling services in the plant facility. After utilization of the low level heat, water at about 110 ° F is recycled back to the quench water system 48.

Quenched gas is further cooled to about 100° F with about 88° F cooling water (depending on ambient conditions) and the bulk of the water vapors and the C6+ products are condensed and separated. The cracked gas at about 5.0 psig proceeds by line 56 to compression. The gas is compressed to about 400-600 psig in four to five stages. For illustration purposes five stages of compression to about 520 psig are assumed. After three stages of compression (58,60, and 62) to about 140 psig, the gas 64 proceeds to caustic scrubber (66) for C02 and H2S removal and further compressed at 68 and 70 to about 520 psig in line 72 and aftercooled to about 100° F. The gas is further cooled in exchanger 74 to about 60 F by refrigeration or cold recovery prior to water/hydrocarbon separation. The gas proceeds to molecular sieve dryer 26 as needed for downstream cryogenic product recovery. At this point about 99% of the benzene and C6,85% of the C5 hydrocarbon and 65% of the C4 hydrocarbons are condensed and separated in lines at 15,17,19,19A and 19B and send to raw pyrolysis gasoline 34.

Water and hydrocarbon liquids, mostly C4, C5, and C6 are condensed in the interstage and after stage cooling of the cracked gas compression Fig. 2, stream 15,17,19,19A and also from dryer prechilling (74) and water is separated (not shown). The combined hydrocarbon liquid 19c combines with aromatic rich stream 34 to feed stream 200 to selective olefin and di- olefin saturation unit 202. The hydro treated stream 36 free of sulfur, proceed to dehexanizer (201) where all C4, C5, and all C6 except cyclohexane and benzene are separated overhead, at an atmospheric cut point of 167°F. This light saturated liquid 200 A recycles back to cracking section 14, (Fig. 1).

Bottom product from 201 fractionation, proceeds to de-cyclohexanizer 205 where benzene, cyclohexane and dimethylpentanes are separated, at an atmospheric cut point of 183 °F.

The overhead product, stream 206 is impure benzene containing typically 2-8 wt% of cyclohexane and dimethylpentanes. This impure benzene is used as a feed for the ethylbenzene 120 (Fig. 5). Toluene rich stream 207, can proceed to battery limits or alternately to toluene fractionation 220. Overhead toluene proceeds to conventional hydro-dealkylation 221 where hydrogen reacts with toluene to form benzene and methane.

With reference to new FIG. 3, about 12710 lb-mol/hr of dry cracked gas at about 500 psig and about 60° F in line 78 with the molecular composition shown in Table 2, proceeds to a chill down train for cryogenic product recovery.

TABLE 2 Component Mol% Hydrogen 16.9 Methane 31.8 Acetylene 0.85 Ethylene 33.0 Ethane 5.65 CO 0.25 Propadiene/Methyl Acetylene 0.35 Propylene 8.90 Propane 0.45 C4 olefins 1.40 Butanes 0.15 C5+ 0.25 In an alternate design (not shown) cracked gas after the 4 stages of compression, at about 270 psig, will go through H20/CO2 removal, molecular sieve drying and than a chill down for

C2/C3 separation in a front end deethanizer. The C 2and lighter fractions are warmed up undergo acetylene hydrogenation to form ethylene and the C3 and heavier hydrocarbon liquids proceed to propylene and C4+ recovery. The acetylene free light gas at about 260 psig is further compressed through the 5th stage to about 520 psig. In yet another alternate design (not shown) the front end separation of the C2 and lighter hydrocarbons will be carried out at about 500 psig using double fractionation system.

In the primary design, as well as alternate designs, the dry cracked gas at about 500 psig and about 60 F in line 78 is chilled down to about-200°F using propylene and ethylene refrigeration, followed by an expander or methane refrigeration (not shown). At this point essentially all the ethylene (99.9%) is condensed in several stages along with the bulk of the methane, and hydrogen rich gas (75% H2) is separated from the crude ethylene liquids which are fed to a demethanizer 80, operating at about 300 to about 500 psig and, for this illustration, preferably about 460 psig. In a conventional design, the overhead product of the demethanizer overhead is essentially methane. some residual hydrogen with very minimal quantity, say 100 vol. ppm, of ethylene. The bottom product 54 is essentially ethylene, ethane, propylene and C3+ hydrocarbons. Methane content is under 100 ppm and hydrogen content is essentially nil. In a conventional design, the ethylene in the overhead of the demethanizer at 48 represents a net ethylene product loss to the fuel gas system, thus a good economical design should minimize its content by appropriate reflux of liquid methane stream 47 at typically about-145°F. The cold for the reflux is provided by ethylene refrigeration at about-150° F which corresponds to slightly above its atmospheric pressure. Typically 99.8% of the ethylene, and essentially 100% of the ethane and acetylene from the charge gas are recovered as a bottom product for further processing and separation. The same is essentially true for the alternate designs except that essentially no C3+ and acetylene are present in the bottom of the demethanizer.

In the conventional design stream 48 the CH4/H2 overhead from the demethanizer at about 460 psig is typically expanding to fuel gas pressure of about 50 psig in a turbo-expander, (not shown) generating motive power as well as refrigeration (needed for the low temperature ethylene condensation and hydrogen separation). The cold is recovered from the H2/CH4 rich gas prior to diversion to the fuel system for subsequent combustion in the cracking furnaces.

In the instant invention all hydrogen separation occurs in the demethanizer, unless the invention is applied toward revamp of an existing plant. The bottom liquid product 54 of the demethanizer 80 at about 50 F proceeds is let down to deethanizer 100 operating at about 280 psig. The ethylene, acetylene and ethane are separated as overhead product 102 and propylene and C3+ hydrocarbons as bottom products 39. The overhead product 102 with about 1.9 wt % acetylene is reheated to 130°F and to passed acetylene hydrogenator 104 with outside hydrogen source 106. The acetylene free, C2 vapor is condensed by preheating the feed in exchange 108

and proceeds to ethylene fractionator 112 at about 240 psig, or lower pressure depending on final disposition of the ethylene product, and the refrigeration system. The above acetylene removal step is not required for the alternate designs, since acetylene is converted upstream of the demethanizer.

The overhead product 114 from the ethylene fractionator 112 is off specification ethylene product. The side draw 79 typically drawn about 8-10 trays below the top in the ethylene fractionator. Residual methane originated from the demethanizer and excess hydrogen from the acetylene converter, are vented (if necessary) from the overhead as off specification ethylene 114.

The off specification ethylene is suitable as a feed to the ethylbenzene plant. The amount of flow after cold recovery in 116 is small. The ethylene is mixed in an ejector 94 with the bulk of the dilute ethylene feed 53 containing about 10% ethylene and about 5 ppm acetylene and propylene, and send to ethylbenzene plant 120. The bottom product 122, essentially ethane is re-vaporize via cold recovery and sent to the cracking section 14. In the alternate design (not shown), demethanizer bottom proceeds directly to the ethylene fractionator 112. The C3+ hydrocarbon product undergoes separation of C3 and C4+ hydrocarbon (not shown). The C 3 product is undergoes hydrogenation of the methyl acetylene and propadiene and proceeds to propylene fractionation (not shown). The overhead product is propylene, the bottom product is propane which is recycled to the cracking section 14.

In the invention the demethanizer is operating in a"sloppy cut"mode, for ethylene and also separate all the hydrogen at the overhead. For illustrative purposes the demethanizer overhead rather than operating with full ethylene recovery at the bottom and essentially no ethylene at the top, has 10 mol% or more ethylene in the overhead and typical propylene content of below 5 ppm by volume. The methane specification for the bottom will be about 100 to about 2,000 mol-ppm. By allowing ethylene to escape from the top, at 10 mol% concentration, about 15% of the ethylene, about 2% of the ethane, and about 8% of the acetylene feeds to the demethanizer, will go overhead. The overhead product gas about 6,890 lb-mol/hr at about-115 ° F and about 450 psig will have the approximate molecular composition shown in Table 3:

TABLE 3 Component Lb-mol/hr Mol % Hydrogen 2147 31.1 CO 31 0.44 Methane 4041 58.6 Acetylene 9 0.13 Ethylene 650 9.5 Ethane 13 0.19 Propylene 0.03 5 ppm With the reference to FIG. 3, the gas is preheated via cold recovery 122 and 124 to about 92°F and further preheated in exchanger 86 to 130 F prior to acetylene reactor 88. The acetylene free gas 52 proceeds to activated carbon beds 90 for removal of C6-C8 trace formed in acetylene reactor 88. For the alternate case, these steps are not required. As further optimization, not shown, side reboiler and side condensors can be used for increasing refrigeration ecomony.

Dilute ethylene can be made as a side draw product.

Propylene and acetylene free gas at about 415 psig in line 53 combines with off specification ethylene from ethylene fractionator in ejector 94 and the combined gas 118 proceeds as feed to the ethylation reactor section 120 of the ethylbenzene plant.

For process control purposes, liquid ethylene product provides up to 10% of the feed to the ethylbenzene plant.

Liquids, mostly C4, C5, and C6 as condensed in the gas compression inter and after coolers FIG. 2.19C combines with 34 to a C4-Cg raw pyrolysis gasoline 200. The raw pyrolysis gasoline is undergoing selective di-olefins and olefins saturation qt. 201. Hydrotreated liquid 36 and C6 boilers below benzene (170°F) are separated at 202, and sent at 203 for cracking at 14. C6+ stream at 204, is sent to dehexanizer 205 where benzene and cyclohexane are separated.

206 lb from heavy C6 and C7 = 207. The benzene cyclohexane, 206 containing over 90 wt% benzene is used as impure benzene feed to the ethylbenzene plant 120.

In the ethylbenzene plant 120, ethylene reacts with benzene feed 206 and stoichiometric excess of benzene. The exothermic reaction forms ethylbenzene and poly ethylated benzene (PEB). In a separate trans alkylation reactor 126 the polyethylated benzene reacts with benzene to form ethylbenzene. After series of products fractionation and purifications (128-130), the final products are: (1) Ethylbenzene with purity above 99.5%; (2) Vent gas 132 depleted of 95- 99% of the ethylene feed and containing 34.5 mol % of hydrogen; and (3) A small amount, about 0.5-2.0%, of the benzene remains converted to polyethylated product commonly referred to as

flux oil (134). The flux oil is routed to pyrolysis fuel oil. The cyclohexane and dimethylpentanes are close boilers to benzene and purged 208 from the benzene recycle loop with 75 wt% benzene. The purge will go to battery limits or to conventional extraction of benzene 212 and benzene 211 will recycle to the feed. The cyclohexane residue 210 will go to battery limits. Additional benzene can be made by separation of toluene. FIG. 2,220 and conversion of toluene to benzene by hydrodelakylation 221 which is a conventional and known process. After toluene conversion, the benzene, will be used as make up about 60% of the requirement for the ethylbenzene production. Without toluene conversion, the benzene will provide about 40% of the requirement. As an alternative, cyclohexane rich purge 213 will go to benzene hydrogenation for cyclohexane production 214.

If high benzene conversion yield is desired, the cyclohexane rich purge 208 can be ethylated in a purge reactor (not shown). The benzene reacts with ethylene to form ethylbenzene and polyethylated benzene. The reaction products will go through a fractionation (not shown).

Benzene cyclohexane and other co-boilers will be separated at an atmospheric cut point of about 183 °F. Ethylbenzene and polyethylated benzene will be recycled to the trans alkylation reaction 126 (Fig. 5).

As another alternative (not shown) cyclohexane can be selectively oxidized to cyclohexanol. The cyclohexanol will be separated by fractionation to be recovered as valuable product.