Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By c content reduction – e.g. – cracking – etc.
Reexamination Certificate
2001-10-23
2004-01-13
Griffin, Walter D. (Department: 1764)
Chemistry of hydrocarbon compounds
Unsaturated compound synthesis
By c content reduction, e.g., cracking, etc.
C585S650000, C585S483000, C585S323000, C208S067000, C208S069000, C208S130000
Reexamination Certificate
active
06677496
ABSTRACT:
BACKGROUND
About 50% of benzene consumption in the petrochemical industry is directed to the production of ethylbenzene, an additional about 25% is dedicated to the production of cumene, and another 15% goes toward the production of cyclohexane. About 4 to 5% of benzene is directed to the production of nitrated products. Ethylbenzene is a precursor for the production of styrene, which is a precursor for the production of polystyrene, and cumene is a precursor for the production of phenol.
Benzene is obtained from various sources. Over 55% of all benzene is attained from to petroleum refining, mostly catalytic reforming of naphtha. Additionally, over 30% of all benzene is obtained from pyrolysis gasoline resulting from steam cracking in olefins production and under 15% is obtained from coke oven gas, originated from coal, as related to iron and steel production. All the above sources are coproducers of toluene, and a significant portion of toluene is converted to benzene by either hydrodealkylation or by coproduction of xylenes.
Production of ethylene by gas crackers, mostly C2-C3 and some C4 feeds, amounts to about 40% of the world ethylene capacity. This results in a relatively small coproduction of benzene compared to benzene coproduced in naphtha and gas oil crackers, which account for 60% of the world's ethylene production capacity. A typical overall benzene yield from ethane cracking is on the order of 0.60 wt % of the ethane feed, and benzene yield from propane cracking is on the order of 3.0 wt % of the propane feed. Benzene yield resulting from naphtha cracking can range from 4 wt % to 10 wt % of the naphtha feed depending the on aromatic content of the naphtha and severity of cracking. The benzene coproduction in naphtha cracking is a coincidental production to ethylene, whereas in the present invention additional ethylene production is coincidental to benzene production. For C2/C3 cracking, any significant downstream alkylation process, such as for producing ethylbenzene, is likely to be deficient in benzene.
Ethane and propane feeds are common in North America and the Arabian Gulf. In these places, benzene produced from petroleum refining would be a major provider of the benzene needed for downstream alkylation processes while the C2/C3 feed will be the major source of ethylene.
In general, benzene of nitration grade, about 99.9 wt % along with other specifications, has been used for nearly all applications, including alkylation for producing ethylbenzene and cumene. As noted above, benzene consumed by nitration processes is under 5%. However, production of ethylbenzene by vapor phase processes as practiced in many locations would require benzene of a high purity level. In recent years, the concept of alkylation of impure benzene produced from pyrolysis gasoline with dilute ethylene in mixed phase alkylation has been proposed, for example, in U.S. Pat. Nos. 5,880,320, 5,977,423 and 6,252,126. The concept of using impure benzene to produce cumene was suggested in U.S. Pat. No. 6,177,600. U.S. Pat. Nos. 5,750,814 and 6,002,057 disclose laboratory scale evidence that catalysts such as zeolite beta or zeolite Y are suitable for mixed phase alkylation of a dilute benzene stream, such as 30 wt % at about 370° F. with dilute ethylene such as 20 vol %. Alkylation of impure benzene with propylene and heavy olefins is disclosed as well.
U.S. Pat. Nos. 6,177,600 and 6,252,126 disclose a method of recovering benzene with over 80% purity, and preferably over 92% purity, where the impure benzene to be used for production of either ethylbenzene or cumene. The impure benzene was formed by hydrotreating and fractionating pyrolysis gasoline, typically containing 30 wt % benzene. Methyl-cyclo-pentane, cyclohexane and di-methyl-pentates account for the bulk of the impurities. An article in May 99 issue of Hydrocarbon Processing entitled: “Integrate ethylbenzene production with an olefins plant” discusses that impurities could consist of 75% Cyclo —C6 and 25% of C7, mostly di-methyl-pentates. All of these C6/C7 components are known to form azeotropes with benzene, and thus separation of cyclohexane and di-methyl-pentanes by conventional fractionation is impossible.
The conventional method of benzene purification and separation from the above azeotropes is by aromatic extraction or extractive distillation processes, such as UOP's Sulfolane, Lurgi's Arosolvan, IFP's DMSO processes and Uhde's Morphylane extractive distallation process. These processes, which are known to be expensive, result in a high recovery of aromatics while producing benzene at purity of over 99.9 wt %. The purity of the benzene is an important issue if ethylbenzene is produced by a vapor phase process resulting in alkylation at about 750° F. Non-aromatic impurities could crack under these alkylation conditions and would potentially contaminate the ethylbenzene product with undesirable alkylates such as cumene. In recent years, the industry has been shifting its mode of alkylation from zeolite vapor phase or AlCl
3
liquid phase to zeolite liquid phase alkylation with either polymer grade pure ethylene or dilute ethylene. The dilute ethylene may come as a coproduct from ethylene production such as ethylene-ethane grade with 60-90 vol % ethylene or ethylene-hydrogen-methane grade at concentrations of 8 to 15 vol %. The dilute ethylene for alkylation could be from fluid catalytic cracking (FCC) refinery source as well. The estimated alkylation temperature ranges from 310° F. to 530° F., depending on ethylene concentration and alkylation pressure. Industry research seems to indicate that alkylation in this temperature range will not crack the assumed non-aromatic impurities in the benzene, resulting from the application of the present invention where the purified benzene is applied. This is even more the case for alkylation below 420° F. and if the impurities are the more stable cycloparaffins, such as methyl cyclopentane or cyclohexane. The conversion of vapor phase alkylation units to liquid or mixed phase alkylation is decreasing the portion of the benzene market where nitration grade or pure benzene is mandatory. This market shift is the major driving force behind the present invention.
As mentioned above, catalytic reforming of naphtha is a major source of production of aromatics, including benzene. Typically, a straight run, full range naphtha resulting from crude oil fractionation has a boiling range of 100 to 350° F. It is recovered as a side cut from atmospheric distillation, typically about 10 to 20% of the crude oil, depending on the boiling curve of the crude oil. This naphtha undergoes further fractionation to separate a cut point of below 200° F., light naphtha. The C7+ cut, typically 75% of the original naphtha cut, undergoes hydrodesulfurization to less than 1 ppm sulfur and is used as a feed for catalytic reforming. In the catalytic reforming, desulfurized naphtha undergoes catalytic and endothermic dehydrogenation at about 850 to 1000° F. and 60 to 75 psig in 3 to 4 successive reactors equipped with interstage reheating. Aside from some cracking to C1-C5, the bulk of the naphtha is converted to aromatics, about 70 wt %, depending on the severity and characteristics of the naphtha. The balance of reforming reactor effluent is C5-C8 non aromatics, of which about 60 to 75% are iso paraffins, including di methyl pentanes. Fractionation and production of benzene with over 75 wt % purity from reformer reactor effluent by conventional distillation may become difficult because of the azeotrope forming characteristics of compounds such as di-methyl-pentanes, cyclohexane and methyl-cyclo pentane. Production of ethylbenzene or cumene from 75 wt % benzene would result in a low benzene yield due to high purge rate that would be required for non aromatics. Consequently, this would result in marginal economics.
To illustrate the conventional fractionation issue the following is a brief summary of binary, benzene and C6/C7 paraffins azeotropic chracteristics in atmospheric pressure. Pure
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