CN104744192B - A kind of liquefied gas and C 5-C 9non-aromatic hydro carbons prepares the system and method for p-Xylol and ethylene glycol - Google Patents
A kind of liquefied gas and C 5-C 9non-aromatic hydro carbons prepares the system and method for p-Xylol and ethylene glycol Download PDFInfo
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- CN104744192B CN104744192B CN201510059794.3A CN201510059794A CN104744192B CN 104744192 B CN104744192 B CN 104744192B CN 201510059794 A CN201510059794 A CN 201510059794A CN 104744192 B CN104744192 B CN 104744192B
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- gas
- ethylene glycol
- hydrogen
- aromizing
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 314
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims description 55
- 239000007789 gas Substances 0.000 claims abstract description 337
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 158
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 134
- 239000001257 hydrogen Substances 0.000 claims abstract description 122
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 109
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000001301 oxygen Substances 0.000 claims abstract description 83
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 83
- 239000007788 liquid Substances 0.000 claims abstract description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 60
- 230000008929 regeneration Effects 0.000 claims abstract description 58
- 238000011069 regeneration method Methods 0.000 claims abstract description 58
- 238000000926 separation method Methods 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 38
- 239000002351 wastewater Substances 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 230000008878 coupling Effects 0.000 claims abstract description 29
- 238000010168 coupling process Methods 0.000 claims abstract description 29
- 238000005859 coupling reaction Methods 0.000 claims abstract description 29
- 239000002912 waste gas Substances 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 101
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 93
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 84
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 74
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 73
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 47
- 150000002431 hydrogen Chemical class 0.000 claims description 37
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 32
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
- 239000003921 oil Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006317 isomerization reaction Methods 0.000 claims description 15
- 239000008096 xylene Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 230000009849 deactivation Effects 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- -1 polyethylene terephthalate Polymers 0.000 abstract description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 4
- 238000005899 aromatization reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 11
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of liquefied gas and C
5-C
9non-aromatic hydro carbons prepares the system of p-Xylol and ethylene glycol, mainly comprises aromizing subsystem, gas-liquid separation subsystem, gas gas isolated subsystem, aromatic hydrocarbons associating subsystem, synthetic gas prepares subsystem, and adopting CO catalytic coupling, subsystem prepared by the ethylene glycol of barkite hydrogenation route; Utilize this system, p-Xylol and the large raw material of ethylene glycol two of the equivalent required for polyethylene terephthalate can be produced with a kind of hydrocarbon raw material; Meanwhile, inner hydrogen, CO and methane etc. can share between different sub-systems, decrease Complicated Flow when original ethylene glycol is produced and a large amount of ingredient requirements; Meanwhile, what produce in ethylene glycol preparation process is used separately as containing oxygen waste gas and containing alcohol waste water the raw material that the medium of catalyst regeneration in aromatization subsystem and synthetic gas prepare subsystem, has not only saved cost but also environmental protection.Utilize this system converting low value hydro carbons, effectively can improve value-added content of product.
Description
Technical field
The invention belongs to chemical technology field, particularly a kind of liquefied gas and C
5-C
9non-aromatic hydro carbons prepares the system and method for p-Xylol and ethylene glycol.
Background technology
Polyethylene terephthalate (PET) is the most important raw material in high-end chemical fibre and the industry of beverage bottle sheet, prepares primarily of p-Xylol and the large raw material of ethylene glycol two and obtains.Traditional p-Xylol is by naphtha reforming, cracking of ethylene by-product, and alcohol ether carries out the technology such as aromizing and first obtains BTX aromatics, and then obtain through Aromatic Hydrocarbon United Plant (comprising Aromatics Extractive Project, xylene isomerization and fractionation by adsorption, the disproportionation of toluene and trimethylbenzene, ethylbenzene transposition or de-ethyl etc.).Because petroleum naphtha source is day by day urgent, produce the raw material more and more lighting of ethene, the aromatic hydrocarbons supply obtained by these two kinds of routes is day by day tight near simultaneously.Meanwhile, by aromaticity content low (50-65%) in petroleum naphtha route gained hydrocarbon mixture, and in dimethylbenzene, p-Xylol content is low, and cause the handled thing doses of Aromatic Hydrocarbon United Plant large, energy consumption is high.And the methane of by-product/ethane gas added value is low, is utilized very well.Methanol/dimethyl ether can be obtained by Coal Chemical Industry, will form supplementing of good aromatics production.But Coal Chemical Industry investment is large, and it is also a need problem to be processed that methyl alcohol and dimethyl ether produce relatively large waste water for aromatic hydrocarbons.
On the other hand, ethylene glycol can prepare oxyethane by oxidation of ethylene, then is hydrolyzed and obtains.Also can by the synthetic gas of Coal Chemical Industry, being separated directly by CO and H2, by CO catalytic coupling oxalic ester, then carries out the route of hydrogenation and obtains.Because ethylene process needs consumption two tons of oil to prepare one ton of ethylene glycol, so be that the potential economic advantages of the ethylene glycol technology of preparing of source material are large with coal, growth momentum is good.But as previously mentioned, producing ethylene glycol needs synthetic gas and huge water, electricity and the general facilities such as vapour and air separation, and investment great achievement is one of limiting element.And what produce in ethylene glycol process is high containing the complicated cost of alcohol wastewater treatment.Meanwhile, derive from can not directly discharging containing oxygen waste gas of CO catalytic coupling in ethylene glycol production link or the regeneration of nitrous ester, processing cost is high.
The liquefied gas (C3-C4 hydrocarbon) obtained by petroleum path, and the amount of the non-aromatic hydro carbons of C5-C9 is very large, economic worth is not high, can as the raw material preparing aromatic hydrocarbons.But current technology is while generation aromatic hydrocarbons, and aromatics yield is not too high, and the methane that inevitably generating portion hydrogen and utility value are not high and ethane, have impact on the economy of process.Meanwhile, at present not with liquefied gas and C5-C8 non-aromatics for raw material, the directly p-Xylol of equivalent of preparation production required for PET and the report of ethylene glycol.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of liquefied gas and C
5-C
9non-aromatic hydro carbons prepares the system and method for p-Xylol and ethylene glycol, can more highly selective by liquefied gas and C
5-C
9aromatic conversion is p-Xylol, and the methane of by-product is by ripe water vapor or oxidation conversion simultaneously, generates synthetic gas, providing raw material, considerably reducing the original plant investment producing ethylene glycol for producing ethylene glycol.
To achieve these goals, the technical solution used in the present invention is:
A kind of liquefied gas and C
5-C
9non-aromatic hydro carbons prepares the system of p-Xylol and ethylene glycol, comprising:
Aromizing subsystem 1, reacts wherein by oxygen-containing gas and reaction raw materials, generates hydrogen and C
1-C
12hydrocarbon mixture, reaction raw materials is liquefied gas and C
5-C
9in non-aromatic hydro carbons any one or with arbitrary proportion mixing multiple;
Gas-liquid separation subsystem 2, its entrance connects the pneumatic outlet of aromizing subsystem 1, and carry out gas-liquid separation, wherein gained liquefied gas is recycled to aromizing subsystem 1;
Aromatic hydrocarbons associating subsystem 3, its entrance connects the liquid exit of gas-liquid separation subsystem 2, carries out the synthesis of p-Xylol wherein;
Gas gas isolated subsystem 4, its entrance connects the pneumatic outlet of gas-liquid separation subsystem 2 and the pneumatic outlet of aromatic hydrocarbons associating subsystem 3, and carry out the separation of gas gas and obtain hydrogen, methane and ethane, wherein hydrogen outlet tieback is to aromatic hydrocarbons associating subsystem 3;
Synthetic gas prepares subsystem 5, and its entrance connects the methane outlet of oxygen-containing gas and gas gas isolated subsystem 4, generates carbon monoxide and hydrogen wherein, and wherein hydrogen outlet tieback is to aromatic hydrocarbons associating subsystem 3;
Subsystem 6 prepared by ethylene glycol, the hydrogen outlet that its entrance connects oxygen-containing gas, the hydrogen outlet of gas gas isolated subsystem 4, synthetic gas prepare subsystem 5 and synthetic gas prepare the carbon monoxide outlet of subsystem 5, carry out the preparation of ethylene glycol wherein, generate containing oxygen waste gas with containing alcohol waste water in process, wherein connect the gas inlet of aromizing subsystem 1 containing oxygen waste gas outlet, prepare the liquid inlet of subsystem 5 containing alcohol wastewater outlet connection synthetic gas.
Produce in described aromatic hydrocarbons associating subsystem 3 raffinate oil, benzene, unnecessary toluene and C
9-C
12hydrocarbon passes through impurities outlet tieback to aromizing subsystem 1.
Present invention also offers a kind of liquefied gas and C
5-C
9non-aromatic hydro carbons prepares the method for p-Xylol and ethylene glycol, comprises the steps:
By liquefied gas and C
5-C
9in non-aromatic hydro carbons any one or with arbitrary proportion mixing multiple pass in aromizing subsystem 1 react, pass into oxygen-containing gas in reaction process, reaction conditions is 500-600 DEG C, 0.1-1MPa, hydro carbons weight space velocity 0.1-30h
-1, one way feed stock conversion is 60-80%, generates hydrogen and C
1-C
12hydrocarbon mixture;
By hydrogen and C
1-C
12hydrocarbon mixture send into gas-liquid separation subsystem 2 and carry out gas-liquid separation, when there being liquefied gas in reaction raw materials, gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle, and gained liquid hydrocarbon passes into aromatic hydrocarbons associating subsystem 3;
Trimethylbenzene in liquid hydrocarbon and toluene are combined in subsystem 3 to react at aromatic hydrocarbons and are generated dimethylbenzene, all dimethylbenzene carries out isomerization conversion and is separated, obtain p-Xylol, the hydrogen produced in reaction process, methane and ethane mixed gas with go out the hydrogen of gas-liquid isolated subsystem 2, methane and ethane and merge, enter gas gas isolated subsystem 4;
In gas gas isolated subsystem 4, hydrogen, methane are separated with ethane, gained ethane is discharged, methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate carbon monoxide and hydrogen, carbon monoxide passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester; The hydrogen going out the hydrogen and gas isolated subsystem 4 of giving vent to anger that synthetic gas prepares subsystem 5 merges, and part passes into ethylene glycol and prepares for barkite hydrogenation generating glycol in subsystem 6, and part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Go out ethylene glycol prepare subsystem 6 containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration; Go out ethylene glycol prepare subsystem 6 containing alcohol waste water, pass into synthetic gas and prepare subsystem 5, be used as the part material of synthesis carbon monoxide and hydrogen.
The C generated in described aromizing subsystem 1
1-C
12hydrocarbon mixture in, p-Xylol accounts for the 35-65% of total hydrocarbon mixture quality, and p-Xylol accounts for the 85-93% of xylene mass.
The catalyzer based on micro-, nano molecular sieve and metal composite being applicable to methanol/dimethyl ether and preparing aromatic hydrocarbons is also added in described aromizing subsystem 1, the coated lid of described catalyst surface accounts for the silicon oxide layer of total catalyst weight 1-20%, load accounts for one or more in the caesium of total catalyst weight 0.01-2%, cerium, yttrium, ruthenium, lanthanum, iron and magnesium again, and load simultaneously accounts for potassium and/or the sodium of total catalyst weight 0.001-0.01%.
After described catalyst deactivation, logical oxygen-containing gas regeneration, regeneration temperature is 360-620 DEG C.
In described aromatic hydrocarbons associating subsystem 3 reaction process gained raffinate oil, benzene, unnecessary toluene and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle.
Obtain as follows based on the product of carbon back quality in described aromatic hydrocarbons associating subsystem 3: 2-5% hydrogen, 10-20% methane; 3-6% ethane, 70-80% p-Xylol.
Compared with prior art, the invention has the beneficial effects as follows:
1, catalyzer of the present invention than current existing liquefied gas through aromatization catalyzer or aromatization of gas catalyzer can more highly selective by liquefied gas and C
5-C
9be converted into p-Xylol.
2, aromizing subsystem combines the methane of subsystem by-product by ripe water vapor or oxidation conversion with aromatic hydrocarbons, generates synthetic gas, providing raw material, considerably reducing the original plant investment producing ethylene glycol for producing ethylene glycol.
3, liquefied gas and C
5-C
9generate the hydrogen of by-product during aromatic hydrocarbons, can be the barkite hydrogenation that ethylene glycol prepared in subsystem and hydrogen source is provided, alleviate synthetic gas and to prepare in subsystem CO by being transformed to H
2ratio, make the CO generated in process
2reduce 20-30%.
4, compared with preparing aromatic hydrocarbons technology with methyl alcohol/dimethanol, the hydrocarbon conversion is that aromatic hydrocarbons does not generate a large amount of waste water, avoids catalyzer and uses in the hot environment having water to exist for a long time, make catalyst life 30-45%.
5, prepared by generating glycol the catalyzer charcoal regeneration be directly used in containing oxygen waste gas in aromizing subsystem in subsystem, both saved gas flow and the conveying machinery load of the latter, and reduced again the former off gas treatment cost and be about 20-30%.
6, prepared by generating glycol the raw material preparing subsystem containing alcohol waste water for the synthesis of gas in subsystem, make cost for wastewater treatment reduce by 80%, the consumption making synthetic gas prepare the required fresh water of subsystem reduces 50-80%.
Accompanying drawing explanation
Fig. 1 is liquefied gas of the present invention and C
5-C
9non-aromatic hydro carbons prepares the system architecture schematic diagram of p-Xylol and ethylene glycol.
Embodiment
Embodiments of the present invention are described in detail below in conjunction with drawings and Examples.
Embodiment 1
As shown in Figure 1, to methanol/dimethyl ether will be applicable to prepare the commercial catalyst based on nano-ZSM-5 and Zn compound of aromatic hydrocarbons, the unbodied silicon oxide layer accounting for total catalyst weight 20% of coated with uniform, then load accounts for iron and 0.001% potassium of total catalyst weight 0.01%.At 560 DEG C, under the condition of pressure 0.4MPa (gauge pressure), in aromizing subsystem 1, transform liquefied gas, wherein, in liquefied gas, the massfraction of propane, propylene, butane, butylene is respectively 35%, and 16%, 30%, 19%, aromizing subsystem 1 can use fluidized-bed reactor.Be 6h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 75%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 93% of xylene mass, and p-Xylol accounts for 46% of total hydrocarbon mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: the hydrogen of 2%, the methane of 20%; The ethane of 6%, the p-Xylol of 72%.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 620 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 2
As shown in Figure 1, by be applicable to methanol/dimethyl ether prepare aromatic hydrocarbons based on micron ZSM-5 and Ag, the commercial catalyst of Mo, the unbodied silicon oxide layer accounting for total catalyst weight 16% of coated with uniform, then load account for the lanthanum of total catalyst weight 0.8%, the cerium of 0.25% and 0.1% potassium.At 500 DEG C, under the condition of pressure 0.5MPa (gauge pressure), transform liquefied gas and C at aromizing subsystem 1 (use fluidized-bed reactor)
5-C
9non-aromatic hydro carbons, wherein C
3, C
4, C
5, C
6, C
7, C
8, C
9the massfraction of component is respectively 20%, and 20%, 25%, 10%, 10%, 8%, 7%; Be 0.4h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 70%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 90% of xylene mass, and p-Xylol accounts for 65% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: the hydrogen of 5%, the methane of 10%; The ethane of 5%, the p-Xylol of 80%.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 360 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 3
As shown in Figure 1, by be applicable to methanol/dimethyl ether prepare aromatic hydrocarbons based on nano-ZSM-5 and Cu, the commercial catalyst of Mo compound, the silicon oxide layer accounting for total catalyst weight 13% of coated with uniform lid crystalline form, load accounts for the ruthenium of total catalyst weight 0.5%, the magnesium of 1.5% again, the potassium of 0.001% and the sodium of 0.01%, form raw catalyst.At 500 DEG C, under the condition of pressure 0.1MPa (gauge pressure), at aromizing subsystem 1 (use fluidized-bed reactor) converting propylene and butylene (massfraction is respectively 60% and 40%); Be 30h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 75%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 92% of xylene mass, and p-Xylol accounts for 61% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: 2% hydrogen, 16% methane; 4% ethane, 78% p-Xylol.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 540 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 4
As shown in Figure 1, by be applicable to methanol/dimethyl ether prepare aromatic hydrocarbons based on nanometer ZSM-11 and Ga, the commercial catalyst of Mn compound, the unbodied silicon oxide layer accounting for total catalyst weight 1% of coated with uniform lid, load accounts for the cerium of total catalyst weight 0.01% again, the lanthanum of 1%, the potassium of 0.005% and the sodium of 0.005%, form new catalyzer.At 560 DEG C, under the condition of pressure 0.7MPa (gauge pressure), transform C at aromizing subsystem 1 (use moving-burden bed reactor)
5-C
8non-aromatic hydro carbons (C
5, C
6, C
7, C
8the massfraction of non-aromatic hydro carbons is respectively 65%, and 15%, 14%, 6%); Be 10h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 60%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 85% of xylene mass, and p-Xylol accounts for 50% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: 4% hydrogen, 16% methane; 6% ethane, 76% p-Xylol.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 600 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 5
As shown in Figure 1, to methanol/dimethyl ether will be applicable to prepare the commercial catalyst based on micron ZSM-11 and Zn compound of aromatic hydrocarbons, the unbodied silicon oxide layer accounting for total catalyst weight 15% of coated with uniform lid, load accounts for the caesium of total catalyst weight 0.5% again, the lanthanum of 1%, the potassium of 0.05% and the sodium of 0.005%, form new catalyzer.At 600 DEG C, under the condition of pressure 0.4MPa (gauge pressure), at aromizing subsystem 1 (use fluidized-bed reactor) Conversion of Propane; Be 2h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 73%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 85% of xylene mass, and p-Xylol accounts for 35% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: 2% hydrogen, 20% methane; 6% ethane, 72% p-Xylol.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 620 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 6
As shown in Figure 1, by be applicable to methanol/dimethyl ether prepare aromatic hydrocarbons based on nano-ZSM-5 and Zn, the commercial catalyst of Cu compound, the unbodied silicon oxide layer accounting for total catalyst weight 10% of coated with uniform lid, again load account for total catalyst weight 0.1% iron with 0.2% lanthanum, the ruthenium of 0.01%, the cerium of 0.02% and 0.1% sodium, form new catalyzer.At 530 DEG C, under the condition of pressure 0.2MPa (gauge pressure), transform C at aromizing subsystem 1 (use moving-burden bed reactor)
7-C
9non-aromatic hydro carbons (C
7, C
8, C
9massfraction be respectively 30%, 20%, 50%); Be 3h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 75%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 88% of xylene mass, and p-Xylol accounts for 55% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: the hydrogen of 3%, the methane of 14%; The ethane of 3%, the p-Xylol of 80%.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 360 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 7
As shown in Figure 1, to methanol/dimethyl ether will be applicable to prepare the commercial catalyst based on nano-ZSM-5 and Cu compound of aromatic hydrocarbons, the unbodied silicon oxide layer accounting for total catalyst weight 1% of coated with uniform lid, load accounts for the caesium of total catalyst weight 0.05%, ruthenium, the cerium of 0.01%, the lanthanum of 0.3% of 0.01% again, the magnesium of 1.6% and the potassium of 0.002% or 0.001% sodium, form new catalyzer.At 530 DEG C, under the condition of pressure 0.8MPa (gauge pressure), transform C at aromizing subsystem 1 (use moving-burden bed reactor)
6non-aromatic hydro carbons; Be 30h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 60%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 85% of xylene mass, and p-Xylol accounts for 50% of quality in THC mixture.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: the hydrogen of 5%, 13% methane; 3% ethane, 79% p-Xylol.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 400 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 8
As shown in Figure 1, to methanol/dimethyl ether will be applicable to prepare the commercial catalyst based on micron ZSM-5 and Pt compound of aromatic hydrocarbons, coated with uniform lid accounts for the crystalline form silicon oxide layer of total catalyst weight 2%, load accounts for the cerium of total catalyst weight 0.1% again, the lanthanum of 0.2%, the iron of 1% and the sodium of 0.001%, form new catalyzer.At 520 DEG C, under the condition of pressure 1MPa (gauge pressure), transform C at aromizing subsystem 1 (use fixed-bed reactor)
7non-aromatic hydro carbons; Be 5h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 69%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 85% of xylene mass, and p-Xylol accounts for 40% of THC mixture weight.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: the hydrogen of 2-5%, the methane of 10-20%; The ethane of 3-6%, the p-Xylol of 70-80%.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 620 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the medium of partially catalyzed agent regeneration, (catalyst regeneration temperature is 360-650
dEG C).Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 9
As shown in Figure 1, by be applicable to methanol/dimethyl ether prepare aromatic hydrocarbons based on nano-ZSM-5 and Zn, Ga, the commercial catalyst of Cu compound, coated with uniform accounts for the pure silicon oxygen molecule screen layers of total catalyst weight 20%, load accounts for the cerium of total catalyst weight 0.001% and the potassium of 0.001% again, forms new catalyzer.At 550 DEG C, under the condition of pressure 0.8MPa (gauge pressure), transform C at aromizing subsystem 1 (use fixed-bed reactor)
8non-aromatic hydro carbons; Be 0.5h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 75%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 89% of xylene mass, and p-Xylol accounts for 48% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: the hydrogen of 3%, the methane of 19%; The ethane of 6%, the p-Xylol of 72%.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 450 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 10
As shown in Figure 1, to methanol/dimethyl ether will be applicable to prepare the commercial catalyst based on nano-ZSM-5 and Zn, Cu compound of aromatic hydrocarbons, the unbodied silicon oxide layer accounting for total catalyst weight 10% of coated with uniform lid, load accounts for lanthanum, the caesium of 0.1%, ruthenium, the yttrium of 0.1%, the cerium of 0.1% of 0.1% of total catalyst weight 0.1% again, the iron of 1%, the magnesium of 0.5%, the potassium of 0.001% and the sodium of 0.01%, form new catalyzer.At 580 DEG C, under the condition of pressure 0.4MPa (gauge pressure), transform C at aromizing subsystem 1 (use fixed-bed reactor)
5non-aromatic hydro carbons; Be 12h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 74%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 90% of xylene mass, and p-Xylol accounts for 45% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: the hydrogen of 4%, the methane of 15%; The ethane of 4%, the p-Xylol of 77%.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 450 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 11
As shown in Figure 1, to methanol/dimethyl ether will be applicable to prepare the commercial catalyst based on nano-ZSM-5 and Ag, Cu compound of aromatic hydrocarbons, the unbodied silicon oxide layer accounting for total catalyst weight 2% of coated with uniform lid, load accounts for the yttrium of total catalyst weight 0.01%, the cerium of 0.4% again, the iron of 0.2%, the magnesium of 0.5% and the potassium of 0.01%, form new catalyzer.At 510 DEG C, under the condition of pressure 0.6MPa (gauge pressure), transform C at aromizing subsystem 1 (use fixed-bed reactor)
4hydrocarbon (by massfraction be respectively 65% and 35% butane and butylene form); Be 7h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 75%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 88% of xylene mass, and p-Xylol accounts for 57% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: 5% hydrogen, 15% methane; 5% ethane, 75% p-Xylol.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 360 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Embodiment 12
As shown in Figure 1, to methanol/dimethyl ether will be applicable to prepare the commercial catalyst based on nano-ZSM-5 and Mn, Cu compound of aromatic hydrocarbons, the unbodied silicon oxide layer accounting for total catalyst weight 12% of coated with uniform lid, load accounts for the yttrium of total catalyst weight 0.05%, the cerium of 0.5% again, the iron of 1%, the magnesium of 0.25% and the sodium of 0.01%, form new catalyzer.At 570 DEG C, under the condition of pressure 1MPa (gauge pressure), transform C at aromizing subsystem 1 (use moving-burden bed reactor)
9non-aromatic hydro carbons; Be 4h at the weight space velocity of hydro carbons
-1condition under, the per pass conversion of raw material is 68%; Generate hydrogen and C
1-C
12hydrocarbon mixture, wherein p-Xylol accounts for 89% of xylene mass, and p-Xylol accounts for 57% of THC mixture quality.
The product gas exported by above-mentioned aromizing subsystem 1 is through gas-liquid separation subsystem 2, and gained liquefied gas returns aromizing subsystem 1 and carries out conversion and cycle; The liquid hydrocarbon that gas-liquid separation subsystem 2 exports passes into aromatic hydrocarbons associating subsystem 3, and wherein trimethylbenzene reacts with the toluene of metering ratio and generates dimethylbenzene, and all dimethylbenzene carries out isomerization conversion and is separated, obtain last para-xylene product after merging.Process gained is raffinated oil, benzene, unnecessary toluene, and C
9-C
12hydrocarbon returns aromizing subsystem 1 and carries out conversion and cycle; The hydrogen that aromatic hydrocarbons associating subsystem 3 exports and hydrogen, methane and ethane that methane/ethane mixed gas and gas-liquid separation subsystem 2 export merge, and enter gas gas isolated subsystem 4.Above-mentioned conversion process, clean generation is as follows based on the product of carbon back quality: 4% hydrogen, 16% methane; 6% ethane, 74% p-Xylol.After catalyst deactivation in aromizing subsystem 1, logical oxygen-containing gas regeneration, temperature is 620 DEG C.
Hydrogen, methane and ethane gas mixture are after gas gas isolated subsystem 3, and gained ethane discharges system, and it is used.Gained methane passes into synthetic gas and prepares subsystem 5, with oxygen-containing gas and derive from ethanol prepare subsystem 6 containing alcohol waste water reaction, generate CO and H
2, and obtain pure CO through being separated further.CO passes into ethylene glycol and prepares subsystem 6, carries out catalytic coupling with oxygen-containing gas, oxalic ester.Synthetic gas is prepared the hydrogen that hydrogen and gas gas isolated subsystem 4 that subsystem 5 exports export and is merged, and partly passes into ethylene glycol and prepares in subsystem 6 for barkite hydrogenation generating glycol.Part passes into aromatic hydrocarbons associating subsystem 3 and is used as process gas.
Ethylene glycol prepare that subsystem 6 exports containing oxygen waste gas, pass into aromizing subsystem 1, as the certain media of catalyst regeneration.Second two prepares the part material preparing subsystem 5 containing alcohol waste water as synthetic gas that subsystem 6 exports.Oxygen-containing gas is used separately as the medium of aromizing subsystem 1 catalyst regeneration, and ethylene glycol is prepared the raw material of CO catalytic coupling and nitrous acid ester regeneration in subsystem 6 and synthetic gas and prepared part material in subsystem 5.
Claims (8)
1. a liquefied gas and C
5-C
9non-aromatic hydro carbons prepares the system of p-Xylol and ethylene glycol, it is characterized in that, comprising:
Aromizing subsystem (1), reacts wherein by oxygen-containing gas and reaction raw materials, generates hydrogen and C
1-C
12hydrocarbon mixture, reaction raw materials is liquefied gas and C
5-C
9in non-aromatic hydro carbons any one or with arbitrary proportion mixing multiple;
Gas-liquid separation subsystem (2), its entrance connects the pneumatic outlet of aromizing subsystem (1), and carry out gas-liquid separation, wherein gained liquefied gas is recycled to aromizing subsystem (1);
Aromatic hydrocarbons associating subsystem (3), its entrance connects the liquid exit of gas-liquid separation subsystem (2), carries out the synthesis of p-Xylol wherein;
Gas gas isolated subsystem (4), its entrance connects the pneumatic outlet of gas-liquid separation subsystem (2) and the pneumatic outlet of aromatic hydrocarbons associating subsystem (3), carry out the separation of gas gas and obtain hydrogen, methane and ethane, wherein hydrogen outlet tieback to aromatic hydrocarbons combines subsystem (3);
Synthetic gas prepares subsystem (5), and its entrance connects the methane outlet of oxygen-containing gas and gas gas isolated subsystem (4), and generate carbon monoxide and hydrogen wherein, wherein hydrogen outlet tieback to aromatic hydrocarbons combines subsystem (3);
Subsystem (6) prepared by ethylene glycol, the hydrogen outlet that its entrance connects oxygen-containing gas, the hydrogen outlet of gas gas isolated subsystem (4), synthetic gas prepare subsystem (5) and synthetic gas prepare the carbon monoxide outlet of subsystem (5), carry out the preparation of ethylene glycol wherein, generate containing oxygen waste gas with containing alcohol waste water in process, wherein connect the gas inlet of aromizing subsystem (1) containing oxygen waste gas outlet, prepare the liquid inlet of subsystem (5) containing alcohol wastewater outlet connection synthetic gas.
2. liquefied gas and C according to claim 1
5-C
9non-aromatic hydro carbons prepares the system of p-Xylol and ethylene glycol, it is characterized in that, produce in described aromatic hydrocarbons associating subsystem (3) raffinate oil, benzene, unnecessary toluene and C
9-C
12hydrocarbon passes through impurities outlet tieback to aromizing subsystem (1).
3. a liquefied gas and C
5-C
9non-aromatic hydro carbons prepares the method for p-Xylol and ethylene glycol, it is characterized in that, comprises the steps:
By liquefied gas and C
5-C
9in non-aromatic hydro carbons any one or multiplely pass in aromizing subsystem (1) with arbitrary proportion mixing, also add in aromizing subsystem (1) be applicable to methanol/dimethyl ether prepare aromatic hydrocarbons based on micro-, the catalyzer of nano molecular sieve and metal composite, the coated lid of described catalyst surface accounts for the silicon oxide layer of total catalyst weight 1-20%, load accounts for the caesium of total catalyst weight 0.01-2% again, cerium, yttrium, ruthenium, lanthanum, one or more in iron and magnesium, load simultaneously accounts for potassium and/or the sodium of total catalyst weight 0.001-0.01%, oxygen-containing gas is passed in reaction process, reaction conditions is 500-600 DEG C, 0.1-1MPa, hydro carbons weight space velocity 0.1-30h
-1, one way feed stock conversion is 60-80%, generates hydrogen and C
1-C
12hydrocarbon mixture,
By hydrogen and C
1-C
12hydrocarbon mixture send into gas-liquid separation subsystem (2) carry out gas-liquid separation, when there being liquefied gas in reaction raw materials, gained liquefied gas returns aromizing subsystem (1) and carries out conversion and cycle, and gained liquid hydrocarbon passes into aromatic hydrocarbons associating subsystem (3);
Trimethylbenzene in liquid hydrocarbon and toluene react and generate dimethylbenzene in aromatic hydrocarbons combines subsystem (3), all dimethylbenzene carries out isomerization conversion and is separated, obtain p-Xylol, the hydrogen produced in reaction process, methane and ethane mixed gas with go out the hydrogen of gas-liquid isolated subsystem (2), methane and ethane and merge, enter gas gas isolated subsystem (4);
In gas gas isolated subsystem (4), hydrogen, methane are separated with ethane, gained ethane is discharged, methane passes into synthetic gas and prepares subsystem (5), with oxygen-containing gas and derive from ethylene glycol prepare subsystem (6) containing alcohol waste water reaction, generate carbon monoxide and hydrogen, carbon monoxide passes into ethylene glycol and prepares subsystem (6), carries out catalytic coupling, oxalic ester with oxygen-containing gas; The hydrogen going out the hydrogen and gas isolated subsystem (4) of giving vent to anger that synthetic gas prepares subsystem (5) merges, part passes into ethylene glycol and prepares for barkite hydrogenation generating glycol in subsystem (6), and part passes into aromatic hydrocarbons associating subsystem (3) as process gas.
4. liquefied gas and C according to claim 3
5-C
9non-aromatic hydro carbons prepares the method for p-Xylol and ethylene glycol, it is characterized in that, go out ethylene glycol prepare subsystem (6) containing oxygen waste gas, pass into aromizing subsystem (1), as the certain media of catalyst regeneration; Go out ethylene glycol prepare subsystem (6) containing alcohol waste water, pass into synthetic gas and prepare subsystem (5), be used as the part material of synthesis carbon monoxide and hydrogen.
5. liquefied gas and C according to claim 3
5-C
9non-aromatic hydro carbons prepares the method for p-Xylol and ethylene glycol, it is characterized in that, the C generated in described aromizing subsystem (1)
1-C
12hydrocarbon mixture in, p-Xylol accounts for the 35-65% of total hydrocarbon mixture quality, and p-Xylol accounts for the 85-93% of xylene mass.
6. liquefied gas and C according to claim 3
5-C
9non-aromatic hydro carbons prepares the method for p-Xylol and ethylene glycol, it is characterized in that, after described catalyst deactivation, logical oxygen-containing gas regeneration, regeneration temperature is 360-620 DEG C.
7. liquefied gas and C according to claim 3
5-C
9non-aromatic hydro carbons prepares the method for p-Xylol and ethylene glycol, it is characterized in that, the middle reaction process gained of described aromatic hydrocarbons associating subsystem (3) is raffinated oil, benzene, unnecessary toluene and C
9-C
12hydrocarbon returns aromizing subsystem (1) and carries out conversion and cycle.
8. liquefied gas and C according to claim 3
5-C
9non-aromatic hydro carbons prepares the method for p-Xylol and ethylene glycol, it is characterized in that, obtains as follows based on the product of carbon back quality: 2-5% hydrogen, 10-20% methane in described aromatic hydrocarbons associating subsystem (3); 3-6% ethane, 70-80% p-Xylol.
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| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| CN102134178A (en) * | 2011-01-21 | 2011-07-27 | 清华大学 | Device and method for preparing ethylbenzene by catalytic conversion of alcohol ether |
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| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| CN102134178A (en) * | 2011-01-21 | 2011-07-27 | 清华大学 | Device and method for preparing ethylbenzene by catalytic conversion of alcohol ether |
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| Title |
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| 中国石化煤化工技术最新进展;陈庆龄等;《催化学报》;20130120;第34卷(第1期);第217-224页 * |
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