CN100358848C - Method of heavy arene hydrogenation dealkylation and alkylation transfer - Google Patents
Method of heavy arene hydrogenation dealkylation and alkylation transfer Download PDFInfo
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- CN100358848C CN100358848C CNB2004100666254A CN200410066625A CN100358848C CN 100358848 C CN100358848 C CN 100358848C CN B2004100666254 A CNB2004100666254 A CN B2004100666254A CN 200410066625 A CN200410066625 A CN 200410066625A CN 100358848 C CN100358848 C CN 100358848C
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- reaction
- transalkylation
- aromatic hydrocarbons
- raw material
- zeolite
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Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006900 dealkylation reaction Methods 0.000 title claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 14
- 238000005804 alkylation reaction Methods 0.000 title claims description 12
- 230000020335 dealkylation Effects 0.000 title abstract 2
- 230000029936 alkylation Effects 0.000 title 1
- 238000010555 transalkylation reaction Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 34
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 239000010457 zeolite Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008096 xylene Substances 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 54
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052680 mordenite Inorganic materials 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- -1 after separating Natural products 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 8
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 8
- 238000007323 disproportionation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 4
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for the dealkylation and the transalkylation of heavyweight aromatic hydrocarbon by hydrogenation, which mainly solves problems existing in the prior art that the permitted content of the heavyweight aromatic hydrocarbon in raw materials is low, and the utilization rate of the heavyweight aromatic hydrocarbon is low. The present invention solves the problems by adopting the technical scheme that the aromatic hydrocarbon of C10 or/and C11 is used as a raw material, and mixed xylene is generated by a reaction by using a catalyst of macropore zeolite on which the metals or the oxides of bismuth and molybdenum are loaded, and the reaction is carried out in a fixed bed reactor under the conditions of the temperature of 300 to 600 DEG C and the pressure of 1.0 to 4.0MPa. The method has the characteristics of simple procedure, high yield of the mixed xylene, low hydrogen/hydrocarbon ratio, etc., and the present invention can be used for the industrial production of the mixed xylene by using the heavyweight aromatic hydrocarbon.
Description
Technical field
The present invention relates to the method that heavy arene hydrogenation takes off alkyl and transalkylation, particularly take off the method that alkyl and transalkylation are produced Mixed XYLENE about carbon ten and above aromatic hydrogenation thereof.
Background technology
Past people is usually C
9A, C
10A and C
10Above aromatic hydrocarbons is referred to as heavy aromatics.Petroleum Aromatics is mainly derived from the byproduct that light oil cracking is produced ethylene unit; The extracting aromatic hydrocarbons of refinery catalytic reforming; The byproduct of toluene disproportionation and transalkylation unit.Comprehensive Utilization of Heavy Aromatics is the problem that people are concerned about, C
9The processing and utilization of A has sophisticated method, is widely used as the raw material of toluene disproportionation and transalkylation reaction, is used for making benzene and dimethylbenzene.Just because of this, in present Aromatic Hydrocarbon United Plant, do not comprised C in used " heavy aromatics " term
9A, but refer in particular to C
10A and C
10Above aromatic hydrocarbons, " heavy aromatics " in this patent is meant C
10A and C
10Above aromatic hydrocarbons.At present, the by product C of Aromatic Hydrocarbon United Plant
10The composition complexity of A fraction is except that C such as first and second benzene that contain 5～20% (weight), trimethylbenzenes
9Outside A and the indane, also contain tens kinds of C
10A and C
10Above component is as durene, dimethyl ethyl benzene, diethylbenzene, methylnaphthalene, dimethylnaphthalene etc.Heavy aromatics is complicated owing to forming, the boiling point height, and purposes is less at present.These components are all improper as the blend composition of gasoline or diesel oil, and only some is as solvent oil, and a part is used to tell durol wherein, and all the other major parts act as a fuel and burn, real genus waste.Aromatic Hydrocarbon United Plant of producing 22.5 ten thousand tons of p-Xylol per year according to estimates, and since the difference of stock oil, the difference of the course of processing, the annual heavy aromatics that produces is 1～30,000 ton, this is a kind of resource of preciousness, and present Aromatic Hydrocarbon United Plant is to C
10A fraction heavy aromatics does not also have suitable treatment process.
In the public clear 51-29131 patent of spy, use MoO
3-NiO/Al
2O
3(13wt%Mo, 5wt%Ni) catalyzer is with C
9A-C
10A (benzene 0.81%, toluene 0.26%, C
8A 0.95%, C
9A 80.96%, C
10A 15.23%) be raw material, under 6MPa and 550 ℃ of reaction conditionss, during reaction product is formed by weight percentage for containing benzene 9.74%, toluene 30.27%, dimethylbenzene 32.33% and non-aromatics 0.16%.In U.S. Pat P4172813, with 3%WO
3, 5%MoO
3-60% mordenite-40% Al
2O
3Be catalyzer, make heavy reformation liquid that hydro-dealkylation and transalkylation reaction take place to select.Its temperature of reaction is 315～538 ℃, and reaction pressure is 150～500Psig, and reaction raw materials contains non-aromatics 0.5%, C
8A 0.4%, toluene 28.3%, and trimethylbenzene 46.6%, the first and second benzene 11.6%, indane adds propyl benzene 2.1%, durene 10.1%, C
10Above aromatic hydrocarbons 0.4%.Only contain C in the raw material
10A 10.1%, contains 28.3% toluene again, 46.6% trimethylbenzene, and therefore topmost reaction is the transalkylation of toluene and trimethylbenzene.Narrated a kind of among the U.S. Pat P4341914 from C
9A or C
7A and C
9The A transalkylation is produced C
8The method of A, the C that tells from the transalkylation reaction effluent
9A, C
10The A circulation is passed through C as the raw material of transalkylation
10The circulation generation transalkylation reaction of A and benzene has improved C
8The output of A.
In above-mentioned document, advance C in the raw material of reactor
10A and C
10The content of above aromatic hydrocarbons is lower, is no more than 20% at most, and topmost reaction still is toluene and C
9The toluene disproportionation of A and transalkylation reaction.
Heavy aromatics, particularly C
10A and C thereof
11The heavy aromatics that A is above, no matter in toluene disproportionation and transalkylation reaction process, perhaps in the hydro-dealkylation reaction process, also follow hydrocracking reaction generation carbon and stable hydrocarbon take place, the aromatic hydrocarbons condensation reaction generates side reactions such as many rings or fused ring compound, and temperature of reaction is high more, side reaction is big more, the macromole condensation product the more, the catalyzer coking also the more, catalyst activity reduction must heal soon.C
10Contain polynuclear compounds such as micro-naphthalene, methylnaphthalene, dimethylnaphthalene in the A fraction, they make catalyst deactivation easily.Therefore, in toluene disproportionation and alkyl transfering process, for slowing down catalyst carbon deposition speed, prolong catalyst life, except that the hydrogen operation was faced in employing, aspect the raw material composition, general requirement was advanced reactor feedstocks C
10A content is no more than 4%, is no more than 8% at most.Indane is the poisonous substance of catalyst for toluene disproportionation and transalkylation, is controlled at below 0.5% usually.
Summary of the invention
Technical problem to be solved by this invention is to allow heavy arene content lower in the raw material that exists in the above-mentioned document, and the problem that the heavy arene utilization ratio is low provides a kind of new heavy arene hydrogenation to take off the method for alkyl and transalkylation.This method has hydro-dealkylation and the transalkylation that is suitable for heavy arene, reaches the characteristics that make full use of heavy arene.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of heavy arene hydrogenation takes off the method for alkyl and transalkylation, with C
10And above aromatic hydrocarbons is that raw material carries out hydro-dealkylation and transalkylation reaction, generates C
6～C
9Aromatic hydrocarbons and C
1～C
4Paraffinic hydrocarbon, after separating, dimethylbenzene is as the product extraction, wherein:
A) raw material C
10And above aromatic hydrocarbons contacts with catalyzer by fixed-bed reactor, and temperature of reaction is 300～600 ℃, and reaction pressure is 1.0～4.0MPa, and the raw material weight air speed is 0.5～5.0 hour
-1, hydrogen/hydrocarbon mol ratio is 1～10;
B) used catalyzer contains SiO in parts by weight
2/ Al
2O
3Mol ratio is 20～90 parts of 10～50 Hydrogen large pore zeolites, on h-type zeolite load 0.05～10 part of bismuth or its oxide compound, 0.05～5 part of the oxide compound of molybdenum, and 0～5 part of at least a chosen from Fe, cobalt, nickel or its oxide compound, the binding agent aluminum oxide is 10～60 parts in catalyzer;
C) reaction product is through the isolated C of deheptanizer
7And the C of following hydrocarbon and dimethylbenzene Tata still
9And above aromatic hydrocarbons is circulated in the reaction feed.
C in the technique scheme
6～C
9Aromatic hydrocarbons is that benzene,toluene,xylene, ethylbenzene, first and second benzene are or/and trimethylbenzene.The present invention adopts bismuth-containing and contains the macro-porous zeolite catalyst of at least a promotor in molybdenum and chosen from Fe, cobalt or the nickel, and the large pore zeolite preferred version that uses is mordenite, β zeolite or omega zeolite, and more preferably scheme is selected from the β zeolite.React employed raw material C
10And the indane weight content is 0～5% in the above aromatic hydrocarbons.The catalyzer that uses in the inventive method has good heavy aromatics hydro-dealkylation function, has good heavy aromatics and benzene, toluene transalkylation function simultaneously.
C
10And the principal reaction that above aromatic hydrogenation takes off alkyl has:
C
6H(CH
3)
5+H
2→C
6H
2(CH
3)
4+CH
4 (1)
C
6H
2(CH
3)
4+H
2→C
6H
3(CH
3)
3+CH
4 (2)
C
6H
3(CH
3)
3+H
2→C
6H
4(CH
3)
2+CH
4 (3)
C
6H
4(CH
3)
2+H
2→C
6H
5CH
3+CH
4 (4)
C
6H
5CH
3+H
2→C
6H
6+CH
4 (5)
C
2H
5-C
6H
3-(CH
3)
2+H
2→C
6H
4(CH
3)
2+C
2H
6 (6)
Between benzene, toluene and the trimethylbenzene that above-mentioned reaction generates, benzene, toluene and C
10Transalkylation reaction between the A mainly contains:
C
6H
6+C
6H
3(CH
3)
3→C
6H
5CH
3+C
6H
4(CH
3)
2 (7)
C
6H
5CH
3+C
6H
3(CH
3)
3→2C
6H
5(CH
3)
2 (8)
C
6H
6+C
6H
2(CH
3)
4→C
6H
5CH
3+C
6H
3(CH
3)
3 (9)
C
6H
5CH
3+C
6H
2(CH
3)
4→C
6H
4(CH
3)
2+C
6H
3(CH
3)
3 (10)
Preparation of Catalyst in the technology of the present invention can obtain by common mechanically mixing or kneading method.
The cheap C of the present invention
10And above aromatic hydrocarbons, by hydro-dealkylation and transalkylation reaction, be converted into the C of higher-value
6A～C
9The more rudimentary aromatic hydrocarbons of A.The C that the following non-aromatics of benzene, toluene and C7 that generates generates with reaction after deheptanizer separates
9A, unreacted C
10And above aromatic hydrocarbons is circulated in the reaction feed, has only Mixed XYLENE in the reaction effluent as the product extraction.Therefore, the present invention is a comprehensive utilization of C
10And above aromatic hydrocarbons, produce Mixed XYLENE C
8The effective ways of A have been obtained better technical effect.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
1 is the raw hydrogen, the C that out-of-bounds come among the figure10And above heavy aromatics, 2 is heavy aromatics hydro-dealkylation of the present invention and transalkylation reaction unit, and 3 is deheptanizer, and 4 is benzenol hydrorefining, 5 C for circulation7And following hydrocarbon, 6 is C8And above hydrocarbon, 7 are the product Mixed XYLENE of technology of the present invention, i.e. C8Aromatic hydrocarbons, 8 is C9And above aromatic hydrocarbons, 9 is C11 +Hydrocarbon. From hydrogen and the C that out-of-bounds comes10And isolated C in above heavy aromatics 1 and the reaction effluent7And following hydrocarbon and C9And above hydrocarbon enters transalkylation of the present invention unit 2 after mixing and carries out heavy aromatics hydro-dealkylation and transalkylation reaction, generates Mixed XYLENE, and reaction effluent separates through deheptanizer, the isolated C of cat head7And following hydrocarbon 5 is circulated in the reaction feed, and extraction is rich in C at the bottom of the tower8 +Benzenol hydrorefining 4 is advanced in A logistics 6, the Mixed XYLENE logistics 7 of overhead extraction, and C is rich in the extraction of tower reactor side line9A logistics 8 is circulated in the reaction feed, and the benzenol hydrorefining tower reactor can extraction or not extraction C11 +Hydrocarbon.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Na
2The O weight content less than 0.15%, SiO
2/ Al
2O
3Ammonium type mordenite powder 77.8 grams of 12,550 ℃ of calcination losses 10% of mol ratio are with Na
2The O weight content less than 0.15%, the pseudo-boehmite (α-Al of calcination loss 30%
2O
3H
2O) 42.9 grams mix.With chemical pure Bismuth trinitrate [Bi (NO
3)
35H
2O] 0.50 gram, 2 milliliters in chemical pure nitric acid, 60 milliliters in water, chemical pure ammonium molybdate [(NH
4)
6Mo
7O
24] 5.77 grams are made into mixing solutions.This mixing solutions is added in the mixture of ammonium type mordenite and pseudo-boehmite, thorough mixing, kneading are evenly carried out extruded moulding, oven dry, pelletizing, calcination activation, make weight ratio and are: Bi
2O
3/ MoO
3The catalyst A of/h-mordenite/aluminum oxide=0.25/5/70/30.
[embodiment 2]
Na
2The O weight content less than 0.15%, SiO
2/ Al
2O
3Ammonium type mordenite powder 77.8 grams of 28,550 ℃ of calcination losses 10% of mol ratio are with Na
2The O weight content less than 0.15%, the pseudo-boehmite (α-Al of calcination loss 30%
2O
3H
2O) 42.9 grams mix.With chemical pure Bismuth trinitrate [Bi (NO
3)
35H
2O] 5.0 grams, 2 milliliters in chemical pure nitric acid, 60 milliliters in water, chemical pure ammonium molybdate [(NH
4)
6Mo
7O
24] 0.58 gram is made into mixing solutions.This mixing solutions is added in the mixture of ammonium type mordenite and pseudo-boehmite, thorough mixing, kneading are evenly carried out extruded moulding, oven dry, pelletizing, calcination activation, make weight ratio and are: Bi
2O
3/ MoO
3The catalyst B of/h-mordenite/aluminum oxide=2.5/0.5/70/30.
[embodiment 3]
Na
2The O weight content less than 0.25%, SiO
2/ Al
2O
3Ammonium type β zeolite powder 44.4 gram and the Na of 38,550 ℃ of calcination losses 10% of mol ratio
2The O weight content less than 0.15%, pseudo-boehmite 85.7 grams of calcination loss 30% mix.With chemical pure Bismuth trinitrate [Bi (NO
3)
35H
2O] 0.7 the gram, chemical pure ammonium molybdate [(NH
4)
6Mo
7O
24] 5.8 the gram, chemical pure nickelous nitrate [Ni (NO
3)
26H
2O] 1.9 grams, 1.5 milliliters in chemical pure nitric acid, water are mixed with mixing solutions for 60 milliliters.This solution is added in the mixture of ammonium type mordenite and pseudo-boehmite, thorough mixing, kneading are evenly carried out extruded moulding, oven dry, pelletizing, calcination activation, make weight ratio and are: Bi
2O
3/ MoO
3The catalyzer C of/NiO/ Hydrogen β Zeolite/alumina=0.35/5.0/0.5/40/60.
[embodiment 4]
Na
2The O weight content less than 0.25%, SiO
2/ Al
2O
3Ammonium type β zeolite powder 44.4 gram and the Na of 21,550 ℃ of calcination losses 10% of mol ratio
2The O weight content less than 0.15%, pseudo-boehmite 85.7 grams of calcination loss 30% mix.With chemical pure Bismuth trinitrate [Bi (NO
3)
35H
2O] 0.7 the gram, chemical pure ammonium molybdate [(NH
4)
6Mo
7O
24] 5.8 the gram, chemical pure nickelous nitrate [Ni (NO
3)
26H
2O] 1.9 grams, 1.5 milliliters in chemical pure nitric acid, water are mixed with mixing solutions for 60 milliliters.This solution is added in the mixture of ammonium type mordenite and pseudo-boehmite, thorough mixing, kneading are evenly carried out extruded moulding, oven dry, pelletizing, calcination activation, make weight ratio and are: Bi
2O
3/ MoO
3The catalyzer D of/NiO/ Hydrogen β Zeolite/alumina=0.35/5.O/0.5/40/60.
[embodiment 5]
Raw material C
10And above aromatic hydrocarbons derives from the petrochemical complex Aromatic Hydrocarbon United Plant, contains first and second benzene, trimethylbenzene, indane, diethylbenzene, dimethyl ethylbenzene, durene, other C
10A and C
11And above heavy aromatics etc., raw material is formed as table 1.
Table 1 raw material C
10And above heavy aromatics is formed weight %
| Title | First and second benzene | Trimethylbenzene | Indane | Diethylbenzene | Dimethylbenzene ethylbenzene | Durene | Other C 10A | ∑C 10A | C 11 + |
| Content | 0.12 | 2.73 | 2.13 | 7.79 | 23.32 | 20.46 | 25.23 | 76.80 | 18.22 |
Carry out above-mentioned aroamtic hydrocarbon raw material hydro-dealkylation and transalkylation reaction performance evaluation with fixed-bed reactor, 20 millimeters of reactor inside diameter φ, 1200 millimeters of length are made with stainless steel tube.Adopt electrically heated, temperature is controlled automatically.Filling 20 gram catalyzer in 5 millimeters granulated glass spherees of reactor bottom filling φ, reaction zone, 5 millimeters granulated glass spherees of top filling φ are as the usefulness of raw material preheating, gasification.Raw material C
10And above heavy aromatics mixes with hydrogen, pass through reactor from top to bottom, hydro-dealkylation and transalkylation reaction take place, and generate more rudimentary aromatic hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene, first and second benzene, trimethylbenzene, and alkane such as a small amount of methane, ethane, propane, butane.This technology is used hydrogen, is that the hydro-dealkylation reaction needed consumes hydrogen on the one hand, and on the other hand, the existence of hydrogen has worked to suppress catalyst carbon deposition simultaneously, in order to prolong the running period of catalyzer.
[embodiment 6～9]
Catalyst A～D that embodiment 1～4 makes, C
10And above aromatic hydrogenation takes off alkyl and transalkylation reaction the results are shown in Table 2.
Table 2 is rich in C
10A hydro-dealkylation and transalkylation reaction result
| |
6 | 7 | 8 | 9 |
| Catalyst reaction temperatures, ℃ reaction pressure, MPa hydrogen/hydrocarbon mol ratio WHSV, hour -1 | A 400 2 6 2.5 | B 360 3 4 1 | C 380 3 5.6 1.5 | D 415 4 5.6 3.2 |
| Product liquid, % by weight non-aromatics benzene toluene ethylbenzene dimethylamino benzophenone ethylbenzene trimethylbenzene indane C10A C 11 + | 2.18 3.98 10.43 0.52 13.11 0.81 9.17 0.30 53.98 5.51 | 1.2 1.63 8.05 1.34 13.66 1.64 10.69 0.18 56.36 5.24 | 2.23 3.35 9.28 1.56 15.7 2.76 12.2 0.35 47.14 5.45 | 3.11 3.43 7.01 2.42 15.66 2.56 12.46 0.11 48.9 4.34 |
| C 6A-C 9A C 10The A transformation efficiency, % C 11The A transformation efficiency, % | 38.02 35.34 72.18 | 37.01 32.49 73.54 | 44.85 43.53 72.48 | 43.54 41.42 78.09 |
C
11 +Be C
11And above hydrocarbon.
The evaluation result of catalyst A～D shows, is that the mordenite of promotor and beta catalyst are to C with bismuth, molybdenum and nickel component
10And the reaction of the hydro-dealkylation of above heavy aromatics has good katalysis.
[embodiment 10～13]
With isolated C7 and following hydrocarbon thereof in the reaction liquid product of heavy aromatics in the table 1 and embodiment 6, mix with different ratios.The raw material data that obtain see Table 3.
Table 3 mixing raw material is formed, weight %
| Component | Non-aromatics | Benzene | Toluene | C 9A | Indane | ∑C 10A | C 11 + |
| Raw material 1 |
1.87 3.28 | 3.42 5.98 | 8.95 15.66 | 2.45 2.13 | 1.83 1.60 | 65.88 57.67 | 15.63 13.69 |
Catalyzer with embodiment 1 and 3 carries out transalkylation and hydro-dealkylation reaction.Reaction result sees Table 4.
Table 4
| Embodiment number | 10 | 11 | 12 | 13 |
| The raw material that catalyzer uses | A raw material 1 | C raw material 1 | A raw material 2 | C |
| Temperature of reaction, ℃ reaction pressure, MPa hydrogen/hydrocarbon mol ratio WHSV, hour -1 | 400 2 6 2.5 | 410 2 6 2.5 | 383 4 3 1.5 | 390 4 3 1.5 |
| Product liquid, % by weight non-aromatics benzene toluene ethylbenzene dimethylamino benzophenone ethylbenzene trimethylbenzene indane C10A C 11 + | 2.53 4.38 9.11 1.65 22.11 1.81 10.17 0.43 43.32 4.51 | 2.12 3.63 9.05 3.34 20.66 3.64 10.69 0.27 42.36 4.24 | 2.53 5.15 11.74 2.23 23.9 1.76 11.32 0.33 37.12 3.91 | 3.01 4.81 11.65 3.12 22.12 3.67 11.29 0.41 36.58 3.34 |
| C8A C 10The A transformation efficiency, % C 11The A transformation efficiency, % | 23.76 34.24 71.14 | 24.00 35.70 72.87 | 26.13 35.63 71.44 | 25.24 36.57 75.60 |
From the distribution of reaction products of embodiment 10～13, along with the raising of C7 in the raw material and following hydrocarbon thereof, heavy aromatics hydro-dealkylation and transalkylation reaction have taken place simultaneously on catalyst A and C, thereby generated a large amount of C
8A (Mixed XYLENE).Therefore, heavy aromatics of the present invention takes off alkyl and alkyl transfering process, can simplify the separation process of reaction product, do not establish stripping tower, benzene tower and heavy aromatics tower, replace toluene tower with deheptanizer, the tower still material of deheptanizer enters benzenol hydrorefining, benzenol hydrorefining cat head extraction Mixed XYLENE, the C of tower still side line extraction
9And above aromatic hydrocarbons can with the C of deheptanizer cat head
7And following hydrocarbon is circulated to together in the reaction feed and continues reaction, thereby increases production Mixed XYLENE effectively.
Claims (5)
1, a kind of heavy arene hydrogenation takes off the method for alkyl and transalkylation, with C
10And above aromatic hydrocarbons is that raw material carries out hydro-dealkylation and transalkylation reaction, generates C
6～C
9Aromatic hydrocarbons and C
1～C
4Paraffinic hydrocarbon, after separating, dimethylbenzene is characterized in that as the product extraction:
A) raw material C
10And above aromatic hydrocarbons contacts with catalyzer by fixed-bed reactor, and temperature of reaction is 300～600 ℃, and reaction pressure is 1.0～4.0MPa, and the raw material weight air speed is 0.5～5.0 hour
-1, hydrogen/hydrocarbon mol ratio is 1～10;
B) used catalyzer contains SiO in parts by weight
2/ Al
2O
3Mol ratio is 20～90 parts of 10～50 Hydrogen large pore zeolites, on h-type zeolite load 0.05～10 part of bismuth or its oxide compound, 0.05～5 part of the oxide compound of molybdenum, and 0～5 part of at least a chosen from Fe, cobalt, nickel or its oxide compound, the binding agent aluminum oxide is 10～60 parts in catalyzer;
C) reaction product is through the isolated C of deheptanizer
7And the C of following hydrocarbon and dimethylbenzene Tata still
9And above aromatic hydrocarbons is circulated in the reaction feed.
2, the method for taking off alkyl and transalkylation according to the described heavy arene hydrogenation of claim 1 is characterized in that C
6～C
9Aromatic hydrocarbons is that benzene,toluene,xylene, ethylbenzene, first and second benzene are or/and trimethylbenzene.
3, the method for taking off alkyl and transalkylation according to the described heavy arene hydrogenation of claim 1 is characterized in that said Hydrogen large pore zeolite is selected from mordenite, β zeolite or omega zeolite.
4, the method for taking off alkyl and transalkylation according to the described heavy arene hydrogenation of claim 3 is characterized in that the Hydrogen large pore zeolite is the β zeolite.
5, the method for taking off alkyl and transalkylation according to the described heavy arene hydrogenation of claim 1 is characterized in that raw material C
10And the indane weight content is 0～5% in the above aromatic hydrocarbons.
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| CN101121144B (en) * | 2006-08-11 | 2010-09-01 | 中国石油化工股份有限公司 | Catalyst for aromatics alkyl transferring and dealkylation to synthesis benzene and xylene |
| CN101172251B (en) * | 2006-11-02 | 2010-05-12 | 中国石油化工股份有限公司 | Arene alkyl transfer and dealkylation catalyst for increasing production of xylol |
| CN105080598B (en) * | 2014-05-08 | 2018-06-22 | 中国石油化工股份有限公司 | A kind of palladium series catalyst and preparation method thereof |
| CN104152179B (en) * | 2014-09-01 | 2015-11-18 | 江苏联东化工股份有限公司 | A kind of production method of high boiling aromatic hydrocarbon solvent oil |
| CN104370677A (en) * | 2014-11-11 | 2015-02-25 | 中国海洋石油总公司 | C10<+> heavy aromatic hydrocarbon lightening combination process method |
| US11485694B2 (en) * | 2019-02-04 | 2022-11-01 | China Petroleum & Chemical Corporation | Dealklylation and transalkylation of mixed phenols to make cresols |
| CN112745932B (en) | 2019-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon |
| CN113150824A (en) * | 2021-04-02 | 2021-07-23 | 福建省格兰尼生物工程股份有限公司 | Cardanol hydrotreating method |
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