CN106187661B - A kind of C8 aromatic hydrocarbon isomerization-separation coupling reaction method - Google Patents
A kind of C8 aromatic hydrocarbon isomerization-separation coupling reaction method Download PDFInfo
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- CN106187661B CN106187661B CN201510213972.3A CN201510213972A CN106187661B CN 106187661 B CN106187661 B CN 106187661B CN 201510213972 A CN201510213972 A CN 201510213972A CN 106187661 B CN106187661 B CN 106187661B
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000000926 separation method Methods 0.000 title claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 21
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 66
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 36
- 239000011574 phosphorus Substances 0.000 claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 16
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 9
- 238000003795 desorption Methods 0.000 claims description 50
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 238000010926 purge Methods 0.000 claims description 22
- 230000006837 decompression Effects 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 abstract description 58
- 230000008878 coupling Effects 0.000 abstract description 12
- 238000010168 coupling process Methods 0.000 abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 28
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000011017 operating method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229940058172 ethylbenzene Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- -1 alkyl arene Chemical class 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
A kind of C8Aromatics isomerization-separation coupling reaction method, including by C8Aromatic hydrocarbons is passed through isomerization catalyst bed layer with gaseous state, at 170~400 DEG C, aromatics isomerization reaction is carried out under conditions of 0.2~2.0MPa, then reaction mass is desorbed, the isomerization catalyst includes the modified hydrogen molecular sieve of 25~98 mass % and the aluminium oxide of 2~75 mass %, the modified hydrogen molecular sieve is phosphorus or phosphorus and magnesium-modified hydrogen type molecular sieve, the content of phosphorus is calculated as 0.5~20 mass % with phosphorus pentoxide in the modified molecular screen, the content of magnesium is calculated as 0.1~10 mass % with magnesia, the molecular sieve is selected from MFI, MEL, EUO, FER, MFS, MTT, at least one of NES and TON structure molecular screen.Isomerization reaction and separation coupling can get the paraxylene that PX content is more than thermodynamic equilibrium value by the method.
Description
Technical field
The present invention relates to a kind of alkyl arene isomerizing methods, specifically, being a kind of C8Aromatics isomerization-separation coupling
Close reaction method.
Background technique
C8Aromatic hydrocarbons is typically from catalytic reforming, steam cracking and toluene disproportionation device, paraxylene (PX) therein
Important industrial chemicals mainly for the production of p-phthalic acid (PTA), dimethyl terephthalate (DMT) (DMT), while still being given birth to
Produce the raw material of coating, dyestuff, pesticide and medicine.C of the PX in various sources8Content is usually no more than 25% in aromatic hydrocarbons, in order to full
The growing demand of foot, industrially using moving-bed adsorption separation or crystallization technique separation mixing C8PX in aromatic hydrocarbons,
OX can be separated by rectifying, and residue, which flows through isomerization process and is converted into PX content, is close to or up to the mixed of thermodynamic equilibrium value
Close C8Aromatic hydrocarbons, and part ethylbenzene (EB) is taken off into alkyl or is converted into dimethylbenzene, isomerization product is recycled back to PX separative unit.
PX concentration is limited by thermodynamical equilibrium in traditional isomerization technology product, and the thermodynamics delivery rate of usually PX is higher, discrimination
The degree of the side reactions such as change, transalkylation and cracking is bigger, C8Arenes selectivity is lower.If isomerization process can obtain PX
Concentration is more than the product of thermodynamic equilibrium value, then can reduce the internal circulating load of Aromatic Hydrocarbon United Plant, reduces energy consumption, improves economic effect
Benefit.
US 4331822 discloses the method for gas phase isomerization under hydroconversion condition, isomerization catalyst Supported Pt Nanoparticles and another kind
Metallic element, the metal are selected from one of metallic elements such as titanium, chromium, zinc, gallium, germanium.This method is due to non-purpose acid catalysis alkane
The generation of group-transfer reaction and ring cracking reaction leads to the loss of dimethylbenzene in isomerization reaction.
The basic principle of pressure-variable adsorption (PSA) is the difference and absorption using gas component adsorpting characteristic on solid material
Amount realizes the separation or purification of gas by periodic pressure alteration with the feature of change in pressure.From Skarstrom
Since circulation and Guerin-Domine are recycled by invention, PSA gas separation and purification technology is as the independent unit of chemical engineering industry
Operation is rapidly developed.PSA with its high degree of automation, flexible operation, low energy consumption many advantages, such as, be widely used at present
In fields such as the preparation of hydrogen, preparing nitrogen by separating air and oxygen-enriched, transformation gas decarbonization, positive isoparaffin separation.
US 6627783B2 disclose it is a kind of using pressure swing adsorption from C8The method of PX is separated in aromatic hydrocarbons.This method is logical
Pressure-variable adsorption is crossed by C8Aromatic hydrocarbons is divided into the logistics containing meta-xylene (MX) and ortho-xylene (OX), and PX content is less than C in the logistics8
20 moles of % of contained PX amount in aromatic hydrocarbons；The PX of absorption and EB are desorbed up to the logistics of PX, MX and neighbour contained therein is rich in
The amount of dimethylbenzene is less than C850 moles of % of total amount both in aromatic hydrocarbons.
US6573418B2 uses pressure-variable adsorption-Simulation moving bed group technology from mixing C8PX and EB is separated in aromatic hydrocarbons.
Mix C8Aroamtic hydrocarbon raw material passes through heating first and enters psa unit with gas phase state, since PX, EB and MX, OX are in adsorbent
On diffusion rate it is different, adsorbent has preference to PX, EB, two streams is obtained, more than one suction for richness MX, OX
Object, another stock are the extract of richness EB, PX；Excess will be inhaled and be sent into isomerization unit；Extract is sent into moving-bed adsorption
Separative unit isolates the PX product of high concentration, and EB is concentrated in raffinate, obtains EB after separating strippant.
USP5110776 discloses a kind of preparation method of phosphorus-modified zeolite catalyst, including molecular sieve is dispersed in pH
In the phosphorus-containing compound aqueous solution of value 2~6, it is mixed with beating with catalyst substrates precursor, then spray drying forming.Point
Mixture of the son screened from the large pore molecular sieves such as X, Y, USY, mesoporous molecular sieve or both, the medium-pore molecular is screened from ZSM-
5, ZSM-11 etc., the catalyst are used for the catalytic cracking of hydro carbons.
USP4250345 discloses a kind of method by toluene methylation selectively production paraxylene, uses phosphorus oxygen chemical combination
Object and the compound modified ZSM-5 molecular sieve of magnesia are catalyst, and the catalyst is for alkylation of toluene methanol reaction, to diformazan
Benzene selective can reach 98%.
Summary of the invention
The object of the present invention is to provide a kind of C8Aromatics isomerization-separation coupling reaction method, the method is by isomerization reaction
With separation coupling, the paraxylene that PX content is more than thermodynamic equilibrium value can get.
C provided by the invention8Aromatics isomerization-separation coupling reaction method, including by C8Aromatic hydrocarbons is passed through isomerization with gaseous state
Catalyst bed carries out aromatics isomerization reaction under conditions of 170~400 DEG C, 0.2~2.0MPa, then makes reaction mass
Desorption, the isomerization catalyst include the modified hydrogen molecular sieve of 25~98 mass % and the aluminium oxide of 2~75 mass %,
The modified hydrogen molecular sieve is phosphorus or phosphorus and magnesium-modified hydrogen type molecular sieve, and the content of phosphorus is in the modified molecular screen with five
It aoxidizes two phosphorus and is calculated as 0.5~20 mass %, the content of magnesium is calculated as 0.1~10 mass % with magnesia, and the molecular sieve is selected from
At least one of MFI, MEL, EUO, FER, MFS, MTT, NES and TON structure molecular screen.
The method of the present invention is catalyst activity component using modified hydrogen type molecular sieve, is used for C8Aromatics isomerization-separation
Coupling reaction has preferably absorption isomerization reaction performance, contains more PX in resulting desorption liquid after desorption.
Detailed description of the invention
Fig. 1 is isomerization-separation coupling reaction each step operation timing figure of the present invention using four partial pressure desorption modes.
Fig. 2 is isomerization-separation coupling reaction each step operation timing figure of the present invention using four decompression desorption modes.
Fig. 3 is each step operation chart of bed 1 in Fig. 1.
Fig. 4 is each step operation chart of bed 1 in Fig. 2.
Specific embodiment
The present invention couples pressure-variable adsorption with aromatics isomerization, using the adsorption section of pressure-variable adsorption separation as isomerization reaction
Section, the loading catalyst in adsorption tower, to carry out isomerization reaction, the mode for reusing transformation desorption separates isomerization product,
Specific operating method are as follows: by C8Aroamtic hydrocarbon raw material is passed through catalyst bed under the conditions of isomerization reaction with gaseous state, with catalyst
Contact carries out isomerization reaction, carries out desorption later, so that isomerization product is detached from catalyst and obtains desorption liquid.The present invention is logical
Introducing phosphorus and magnesium modulation molecular sieve pore passage size and acidity are crossed, duct is further decreased, constrains the diffusion of MX and OX, raising pair
The selectivity of PX, while molecular sieve outer surface acidity is reduced, to reduce the hair of the non-selective isomerization reaction of molecular sieve outer surface
It is raw, compared with existing C8Aromatics isomerization process, PX content can substantially be more than thermodynamic equilibrium value, different pineization in gained desorption liquid
The coupling of reaction and adsorbing separation can not reduce equipment investment, simplify operating procedure.
The method of the present invention is by C8Aroamtic hydrocarbon raw material is passed through isomerization catalyst bed layer, is allowed to carry out under the effect of the catalyst different
Structureization reaction, while also with the Preferential adsorption to PX in isomerization product.
Preferably 210~400 DEG C of the temperature of the isomerization reaction, pressure preferably 0.6~1.5MPa, C8Aromatic hydrocarbons, which enters, urges
The volume space velocity of agent bed is 0.5~40 hour-1, preferably 0.5~20 hour-1, it is 1.0~10 hours more preferable-1。
C of the present invention8Aromatic hydrocarbons enter catalyst bed carry out isomerization reaction method can there are two types of, the first be
Isomerization reaction is carried out in fill process, isomerization reaction is carried out with charging.
Second is first by C8Aromatic hydrocarbons is passed through catalyst bed, then stops feeding, and makes C8Aromatic hydrocarbons stops in catalyst bed
It stays, further progress isomerization reaction.The present invention claims this section to stop in the reactor without the isomery carried out in the case of material disengaging
Changing reaction is adsorption reaction.The C8When the time that aromatic hydrocarbons stops progress adsorption reaction in catalyst bed preferably feeds
Between 2~20 times, it is 3~15 times more preferable.
After the completion of isomerization reaction, catalyst bed is desorbed in the method for the present invention, and to obtain, PX content is high to be taken off
Attached liquid.
The present invention makes the method that material is desorbed after isomerization reaction that can be partial pressure desorption or decompression desorption.
The decompression desorption is to reduce bed layer pressure, makes to select absorbed component desorption.The present invention is preferably by pressure reduction
The desorption for carrying out reacting rear material to 20~50%, preferably the 25~50% of reaction initial pressure.Decompression desorption before, preferably into
Row is forward bled off pressure, i.e., along direction identical with feedstock direction discharges material, reduces bed layer pressure, non-selective to exclude catalyst
Material in adsorption volume.It forward bleeds off pressure gained logistics and is re-used as isomerization reaction charging.Along being desorbed after putting, take off
Preferably catalyst bed is inversely purged with purge gass while attached.
The partial pressure desorption is to be passed through non-reactive gas to catalyst bed, makes to be desorbed object partial pressure reduction, but bed
Layer gross pressure is basically unchanged.Before partial pressure desorption, it is preferably pressed into non-reactive gas purging catalyst bed, to exclude catalyst
Material in non-selective adsorption volume, purging gained logistics are re-used as isomerization reaction charging.It is described to be desorbed for dividing
Non-reactive gas be 1~60 times, preferably 2~40 times of the non-selective volume of catalyst bed.
The volume space velocity for purging the non-reactive gas of catalyst bed is 30~120 hours-1, preferably 40~
100 hours-1, purge gas dosage is 1~50 times, preferably 4~40 times of the non-selective volume of catalyst bed.
The non-selective volume refers to the sky of bed in the volume and catalyst of not loading catalyst member in reactor
The sum of gap rate (volume between catalyst granules).
The method of the present invention is used to divide desorption and the non-reactive gas of purging bed is selected from nitrogen, hydrogen, argon gas, first
At least one of alkane, ethane, propane and carbon dioxide, preferably hydrogen.
In the method for the present invention, C8The time of aromatic hydrocarbons progress isomerization reaction is 0.8~10 times of desorption time, is preferably
1.0~5 times.
Used catalyst of the present invention includes active component and aluminium oxide, and the active component is modified hydrogen molecular sieve, institute
It states molecular sieve and is selected from least one of MFI, MEL, EUO, FER, MFS, MTT, NES and TON topological structure molecular sieve, it is described
Modifying element is phosphorus or phosphorus and magnesium, and phosphorus content is in terms of phosphorus pentoxide in modified molecular screen, and content of magnesium is in terms of magnesium dioxide.If changing
Property molecular sieve when being P Modification, then preferably 2~15 mass % of the phosphorus content in terms of phosphorus pentoxide；If modified molecular screen be phosphorus and
When magnesium is modified simultaneously, the content of phosphorus preferably 2~15 mass %, more preferable 3~10 mass %, content of magnesium in terms of phosphorus pentoxide
Preferably 1~5 mass % in terms of magnesia.The crystallinity of the molecular sieve is more excellent not less than 65%, preferably not less than 75%
Choosing is not less than 85%.
The modified hydrogen molecular sieve of 70~98 mass % and the oxidation of 2~30 mass % are preferably included in the catalyst
Aluminium.
Isomerization catalyst of the present invention can also load 0.01~0.1 mass %'s, preferably 0.01~0.05 mass %
The load capacity of platinum, platinum is calculated on the basis of the catalyst of not platiniferous.
The preparation method of phosphorus modified molecular sieves of the present invention includes: by the hydrogen type molecular sieve phosphorus-containing compound for being dissolved in water
Solution dipping.Impregnation pressure preferably 0.1~1.0MPa, preferably 75~180 DEG C of dipping temperature, maceration extract and molecular sieve when dipping
Liquid/solid volume ratio be 0.7~3.0, dip time preferably 5~24 hours.Obtained solid obtains phosphorus and changes through drying, roasting after dipping
The molecular sieve of property.The phosphorus-containing compound for dipping is selected from ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum phosphate, phosphorus
One or more of acid anhydrides, phosphorous acid, ammonium phosphite and phosphoric acid.
The preparation method of the phosphorus and magnesium composite modified molecular sieve preferably first carries out P Modification to molecular sieve, then carries out magnesium and change
Property.The method that magnesium is introduced in phosphorus modified molecular sieves is to impregnate phosphorus modified molecular sieves magnesium-containing compound solution, impregnation pressure
It is preferred that 0.1~1.0MPa, preferably 75~180 DEG C of dipping temperature, the liquid/solid volume ratio of maceration extract and molecular sieve is 0.7 when dipping
~3.0, dip time preferably 5~24 hours.The magnesium-containing compound is in magnesium chloride, magnesium nitrate, magnesium sulfate and magnesium acetate
One or more.After filtering, dry, roasting obtains phosphorus and magnesium-modified molecular sieve to obtained solid after dipping.
It is above-mentioned prepare modified molecular screen during, the drying temperature be 80~130 DEG C, preferably 100~120 DEG C, when
Between preferably 1~15 hour, more preferable 2~10 hours, maturing temperature be 400~700 DEG C, preferably 450~600 DEG C, the time preferably 1
~15 hours, more preferable 2~8 hours.
The preferred MFI molecular sieve of molecular sieve of the present invention or EUO molecular sieve, the preferred ZSM-5 of MFI molecular sieve are described
The silica/alumina molar ratio of ZSM-5 molecular sieve be 50~250, preferably 60~150, the preferred EU-1 of EUO molecular sieve,
Its silica/alumina molar ratio preferably 30~60.
The preparation method of the catalyst includes mixing modified molecular screen with aluminium oxide, suitable quantity of water kneading is added, preferably
Acid is added, preferably nitric acid is peptizing agent, extruded moulding, then dry, roasting.
The method for preparing the catalyst of Supported Pt Nanoparticles are as follows: impregnate the catalyst containing modified molecular screen with compound containing platinum, institute
The preferred chloroplatinic acid of the compound containing platinum stated or ammonium chloroplatinate.Solid roasts after drying after dipping.The catalyst of Supported Pt Nanoparticles makes
With preceding needing to restore, reduction temperature is 400~550 DEG C.
The drying temperature is 80~130 DEG C, preferably 100~120 DEG C, and maturing temperature is 400~700 DEG C, preferably 450
~600 DEG C.
C of the present invention for isomerization reaction8The main component of aromatic hydrocarbons is ortho-xylene and meta-xylene, wherein right
The content of dimethylbenzene is preferably smaller than 15 mass % no more than 5 mass %, preferably no greater than 3 mass %, non-aromatic hydrocarbon content.
As the C8When containing ethylbenzene in aromatic hydrocarbons, ethyl-benzene level is preferably no greater than 60 mass %, more preferably no more than 30
Quality % preferably carries out isomerization reaction under hydro condition, react required hydrogen/hydrocarbon molar ratio be 0.1~15, preferably 1.0~
10, catalyst used preferably uses the catalyst of Supported Pt Nanoparticles.
Reaction of the present invention operates continuously in the n reactor equipped with isomerization catalyst to be carried out, each reaction
Device repeats complete operational sequence by 1/n time interval.
Illustrate the present invention with reference to the accompanying drawing.
C8Catalyst bed is entered with gas phase after aroamtic hydrocarbon raw material is heated, it is de- to carry out four partial pressures of use as shown in Figure 1
The isomerization of subsidiary formula formula-separation coupling reacts each step operational sequence.There are four the number of bed, each beds for the left first row column of Fig. 1
Layer carries out FOUR EASY STEPS, is from left to right the sequencing of its place bed FOUR EASY STEPS, i.e. timing in every row.With bed 1
For illustrate the operation timing, isomerate feeds are introduced into catalyst bed, complete feed step, then stop feeding, are adsorbed
Reaction, after adsorption reaction, purges catalyst bed with non-reactive gas, then is passed through non-reactive gas reduction and is taken off
Addendum partial pressure, is desorbed catalyst bed.The charging and adsorption reaction can also a step complete, i.e., in lower charging
Charging is completed under air speed, and raw material is made to complete isomerization reaction in fill process.
Fig. 2 is the timing diagram that the present invention reacts each step operation using isomerization-separation coupling of four decompression desorption modes.
It is essentially identical with Fig. 1 operation, the difference is that forward being bled off pressure to catalyst bed after adsorption reaction (along putting) to exclude non-choosing
Material in selecting property volume, then reduces bed layer pressure, carries out desorption, after the completion of desorption, then will with non-reactive gas
Bed layer pressure rises to reaction pressure, i.e. progress boosting step.
In Fig. 1, Fig. 2, the length of time of each step of proportional representation shared by each operating procedure length is respectively walked in practical operation
The rapid specific time can be set as required.
It is above-mentioned only to lift 4 Tower Systems the present invention will be described, but the present invention is not limited thereto；N platform can be used in the present invention
Tower is operated, and the 1/n time cycle of every tower interval carries out complete operation process.
The present invention is further illustrated below by example, but the present invention is not limited thereto.
Example 1
Following instance prepares P Modification catalyst of the present invention.
500 milliliters are prepared with P2O5The phosphorus content of meter be 5 mass % ammonium dihydrogen phosphate aqueous solution, by 450 grams of silica/
The HZSM-5 molecular sieve that alumina molar ratio is 80, crystallinity is 85% is added thereto, and is impregnated under the conditions of 120 DEG C, 0.5MPa
20 hours, solid was 8 hours dry at 120 DEG C after filtering, roasts 5 hours for 550 DEG C in air atmosphere, obtains P2O5Content is 4.5 matter
Measure the HZSM-5 molecular sieve Z-1 of %.
The molecular sieve Z-1 of above-mentioned P Modification is mixed with aluminium oxide according to the mass ratio of 85:15, is by solid-liquid mass ratio
The amount of 3:1 is added the aqueous solution of nitric acid kneading of 4 mass %, extruded moulding, 120 DEG C drying 6 hours, pelletizing, 550 DEG C to roast 6 small
When, catalyst A-1 is made.
Example 2
The HZSM-5 molecular sieve of P Modification is prepared by the method for example 1, the difference is that ammonium dihydrogen phosphate aqueous solution used
In with P2O5The phosphorus content of meter is 14 mass %, and P is made2O5Content is the HZSM-5 molecular sieve Z-2 of 13.5 mass %.
Take molecular sieve Z-2 to mix with aluminium oxide according to the mass ratio of 90:10, then by the method kneading of example 1, extrusion at
Type, drying roast obtained catalyst A-2.
Example 3
500 milliliters are prepared with P2O5The phosphorus content of meter is the ammonium dibasic phosphate aqueous solution of 20 mass %, and 450 grams are aoxidized
The HZSM-5 molecular sieve that silicon/alumina molar ratio is 100, crystallinity is 83% is added thereto, small in normal pressure, 30 DEG C of dippings 20
When, it is 8 hours dry at 120 DEG C after filtering, it is roasted 5 hours for 550 DEG C in air atmosphere, obtains P2O5Content is 18.5 mass %'s
HZSM-5 molecular sieve Z-3.
The molecular sieve Z-3 of above-mentioned P Modification is mixed with aluminium oxide according to the mass ratio of 95:5, by solid-liquid mass ratio 3:1
Amount be added the aqueous solution of nitric acid kneading of 4 mass %, extruded moulding, by strip 6 hours dry, pelletizing at 120 DEG C, 550 DEG C
Catalyst A-3 is made in roasting 6 hours.
Example 4
500 milliliters are prepared with P2O5The phosphorus content of meter is the ammonium dibasic phosphate aqueous solution of 15 mass %, and 450 grams are aoxidized
The Hydrogen EU-1 molecular sieve that silicon/alumina molar ratio is 40, crystallinity is 86% is added thereto, small in normal pressure, 30 DEG C of dippings 20
When, it is 8 hours dry at 120 DEG C after filtering, it is roasted 5 hours for 550 DEG C in air atmosphere, obtains P2O5Content is the hydrogen of 14 mass %
Type EU-1 molecular sieve Z-4.
The molecular sieve Z-4 of above-mentioned P Modification is mixed with aluminium oxide according to the mass ratio of 85:15, by solid-liquid mass ratio 3:1
Amount be added the aqueous solution of nitric acid kneading of 4 mass %, extruded moulding, by strip 6 hours dry, pelletizing at 120 DEG C, 550 DEG C
Catalyst A-4 is made in roasting 6 hours.
Example 5
Following instance prepares the magnesium-modified catalyst of phosphorus-.
The Adlerika that 500 milliliters of content of magnesium in terms of magnesia are 5 mass % is prepared, the resulting phosphorus of example 1 is changed
Property HZSM-5 molecular sieve Z-1 be impregnated in above-mentioned solution, impregnated 20 hours in 0.1MPa, 30 DEG C, 120 DEG C of dryings 6 are small after filtering
When, it roasts 6 hours for 550 DEG C in air atmosphere, the magnesium-modified HZSM-5 molecular sieve S-1 of phosphorus-is made, wherein phosphorus content is with P2O5Meter
For 3.5 mass %, content of magnesium is calculated as 2 mass % with MgO.
The magnesium-modified HZSM-5 molecular sieve S-1 of above-mentioned phosphorus-is mixed with aluminium oxide according to the mass ratio of 85:15, by solid-liquid matter
The aqueous solution of nitric acid kneading that 4 mass % are added in the amount than 3:1 is measured, extruded moulding is 6 hours dry at 120 DEG C by strip, cuts
Grain, 550 DEG C roast 6 hours, and catalyst B-1 is made.
Example 6
The Adlerika that 500 milliliters of content of magnesium in terms of magnesia are 10 mass % is prepared, by 3 gained molecular sieve of example
Z-3 is impregnated in wherein, is impregnated 20 hours in 0.1MPa, 30 DEG C, 120 DEG C drying 6 hours after filtering, 550 DEG C of roastings in air atmosphere
It burns 6 hours, the magnesium-modified HZSM-5 molecular sieve S-2 of phosphorus-is made, wherein phosphorus content is with P2O5Be calculated as 15.5 mass %, content of magnesium with
MgO is calculated as 6 mass %.
Above-mentioned S-2 molecular sieve and aluminium oxide are prepared into catalyst by the method for example 5, catalyst B-2 is made.
Example 7
Following instance preparation carries the catalyst of platinum.
1 gained Phosphorous Modified HZSM-5 molecular sieve Z-1 of example is mixed with aluminium oxide by the mass ratio of 85:15, by solid-liquid matter
The amount than 3:1 of measuring is added the aqueous solution of nitric acid kneading of 4 mass %, extruded moulding, 120 DEG C drying 6 hours, pelletizing, above-mentioned catalysis
550 DEG C of agent obtain catalyst in roasting 6 hours, are impregnated with the platinum acid chloride solution that concentration is 3.5 mg/mls, its is made to load 0.04 matter
Measure the Pt of %, 120 DEG C drying 6 hours, roasted 4 hours in 500 DEG C of air, then at this temperature with hydrogen reducing 4 hours, obtain
To isomerization catalyst C-1.
Example 8
The magnesium-modified HZSM-5 molecular sieve S-2 of 6 gained phosphorus of example-is mixed with aluminium oxide according to the mass ratio of 85:15, is pressed
The amount of solid-liquid mass ratio 3:1 is added the aqueous solution of nitric acid kneading of 4 mass %, extruded moulding, 120 DEG C drying 6 hours, pelletizing,
550 DEG C obtain catalyst in roasting 6 hours.Above-mentioned catalyst is impregnated with the platinum acid chloride solution that concentration is 3.0 mg/mls, keeps it negative
Carry the Pt of 0.03 mass %, 120 DEG C drying 6 hours, roasted 4 hours in 500 DEG C of air atmospheres, now use hydrogen at this temperature
Gas restores 4 hours, obtains isomerization catalyst C-2.
Example 9~15
It is anti-to carry out isomerization-separation coupling of the invention using four partial pressure desorption modes for step timing as shown in Figure 1
It answers.
The reactor of isomerization catalyst is loaded using four, reactor ratio of height to diameter is 8:1, each reactor catalyst dress
Matrix amount is 50 grams, and catalyst bed volume is 68 milliliters.Each reactor successively fed, adsorption reaction, purging, desorption
Step.Isomerate feeds used are containing the meta-xylene (MX) of 55 mass %, the ortho-xylene (OX) of 35 mass %, 5 mass %
Paraxylene (PX) and 5 mass % non-aromaticss.
Below by taking adsorbent bed 1 in Fig. 1 as an example, operation chart as shown in Figure 3 illustrates 1 isomerization of bed-separation coupling
Each operating procedure of reaction:
Charging: opening valve V1, is entered with gas phase state from 1 bottom inlet end of bed after raw material is heated by pipeline P1 and is urged
Agent bed, feed time are 80 seconds.
Adsorption reaction: closing valve V1, and raw material carries out adsorption reaction in catalyst bed, i.e., under the action of catalyst into
Row isomerization reaction, time are 240 seconds.
Purging: opening valve V2, V3, and purging with gas-hydrogen is passed through bed 1 by pipeline P2, the Hydrogen Vapor Pressure being passed through and
Stage of reaction bed layer pressure is identical, and purge time is 80 seconds.It purges resulting mixture to be discharged through pipeline P3, be separated into high pressure
Device, the component after separating hydrogen are returned by pipeline P1, and as reaction feed, hydrogen is recycled.
Desorption: closing valve V2, V3, opening valve V4, V5, and hydrogen is inversely passed through bed through pipeline P4, makes the component in bed
Desorption, the Hydrogen Vapor Pressure being passed through is identical as stage of reaction bed layer pressure, and desorption time is 240 seconds, and desorption component is arranged by pipeline P5
Out, desorption liquid is obtained after separating hydrogen, hydrogen recycles.
Each example used catalyst, isomerization reaction condition, purging and desorption amounts of hydrogen used and reaction result are shown in Table 1.
Example 16~20
It is anti-to carry out isomerization-separation coupling of the invention using four decompression desorption modes for step timing as shown in Figure 2
It answers.
With example 9, feed volume is 6 milliliters for reactor used volume, loaded catalyst and raw material composition, reaction temperature
Degree is 245 DEG C, pressure 0.8MPa.
Below by taking bed 1 in Fig. 2 as an example, operation chart as shown in Figure 4 illustrates that 1 isomerization of bed-separation coupling is anti-
Each operating procedure answered:
Charging and adsorption reaction step: charging and sorption reaction time totally 560 seconds.Valve V1 is opened when charging, at this time bed
Layer 4 is carrying out rapid along strideing, and valve V2, V3 are in the open state, enters through pipeline P3 along putting surge tank 5 along obtained component is put,
Mixed after pressurized with raw material, then it is heated after by pipeline P1 bed 1 is passed through from 1 bottom inlet end of bed with gas phase state, into
Close valve V1, V3 after material, bed 4 along stride it is rapid after close valve V2；It keeps valve V1 in closed state, adsorb anti-
It answers, i.e., carries out isomerization reaction under the action of catalyst.
It is suitable to put: to open valve V3, V4 and simultaneously adjust the rapid along strideing of its aperture progress bed 1, make the object in non-selective volume
Material is discharged by V4 along putting surge tank 5, then is discharged into P1 pipeline through V3, is 140 seconds along the time is put, at this time bed 4 be in into
Expect step, bed 1 be sent into bed 4 through pipeline P1 after obtained component mix with raw material along putting, it is suitable put after closing valve V3,
V4。
Desorption: valve V5, V6 are opened, bed 1 carries out inversely being depressured desorption, while inversely purging using hydrogen through pipeline P4
Bed, Hydrogen Vapor Pressure are mutually all 0.8MPa with stage of reaction bed layer pressure, and purge gass volume space velocity is 70h-1, purging gas consumption is
28 times of the non-selective volume of bed.The desorption time is 280 seconds, and gained desorption liquid is through pipeline P5 bleeder.
Boosting: after desorption, closing valve V5, and valve V6 is in the open state and adjusts aperture, using from pipeline
The 0.8MPa hydrogen of P4 boosts to bed, and the time used in boosting step is 140 seconds, after boosting, closes valve V6, bed
1 pressure reaches reaction initial pressure, so far completes a circulation step.
Each example used catalyst, isomerization reaction condition, desorption manipulation condition and reaction result are shown in Table 2.
Example 21~23
It is anti-to carry out isomerization-separation coupling of the invention using four decompression desorption modes for step timing as shown in Figure 2
It answers.
The reactor of isomerization catalyst is loaded using four, reactor ratio of height to diameter is 8:1, each reactor catalyst dress
Matrix amount is 50 grams, and the non-selective volume of catalyst bed is 13 milliliters.
Isomerate feeds contain the PX of the MX of 50 mass %, the OX of 30 mass %, the ethylbenzene (EB) of 10 mass %, 5 mass %
With the non-aromatics of 5 mass %, single feed volume is 7 milliliters, and reaction carries out under conditions of facing hydrogen, and hydrogen/hydrocarbon molar ratio is 3.
Below by taking bed 1 in Fig. 2 as an example, operation chart as shown in Figure 4 illustrates that 1 isomerization of bed-separation coupling is anti-
Each operating procedure answered:
Charging and adsorption reaction step: charging and sorption reaction time totally 560 seconds.Valve V1 is opened when charging, at this time bed
Layer 4 is carrying out rapid along strideing, and valve V2, V3 are in the open state, and gained enters along group lease making pipeline P3 is put along putting surge tank 5,
Along put component it is pressurized after mixed for 3 raw material with hydrogen/hydrocarbon molar ratio, it is heated after by pipeline P1 with gas phase state from bed 1
Bottom inlet end is passed through bed 1, closes valve V1, V3 after charging, bed 4 along stride it is rapid after close valve V2；Keep valve
V1 closed state carries out adsorption reaction step, i.e., carries out isomerization reaction under the action of catalyst.
It is suitable to put: to open valve V3, V4 and simultaneously adjust the progress of its aperture along strideing suddenly, arrange the material in non-selective volume by V4
Surge tank 5 is put into suitable out, then is discharged into P1 pipeline through V3, is 140 seconds along the time is put, bed 4 is in feed step at this time, will
Bed 1 is 0.3MPa along 1 pressure of bed at the end of putting along putting through pipeline P1 feeding bed 4 after obtained component is mixed with raw material,
Along closing valve V3, V4 after putting.
Desorption: opening valve V5, V6, and bed 1 carries out inversely being depressured desorption, while reverse using the hydrogen from pipeline P4
Bed is purged, Hydrogen Vapor Pressure is identical as stage of reaction bed layer pressure, and purge gass volume space velocity is 80h-1, purging gas consumption is bed
32 times of the non-selective volume of layer.The desorption time is 280 seconds, and gained desorption liquid is through pipeline P5 bleeder.
Boosting: after desorption, closing valve V5, and valve V6 is in the open state and adjusts aperture, using from pipeline
The hydrogen of P4 boosts to bed, and Hydrogen Vapor Pressure is identical as stage of reaction bed layer pressure, and the time used in boosting step is 140
Second, after boosting, valve V6 is closed, 1 pressure of bed reaches reaction initial pressure, so far completes a circulation step.
Each example isomerization reaction condition, desorption manipulation condition and reaction result are shown in Table 3.Wherein
EB conversion ratio is calculated according to following formula:
Table 1
Table 2
Table 3
Claims (12)
1. a kind of C8Aromatics isomerization-separation coupling reaction method, including by C8Aromatic hydrocarbons is passed through isomerization catalyst bed with gaseous state
Layer carries out aromatics isomerization reaction under conditions of 170~400 DEG C, 0.2~2.0MPa, reaction mass then is desorbed, described
Isomerization catalyst include the modified hydrogen molecular sieve of 25~98 mass % and the aluminium oxide of 2~75 mass %, described changes
Property hydrogen type molecular sieve be phosphorus or phosphorus and magnesium-modified hydrogen type molecular sieve, the content of phosphorus is in the modified molecular screen with phosphorus pentoxide
Be calculated as 0.5~20 mass %, the content of magnesium is calculated as 0.1~10 mass % with magnesia, the molecular sieve be selected from MFI, MEL,
At least one of EUO, FER, MFS, MTT, NES and TON structure molecular screen.
2. according to the method for claim 1, it is characterised in that the isomerization catalyst is also loaded 0.01~0.1 mass %
Platinum.
3. according to the method for claim 1, it is characterised in that the C8Aromatic hydrocarbons is passed through the volume of isomerization catalyst bed layer
Air speed is 0.5~40 hour-1。
4. according to the method for claim 1, it is characterised in that the C8After aromatic hydrocarbons is passed through isomerization catalyst bed layer, stop
It only feeds, makes C8Aromatic hydrocarbons stops in catalyst bed carries out adsorption reaction, is then desorbed again, the stop is inhaled
The time of reaction enclosure is 2~20 times of feed time.
5. according to the method for claim 1, it is characterised in that the method partial pressure desorption that reaction mass is desorbed
Or decompression desorption.
6. according to the method for claim 5, it is characterised in that the described partial pressure desorption be passed through to catalyst bed it is non-anti-
Answering property gas is desorbed the partial pressure of object to reduce.
7. according to the method for claim 5, it is characterised in that the decompression desorption is that bed layer pressure is made to be reduced to reaction
The 20~90% of initial pressure.
8. according to the method for claim 5, it is characterised in that before reaction mass carries out partial pressure desorption, with non-reacted gas
Body purges catalyst bed, and purge gas dosage is 1~100 times of the non-selective volume of catalyst bed, and purge gas passes through
The volume space velocity of catalyst bed is 2~500 hours-1, purging gained logistics, which returns, to be fed.
9. according to method described in claim 5 or 7, it is characterised in that it is first forward bled off pressure before carrying out decompression desorption, it is suitable to put
After bed layer pressure be initial pressure 20~50%, forward bleed off pressure gained logistics return charging.
10. according to method described in claim 6 or 8, it is characterised in that the non-reactive gas be selected from nitrogen, hydrogen,
One of argon gas, methane, ethane, propane and carbon dioxide.
11. according to the method for claim 1, it is characterised in that the C8When containing ethylbenzene in aromatic hydrocarbons, in the condition for facing hydrogen
Lower carry out isomerization reaction, hydrogen/hydrocarbon molar ratio are 0.1~20.
12. according to the method for claim 1, it is characterised in that the aromatics isomerization reaction is being equipped with isomerization catalytic
It is carried out in n reactor of agent, each 1/n time interval in reactor interval repeats complete operational sequence.
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| US6660896B1 (en) * | 2003-04-16 | 2003-12-09 | Exxonmobil Chemical Patents Inc. | Isomerization of ethylbenzene and xylenes |
| CN102452881A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for isomerizing side chain of carbon octaalkyl aromatic hydrocarbon |
| CN102451747A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Side chain isomerization catalyst for carbon octaalkyl aromatic hydrocarbon and preparation method thereof |
| CN104513118A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | Method for adsorbing and separating para-xylene and ethyl benzene |
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