CN107159278A - A kind of method of olefin(e) oligomerization - Google Patents
A kind of method of olefin(e) oligomerization Download PDFInfo
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- CN107159278A CN107159278A CN201710408030.XA CN201710408030A CN107159278A CN 107159278 A CN107159278 A CN 107159278A CN 201710408030 A CN201710408030 A CN 201710408030A CN 107159278 A CN107159278 A CN 107159278A
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- Prior art keywords
- olefin
- catalyst
- oligomerization
- alumina support
- macroporous structure
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 55
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 48
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 19
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 17
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 17
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 62
- 229920001661 Chitosan Polymers 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 22
- 239000011591 potassium Substances 0.000 claims description 22
- 229910052700 potassium Inorganic materials 0.000 claims description 22
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 17
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 229910001593 boehmite Inorganic materials 0.000 claims description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 10
- 235000010333 potassium nitrate Nutrition 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 238000002803 maceration Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 239000002671 adjuvant Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 239000000539 dimer Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 239000013638 trimer Substances 0.000 abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052573 porcelain Inorganic materials 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- 229940053662 nickel sulfate Drugs 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical class O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- -1 allylic olefin Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOJYUFGTMHSFEE-YONYXQDTSA-M Cytarabine ocfosphate Chemical compound [Na+].O[C@H]1[C@H](O)[C@@H](COP([O-])(=O)OCCCCCCCCCCCCCCCCCC)O[C@H]1N1C(=O)N=C(N)C=C1 JOJYUFGTMHSFEE-YONYXQDTSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/16—Acids of sulfur; Salts thereof; Sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of olefin(e) oligomerization, using fixed bed reactors；The catalyst is ferric sulfate and nickel sulfate loaded catalyst, and carrier is the aluminum oxide with macroporous structure, and its oligomerization process condition is：165 215 DEG C of reaction temperature, the 6.0MPa of reaction pressure 1.2, the 9.8h of volume space velocity 2.2‑1.Oligomerisation reaction process conditions are gentle, under conditions of olefin conversion is higher, and dimer selectivity is high, and trimer is selectively low, and the activity stability of catalyst is good.
Description
Technical field
The present invention relates to a kind of method of olefin(e) oligomerization, more specifically using a kind of with the aluminum oxide with macroporous structure
For the olefin oligomerization catalyst of carrier, the oligomerisation reaction for alkene.
Background technology
Low-carbon alkene oligomerisation is one of important chemical process, wherein the oligomerisation production of butylene in oil refining and Organic Chemical Industry
Thing is important chemical intermediate, can be used for production oligomerisation gasoline and diesel oil, be also used as production detergent, plasticizer,
The important intermediate of additive and agricultural chemicals.Butene oligomerization catalyst mainly has Ziggler types homogeneous catalyst, solid phosphoric acid catalysis
The multiple catalysts such as agent, zeolite molecular sieve catalyst and loaded catalyst.
The composite of zinc oxide and aluminum oxide is frequently as the carrier material of catalyst, and application field is extensive.Spinel-type
Composite oxides are the up-and-coming inorganic non-metallic materials of a class, and height is widely used in a series of good characteristics
The fields such as adiabator, catalyst and catalyst carrier.The conventional preparation method of the domestic and international material includes infusion process, mechanical mixture
Method, coprecipitation and peptisation.Wherein, because infusion process and mechanical mixing use alumina material as predecessor, pass through
The specific surface area of alumina material is adjusted, both approaches can prepare the composite of high specific surface area, but be due to multiple
Aluminum oxide and zinc oxide interaction in condensation material is weaker, and the loss of zinc oxide is easily produced during use, is typically to adopt
The two is promoted to form spinelle to avoid the loss of zinc oxide with the method for high-temperature roasting；And coprecipitation and peptisation are used and contained
The compound of aluminum and zinc prepares zinc-aluminium precursor by precipitation or peptization, and aluminum and zinc is stronger by reacting generation in preparation process
Interaction the zinc oxide during use can be avoided to be lost in, but the specific surface area that peptisation prepares material is minimum, makes
It is restricted when it is used as catalysis material.
European patent EP 0371983 uses specific surface area 52m2/ g, the granular SiO that aperture is 60nm2Phosphorus is prepared for for carrier
Acid/SiO2Catalyst, for olefin oligomerization gasoline.
United States Patent (USP) US4100220, US4463211 report anti-using cation exchange resin catalyst as butene oligomerization
The catalyst answered, but HMW oligomer easily block reaction duct, and resin matrix alkylation can cause its activity decrease compared with
It hurry up, the heat-resisting quantity of resin is poor in addition, constrain its application.Mobil companies exploitation MOGO techniques (US4150063 and
US4254298) use silica alumina ratio for 79 ZSM-5 molecular sieve catalyst, obtained by changing process conditions with gasoline and bavin
Product based on oil, but because oligomerisation in course of reaction, cracking copolyreaction are present, product carbon number distribution is too wide, selectivity compared with
Difference.
Chinese patent CN1721073A discloses a kind of catalyst of suitable butene oligomerization reaction, by using with YO2/
M2O3The hetero atom ZSM-5 molecular sieve that mol ratio is 50-200 is the active main body of catalyst, and M is triad, and Y is tetravalence member
The butene oligomerization catalyst of element.
Chinese patent CN104324734A discloses a kind of butene oligomerization reaction synthesis C8 and C12 catalyst preparation side
Method, using equi-volume impregnating by Fe (NO3)3First carry out dissolving and be impregnated into γ-Al2O3On, after drying, roasting, then will
(NH4)2SO4Dissolving is impregnated into Fe (NO3)3On/γ-Al2O3,1- butene oligomerization catalyst is obtained after drying and roasting.
The subject matter that above-mentioned catalyst is present is found during butene oligomerization is：Solid acid catalyst SPAC is current
Extensive catalyst is used in butene oligomerization reaction, but it can not regenerate after having argillization, caking, inactivation；Heterogeneous catalyst
Oligomerisation reaction activity and selectivity of product are high, but easily inactivation；Loaded catalyst and ionic-liquid catalyst are preferable due to its
Reactivity worth, it is wide in recent years concerned.
The content of the invention
The invention provides a kind of oligomerization of alkene, dimer is produced for olefin(e) oligomerization.Comprise the following steps：
By treated ferric sulfate-sulfuric acid ni-type Catalyst packing in fixed bed reactors, after airtight experiment is qualified
Start the raw material into olefin-containing, oligomerisation reaction is carried out under reaction process condition, reactor product carries out chromatography.
Fixed bed reactors of the present invention, are fixed bed adiabatic reactor or fixed bed isothermal reactor, preferably solid
Fixed bed adiabatic reactor.
Described allylic olefin oligomerisation reaction, its process conditions is：165-215 DEG C of reaction temperature, reaction pressure 1.2-
6.0MPa, volume space velocity 2.2-9.8h-1；
It is preferred that, 182-198 DEG C of reaction temperature, reaction pressure 2.6-4.3MPa, volume space velocity 4.2-6.8h-1。
Catalyst of the present invention is ferric sulfate and the nickel sulfate being carried on the alumina support with macroporous structure
Base catalyst.
The composition of the catalyst is with oxidation material gauge, including following component：Alumina support with macroporous structure
81.0-96.0wt%, active component ferric sulfate 2.5-11.5wt%, nickel sulfate 1.5-7.5wt%；
It is preferred that, the alumina support with macroporous structure accounts for 85.0-95.0wt%, active component ferric sulfate 3.5-
11.0wt%, nickel sulfate 2.5-5.5wt%.
A kind of olefin oligomerization catalyst of the present invention and preparation method, comprise the following steps：
Ferric sulfate and nickel sulfate soluble-salt are made into maceration extract, alumina support of the dipping with macroporous structure, 110-
Calcination process obtains olefin oligomerization catalyst in 4-8 hours at 130 DEG C of drying process 4-8 hours, 450 DEG C -600 DEG C；
Alumina support of the present invention with macroporous structure, using chitosan as expanding agent, synthesizes with big
The alumina support of pore structure.
Contain adjuvant component phosphorus, lanthanum and potassium, auxiliary agent group in alumina support of the present invention with macroporous structure, carrier
The content of phosphorus, lanthanum and potassium is divided to account for the percentage composition respectively P of carrier quality2O50.1-2.0wt%, La2O30.2-2.4wt%；
K2O 0.1-2.5wt%, preferably pore-size distribution 60-180nm, 65-150nm, macropore ratio 2-75%, preferably 5-65%, pore volume
0.8-2.0ml/g, preferably 0.8-1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m2/ g, carrier is poly- using shell
Sugar is used as expanding agent.
Alumina support of the present invention with macroporous structure, aperture can by change expanding agent addition and
The molecular size range of expanding agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-
The scopes such as 160nm, 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, 35-50%, the model such as 55-75%
Enclose.
The preparation method of alumina support of the present invention with macroporous structure, comprises the following steps：First, it is molten with acid
Boehmite and sesbania powder, are then added in kneader and are well mixed, add phosphoric acid, lanthanum nitrate by liquid acidified chitosan
With the mixed solution of potassium nitrate, finally the acid solution of chitosan-containing is added in boehmite powder and mediated uniformly, containing expansion
The addition of the acid solution of hole agent is 0.1-8wt%, the preferably 0.2-5.0wt% of boehmite, by extrusion-shaping-dry
Dry-roasting, obtains the alumina support with macroporous structure.
The process of the acid solution acidified chitosan is as follows：First by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise afterwards, until chitosan dissolving is complete, the acid solution containing expanding agent is obtained.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The addition of acid is advisable with that can be completely dissolved chitosan.Also may be used
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.More than ultrasonic oscillation 10min, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Ripple shakes or magnetic agitation, and expanding agent good dispersion, alumina support is more prone to macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.
The addition of the sesbania powder is the 0.1-7wt% of boehmite.
Mediate or extrusion technique is that the acid solution containing expanding agent configured is added in sesbania powder and boehmite
Well mixed, extrusion, shaping afterwards is dried 3-9 hours, 650-800 DEG C is calcined 4-8 hours, finally gives by 100-160 DEG C
Alumina support with macroporous structure.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure,
Also contain meso-hole structure simultaneously, macropore range is in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%, be it is a kind of containing being situated between-it is big
The alumina support in hole, and the not homogeneous aperture structure in aperture.
The alumina support with macroporous structure obtained using above-mentioned preparation method, can also be using lanthanum and potassium to carrier
Surface is modified, and the concentration of lanthanum and potassium is unsuitable too high, and preferably configuration concentration is less than lanthanum nitrate and nitric acid when preparing carrier
Aqueous solutions of potassium sprays carrier surface, and carrier surface modification is preferably carried out as follows：Configure containing lanthanum nitrate and potassium nitrate
Alumina support of the aqueous solution spray with macroporous structure, obtains used additives lanthanum through drying, roasting and potassium carries out surface modification
La in alumina support, alumina support of the control with macroporous structure2O5And K2O content respectively in 0.2-2.4wt% and
In the range of 0.1-2.5wt%, and make carrier surface La2O5And K2O content is internal La2O5And K21.2-1.4 times of O content.
Compared with prior art, the present invention has advantages below：
1st, alumina support of the present invention is using chitosan as expanding agent, and expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is adapted to industrialized production.The obtained alumina support with macroporous structure, pore size can adjust, and macropore ratio can
Effectively to control.And carrier is also containing mesoporous, is a kind of Jie-macropore alumina supporter.The alumina support of the structure is anti-
There is more preferable activated centre dispersive property, anti-impurity performance and long period stability in answering.
2nd, the present invention can also introduce phosphorus, lanthanum and potassium in alumina support, the obtained aluminum oxide with macroporous structure
Carrier, the carrier is prepared into olefin oligomerization catalyst, with more preferable oligomerization activity, selectivity and stability.
3rd, the alumina support with macroporous structure that the present invention is obtained, using lanthanum and potassium to the oxidation with macroporous structure
Alumina supporter surface is modified, and makes carrier surface La2O5And K2O content is internal La2O5And K21.2-1.4 times of O content.
Carrier surface is modified by the way of spray, is capable of the partial pore of effective peptization carrier surface, is so conducive to subtracting
The micropore ratio of few carrier surface, improves carrier surface Jie-macropore ratio, promotes carrier surface to produce more active sites and bears
Load center, effectively improves catalyst activity.
4th, the olefin oligomerization catalyst carrier that the present invention is provided is the alumina support with Jie-macroporous structure, catalyst
Oligomerisation reaction mild condition, olefin conversion is high, target dimer is selectively good, and reaction stability is good, long period reactivity worth
It is good.
Brief description of the drawings
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Embodiment
A kind of method of olefin(e) oligomerization of the invention is described in further detail with comparative example by the following examples.
But these embodiments are not regarded as limiting of the invention.
Analysis method and standard：
Raw material and product form analysis method：Gas chromatography.
Primary raw material used in catalyst is prepared to originate：Reagent of the present invention is commercially available prod.
Feedstock oil is olefin feedstock, and olefin(e) centent is more than 80%.
Embodiment 1
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water first, acetic acid is added dropwise afterwards, until
Chitosan dissolving is complete, obtains the acid solution containing expanding agent.A certain amount of phosphoric acid and potassium nitrate are weighed respectively, by phosphoric acid and potassium nitrate
It is dissolved completely in 70g distilled water and is made into the phosphorous and potassium aqueous solution.Weigh 350g boehmites powder and 20.0g sesbania powders add
Enter into kneader, and be well mixed, add the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, finally by chitosan-containing
Acid solution, which is added in boehmite powder, to be mediated uniformly, is clover shape by kneading-extruded moulding.It is dry at 120 DEG C
Dry 8 hours, 700 DEG C were calcined 4 hours, obtain the alumina support 1 of phosphorous, lanthanum and potassium.P in carrier 12O50.5wt%, La2O3
1.2%, K2O 1.8wt%.Alumina support specific surface area with macroporous structure is shown in Table 1 with pore-size distribution.
The water ferric sulfate of 6.4g six is taken, 11.1g nickel sulfate hexahydrates are added in 30ml distilled water, then diluted with deionized water,
Maceration extract alumina support 100g of the dipping with macroporous structure is made into, obtained catalyst precursor is after 120 DEG C dry 6h
6h is calcined at 450 DEG C, alkene alkene catalyst for oligomerization 1 is obtained.Catalyst 1 is mainly constituted：Ferric sulfate 5.0wt%, nickel sulfate
2.5wt%, the alumina support 92.5wt% with macroporous structure.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into olefin feedstock, and carry out under certain process conditions olefin oligomerization.
The process conditions of olefin oligomerization are：175 DEG C of reaction temperature, reaction pressure 3.0MPa, volume space velocity 5.0h-1。
Sampling analysis after about 55h is reacted, the reactor product property of catalyst 1 is as follows：The conversion ratio of alkene is 95.6%, the selection of dimer
Property be 72.6%, the selectivity of trimer is 27.4%.The reactivity of catalyst is suitable, and dimer selectivity is high, reacts bar
Part is gentle.Reaction operation 500h, the conversion ratio of alkene is 93.4%, and the selectivity of dimer is 73.4%, the selection of trimer
Property is 27.0%.Long-term operation result shows：The activity stability of the catalyst reaction of non-surface modification is declined slightly, whole
Body performance is still good.
Embodiment 2
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water, acetic acid is added dropwise afterwards, until shell gathers
Sugar dissolving is complete, obtains the acid solution containing expanding agent.A certain amount of phosphoric acid and potassium nitrate are weighed respectively, by phosphoric acid, lanthanum nitrate and nitre
Sour potassium, which is dissolved completely in 70g distilled water, is made into the phosphorous and potassium aqueous solution.Weigh 350g boehmite powder and 20.0g fields
Cyanines powder is added in kneader, and is well mixed, and adds the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, will finally contain shell
The acid solution of glycan, which is added in boehmite powder, to be mediated uniformly, is clover shape by kneading-extruded moulding.
120 DEG C of dryings 8 hours, 700 DEG C are calcined 4 hours, obtain the alumina support 2 of phosphorous, lanthanum and potassium.P in carrier 22O5
1.5wt%, La2O30.5%, K2O 0.6wt%.
Lanthanum and potassium is recycled to be modified carrier surface, configuring the aqueous solution spray containing lanthanum nitrate and potassium nitrate has greatly
The alumina support of pore structure, is dried 8 hours through 120 DEG C, and 700 DEG C of roastings obtain used additives phosphorus for 4 hours and potassium carries out surface and changed
The alumina support 2 of property, carrier surface P2O5And K2O content is internal P2O5And K21.2 times of O content.With macroporous structure
Alumina support specific surface area and pore-size distribution be shown in Table 1.
Six water ferric sulfate are taken, nickel sulfate hexahydrate is added in 30ml distilled water, then diluted with deionized water, is made into maceration extract
Alumina support 100g of the dipping with macroporous structure, obtained catalyst precursor is calcined after drying 6h at 130 DEG C at 500 DEG C
6h, obtains alkene alkene catalyst for oligomerization 2.Catalyst 2 is mainly constituted：Ferric sulfate 8.0wt%, nickel sulfate 3.0wt%, with macropore knot
The alumina support 89.0wt% of structure.
By catalyst 2 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into olefin feedstock, and carry out under certain process conditions olefin oligomerization.
The process conditions of olefin oligomerization are：190 DEG C of reaction temperature, reaction pressure 3.0MPa, volume space velocity 6.0h-1。
Sampling analysis after about 55h is reacted, the reactor product property of catalyst 2 is as follows：The conversion ratio of alkene is 99.6%, the selection of dimer
Property be 71.3%, the selectivity of trimer is 28.5%.The reactivity of catalyst is suitable, and dimer selectivity is high, reacts bar
Part is gentle.Reaction operation 500h, the conversion ratio of alkene is 98.8%, and the selectivity of dimer is 72.8%, the selection of trimer
Property is 27.8%.Long-term operation result shows：The activity stability of catalyst reaction is good, and service cycle is long, excellent performance.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.Difference is water soluble chitosan expanding agent being replaced by
Water-insoluble chitosan expanding agent, chitosan formic acid liquid magnetic stirrer 30 minutes, obtains the oxygen with macroporous structure
Change alumina supporter 3.The content of adjuvant component phosphorus, lanthanum and potassium accounts for the percentage composition respectively P of carrier quality in carrier2O51.2wt%,
La2O31.5%, K2O 1.4wt%.Its specific surface area is shown in Table 1 with pore-size distribution.
Six water ferric sulfate are taken, nickel sulfate hexahydrate is configured to maceration extract, and dipping has the alumina support 100g of macroporous structure,
Specific steps are with embodiment 1.Catalyst is calcined 7.0h after 130 DEG C of drying 7h at 550 DEG C, obtains olefin oligomerization catalyst 3.
Catalyst 3 is mainly constituted：Ferric sulfate 6.0wt%, nickel sulfate 4.5wt%, the alumina support 89.5wt% with macroporous structure.
By catalyst 3 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into olefin feedstock, and carry out under certain process conditions olefin oligomerization.
The process conditions of olefin oligomerization are：195 DEG C of reaction temperature, reaction pressure 4.0MPa, volume space velocity 4.0h-1。
Sampling analysis after about 55h is reacted, the reactor product property of catalyst 3 is as follows：The conversion ratio of alkene is 97.7%, the selection of dimer
Property be 72.3%, the selectivity of trimer is 28.2%.The reactivity of catalyst is suitable, and dimer selectivity is high, reacts bar
Part is gentle.Reaction operation 500h, the conversion ratio of alkene is 94.2%, and the selectivity of dimer is 72.7%, the selection of trimer
Property is 28.1%.Long-term operation result shows：The activity stability of the catalyst reaction of non-surface modification is declined slightly, whole
Body is functional.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 1.Difference is water soluble chitosan expanding agent being replaced by
Water-insoluble chitosan expanding agent, chitosan acetic acid solution ultrasonic oscillation 15 minutes.Obtain the aluminum oxide with macroporous structure
Carrier.The content of adjuvant component phosphorus, lanthanum and potassium accounts for the percentage composition respectively P of carrier quality in carrier2O51.0wt%, La2O3
0.4%, K2O 0.6wt%.Recycle lanthanum and potassium to be modified carrier surface, obtain carrier 4, the Surface L a of carrier 42O3And K2O
Content be internal La2O3And K21.4 times of O content.The specific surface area of alumina support 4 and pore-size distribution with macroporous structure
It is shown in Table 1.
Six water ferric sulfate are taken, nickel sulfate hexahydrate is configured to maceration extract, and dipping has the alumina support 100g of macroporous structure,
Specific steps are with embodiment 1.Catalyst is calcined 8.0h after 130 DEG C of drying 4h at 550 DEG C, obtains olefin oligomerization catalyst 4.
Catalyst is mainly constituted：Ferric sulfate 7.0wt%, nickel sulfate 3.5wt%, the alumina support 89.5wt% with macroporous structure.
By catalyst 4 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into olefin feedstock, and carry out under certain process conditions olefin oligomerization.
The process conditions of olefin oligomerization are：200 DEG C of reaction temperature, reaction pressure 4.0MPa, volume space velocity 7.0h-1。
Sampling analysis after about 55h is reacted, the reactor product property of catalyst 4 is as follows：The conversion ratio of alkene is 99.4%, the selection of dimer
Property be 78.4%, the selectivity of trimer is 27.5%.The reactivity of catalyst is suitable, and dimer selectivity is high, reacts bar
Part is gentle.Reaction operation 500h, the conversion ratio of alkene is 97.8%, and the selectivity of dimer is 78.8%, the selection of trimer
Property is 26.8%.Long-term operation result shows：The activity stability of the catalyst reaction of non-surface modification is declined slightly, whole
Body performance is still good.
Table 1 has the alumina support specific surface area and pore-size distribution of macroporous structure
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (9)
1. a kind of method of olefin(e) oligomerization, it is characterised in that comprise the following steps：
By treated ferric sulfate-sulfuric acid ni-type Catalyst packing in fixed bed reactors, start after airtight experiment is qualified
Enter the raw material of olefin-containing, oligomerisation reaction is carried out under reaction process condition, reactor product carries out chromatography；
Described catalyst active center is ferric sulfate and nickel sulfate, and catalyst carrier is the carrying alumina with macroporous structure
Body, the composition of catalyst is with oxidation material gauge, including following component：Alumina support 81.0- with macroporous structure
96.0wt%, carrier uses chitosan as expanding agent, active component ferric sulfate 2.5-11.5wt%, nickel sulfate 1.5-
7.5wt%；
The preparation method of described catalyst, comprises the following steps：
Ferric sulfate and nickel sulfate soluble-salt are made into maceration extract, alumina support of the dipping with macroporous structure, 110-130 DEG C
Calcination process obtains olefin oligomerization catalyst in 4-8 hours at drying process 4-8 hours, 450 DEG C -600 DEG C；
The described alumina support with macroporous structure, the method for being prepared by the following procedure is obtained：
First, acid solution acidified chitosan is used, then boehmite and sesbania powder are added in kneader and are well mixed, then
The mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate is added, the acid solution of chitosan-containing is finally added to boehmite powder
Middle to mediate uniform, the addition of the acid solution containing expanding agent is the 0.1-8wt% of boehmite, by extrusion-shaping-dry
Dry-roasting, obtains the alumina support with macroporous structure；
Described olefin oligomerization, its process conditions is：165-215 DEG C of reaction temperature, reaction pressure 1.2-6.0MPa, volume
Air speed 2.2-9.8h-1。
2. a kind of method of olefin(e) oligomerization according to claim 1, it is characterised in that：
Described fixed bed reactors, are fixed bed adiabatic reactor or fixed bed isothermal reactor；
Described olefin oligomerization, its process conditions is：182-198 DEG C of reaction temperature, reaction pressure 2.6-4.3MPa, volume
Air speed 4.2-6.8h-1。
3. a kind of method of olefin(e) oligomerization according to claim 1, it is characterised in that：
The composition of described olefin oligomerization catalyst is with oxidation material gauge, including following component, the oxidation with macroporous structure
Alumina supporter accounts for 85.0-95.0wt%, active component ferric sulfate 3.5-11.0wt%, nickel sulfate 2.5-5.5wt%；
Described to have containing adjuvant component phosphorus, lanthanum and potassium in macropore alumina supporter, the content of adjuvant component phosphorus, lanthanum and potassium accounts for load
The percentage composition of weight is respectively P2O50.1-2.0wt%, La2O30.2-2.4wt% and K2O 0.1-2.5wt%；
The pore-size distribution 60-180nm of the catalyst, macropore ratio 2-75%, pore volume 0.8-2.0ml/g, specific surface area 250-
300m2/g。
4. a kind of method of olefin(e) oligomerization according to claim 3, it is characterised in that：The oxidation with macroporous structure
Alumina supporter, the alumina support with macroporous structure obtained to claim 3, is changed using lanthanum and potassium to carrier surface
Property：Alumina support of the aqueous solution spray with macroporous structure containing lanthanum nitrate and potassium nitrate is configured, is used through drying, roasting
Auxiliary agent lanthanum and potassium carry out La in the alumina support of surface modification, alumina support of the control with macroporous structure2O3And K2O contains
Amount is respectively in the range of 0.2-2.4wt% and 0.1-2.5wt%, and make carrier surface La2O3And K2O content is internal
La2O3And K21.2-1.4 times of O content.
5. a kind of method of olefin(e) oligomerization according to claim 3, it is characterised in that：The aperture of the alumina support point
Cloth is in 65-150nm, macropore ratio 5-65%, pore volume 0.8-1.3ml/g.
6. a kind of method of olefin(e) oligomerization according to claim 3, it is characterised in that：；Alumina support also contains simultaneously
Meso-hole structure, macropore range is in 2-50nm, mesoporous ratio 15-75%.
7. a kind of method of olefin(e) oligomerization according to claim 1, it is characterised in that：The acid solution acidified chitosan
Process is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, acid is added dropwise afterwards, until chitosan is molten
Solution is complete, obtains the acid solution containing expanding agent.
8. a kind of method of olefin(e) oligomerization according to claim 7, it is characterised in that：The acid is acetic acid, formic acid, apple
One or more in acid or lactic acid, chitosan acid solution ultrasonic oscillation or magnetic agitation.
9. a kind of method of olefin(e) oligomerization according to claim 2, it is characterised in that：Described fixed bed reactors are solid
Fixed bed adiabatic reactor.
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