CN104151123B - Method for preparing tetramethylethylene through isobutene metathesis - Google Patents
Method for preparing tetramethylethylene through isobutene metathesis Download PDFInfo
- Publication number
- CN104151123B CN104151123B CN201310179945.XA CN201310179945A CN104151123B CN 104151123 B CN104151123 B CN 104151123B CN 201310179945 A CN201310179945 A CN 201310179945A CN 104151123 B CN104151123 B CN 104151123B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- isobutene
- reaction
- weight
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 128
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000005649 metathesis reaction Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- 239000002994 raw material Substances 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 4
- 150000001336 alkenes Chemical class 0.000 claims description 65
- 230000004913 activation Effects 0.000 claims description 26
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000007323 disproportionation reaction Methods 0.000 description 53
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 37
- 238000011156 evaluation Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 23
- 238000000465 moulding Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 239000005696 Diammonium phosphate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 6
- 235000019838 diammonium phosphate Nutrition 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910019571 Re2O7 Inorganic materials 0.000 description 1
- 241001062233 Salmonella enterica subsp. enterica serovar Texas Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of method for preparing tetramethylethylene through isobutene metathesis, the problem that mainly present in solution prior art, target product selectivity is low.The present invention is raw material by using isobutene., and in fixed bed reactors, reaction temperature is 80～200 DEG C, and reaction pressure is 0.2～0.8MPa, and weight space velocity is 1～20 hour‑1Under the conditions of, raw material and catalyst haptoreaction generate the effluent containing tetramethyl-ethylene, and wherein used catalyst is in terms of parts by weight, including following components: a) molybdenum oxide of 5 ~ 49 parts；B) 1 ~ 8 part of phosphorus pentoxide, c) technical scheme of the alumina support of 50 ~ 94 parts, preferably solve this problem, can be used for the commercial production of preparing tetramethylethylene through isobutene metathesis.
Description
Technical field
The present invention relates to a kind of method for preparing tetramethylethylene through isobutene metathesis.
Background technology
Olefin(e) disproportionation (Olefin metathesis) is the conversion process of a kind of alkene.By at transition-metal catalyst
Under the effect of (such as W, Mo, Re etc.), the fracture of C=C double bond and re-forming in alkene, thus new olefin product can be obtained.
As far back as 1931, Schneider and Frolich was when 1130K carries out propylene cracking, it was observed that occur in that in product
Ethylene and butylene, this is the first time report about olefin(e) disproportionation phenomenon；In the sixties, successively it is found that at heterogeneous catalyst again
(MoO3/Al2O3) and homogeneous catalyst effect under propylene disproportionation reaction.Hereafter, substantial amounts of research work shows, numerous mistakes
Crossing metallic compound and all have catalysis activity to olefin dismutation reaction, wherein the catalytic performance of W, Mo and Re is optimal.
In the sixties, olefin dismutation reaction has obtained commercial Application the most.Phillips Petroleum company in 1966
Begin to use triolefin technique (The Triolefin Process), by propylene disproportionation can produce highly purified ethylene and
Butene-2.This reaction is carried out in fixed bed, reaction temperature 350 ~ 425 DEG C, and catalyst is WO3/SiO2, and with sodium to catalyst table
Face is modified, thus the double bond of alkene can be stoped to shift (isomerization) reaction, improves reaction yield.But due to Market Situation
Change, the demand of propylene is increased so that the economic benefit using this method to produce ethylene declines, and therefore this reaction unit exists
1972 out of service.
In recent years, along with being continuously increased of whole world propylene demand, use the production of propylene amount of traditional method can not expire
The demand of foot propylene, hence with the inverse process of " triolefin technique ", is i.e. reacted by the cross disproportionation of ethylene and butylene and produces propylene
Technology attract attention again.Its reaction equation is expressed as follows:
From the end of the year 1985, Lyondell company has run a set of annual output at the Channelveiw in U.S. Texas state
The production of propylene device of 136,000 tons, this technique uses the cross disproportionation of ethylene and butene-2 to produce propylene, Qi Zhongding just
Alkene-2 is to be generated by ethylene dimerization.1996, this technology of ABB Lummus corporate buyout, rename as olefin conversion technologies
(OCT).To 2007, this technology 10 covering devices the most in the world obtain industrialization, and has 15 sets yet to be built or sign
Conclude an agreement.This technique of Lummus it is said and can reach techniques below index: in reaction temperature 290 DEG C, pressure 3.0MPa, second
Alkene: butylene is (1.7-2): under conditions of 1, butene conversion is up to more than 70%, and Propylene Selectivity reaches 95%, and catalyst regenerates
Cycle reaches more than 720h.
On this basis, ABB Lummus announces to develop preparing hexane by disproportionating butylene technology, and this is it is a technical advantage that be not required to
Wanting consumption of ethylene, directly produce ethylene and higher hexene-1 of added value with n-butene, product 1-hexene can be as polyethylene
The excellent comonomer produced.This technology uses following flow process: the first step is that the butene-2 in C4 material is at isomerization catalyst
Butene-1 is generated under effect；Second step, 1-butylene self disproportionation generates ethylene and hexene-3；Finally, the hexene-3 of generation is again
There is double bond isomerization reaction, generate final products hexene-1.Chemical equation is expressed as follows:
Above-mentioned disproportionation reaction catalyzer uses WO3/SiO2, reaction temperature 300 ~ 400 DEG C, pressure is 0.5 ~ 1.0MPa.Butylene
All using MgO catalyst, reaction temperature 300 ~ 400 DEG C with hexene isomerization catalyst, pressure is 0.5 ~ 1.0MPa.2004 2
The moon ~ in April, 2006, Lummus and middle petrochemical industry cooperation, carried out the pilot scale research of preparing hexane by disproportionating butylene technology in Plant of Tianjin Petrochemical Company.
Tetramethyl-ethylene, as the olefin product of a kind of high added value, can be used for the intermediate of pesticide and spice, is synthesis
The primary raw material of chrysanthemumic acid.It is used for again producing spice and other agricultural chemicals etc. simultaneously, especially replaces neohexene to produce with it and tell
Receive musk odorant, there is the advantage such as low cost, constant product quality.The synthesis of tetramethyl-ethylene is paid attention to very much.The most industrial
The customary preparation methods of tetramethyl-ethylene is to close reaction by propylene dimerization to generate, and the catalyst of employing is the catalysis that all matches
Agent.By olefin(e) disproportionation technology, C4 alkene low value-added for relative surplus can be changed into the tetramethyl-ethylene of high added value.
In typical olefin hydrocarbon apparatus, there is front-end demethanization tower, be used for removing methane and hydrogen, be followed by dethanizer, be used for
Rejecting ethane, ethylene and acetylene；The mixture of the compound in having C3 to C6 carbon number range from the tower bottom product of dethanizer
Composition, can be separated by fractional distillation this mixture.
Being separated by fractional distillation in the C4 logistics obtained containing isobutene., isobutene. can be by following step from C4 logistics
Rapid separation: use catalytic distillation hydrogenation isomerization Deisobutenizer system to separate, by 1-butylene is isomerized to 2-butylene, carry
The volatility difference of high n-butene and isobutene., thus separate isobutene. expeditiously and reclaim n-butene.
Traditional tetramethyl-ethylene production technology is obtained by dimerization of propylene, puts into propylene, add in dimerization still
Enter the catalyst that all matches, under agitation carry out catalytic polymerization, when in still, pressure drops to below 0.01MPa, will thing
Material stopped reaction, oil reservoir slightly steams, and removes trimerization and four poly-product i.e. C9～C19.Alkene, collects the fraction of 53～75 DEG C
For crude product, the most mainly 2,3-neohexene-1, then carrying out isoversion, reaction temperature controls 85～90
DEG C so that it is middle product is changed into 2,3-neohexene-2, i.e. tetramethyl butene-2, then carries out rectification, collects 71～74 DEG C and evaporates
Point, i.e. finished product 2,3-neohexene-2, the remaining by-product C6 alkene for other
US20030204124 discloses a kind of technology preparing tetramethyl-ethylene with isobutene. for raw material.This technology uses
Catalyst to have loaded the oxide of cobalt, molybdenum or rhenium, catalyst carrier and reaction condition the openest.
US20030204123 also discloses that a kind of method of preparing tetramethylethylene through isobutene metathesis, and what this technology used urges
Agent has loaded the oxide of cobalt, molybdenum or rhenium.
CN 102372575A discloses a kind of method of preparing tetramethylethylene through isobutene metathesis, mainly solves conventional art
Present in the low problem of catalyst activity.The present invention is by using with isobutene. as raw material, in fixed bed reactors, and reaction
Temperature is 350～450 DEG C, and reaction pressure is calculated as 0～1MPa with absolute pressure, and weight space velocity is 1～20 hour-1Under the conditions of, raw material and
Catalyst haptoreaction generates containing tetramethyl-ethylene, the effluent of i.e. 2,3-dimethyl-2-butylene, and wherein used catalyst is with weight
Amount number meter is containing 1～30 part of tungsten oxide and 70～99 parts of SiO2Carrier, wherein the specific surface area of catalyst is 250～500 meters2/
Gram technical scheme, preferably solve this problem, can be used for the commercial production of preparing tetramethylethylene through isobutene metathesis.
The method of a CN 102464551A preparing tetramethylethylene through isobutene metathesis, mainly solves to exist in conventional art
Target product yield low, problem that reaction temperature is high.The present invention is by using with isobutene. as raw material, at fixed bed reactors
In, reaction temperature is 20～120 DEG C, and reaction pressure is calculated as 0.2～3MPa with absolute pressure, and weight space velocity is 1～20 hour-1Condition
Under, raw material and catalyst haptoreaction generate the effluent containing tetramethyl-ethylene, wherein used catalyst bag in terms of parts by weight
Include 1～30 part of Re2O7With 70～99 parts of Al2O3The technical scheme of carrier, preferably solves this problem, can be used for isobutene.
It is disproportionated the commercial production of tetramethyl-ethylene processed.
When for preparing tetramethylethylene through isobutene metathesis, all there is target product weight and select in the method in document above
The problem that property is low.
Summary of the invention
The technical problem to be solved is the problem that target product selectivity is low present in prior art, it is provided that
A kind of method of new preparing tetramethylethylene through isobutene metathesis.When the method is used for preparing tetramethylethylene through isobutene metathesis reaction,
There is the advantage that target product selectivity is high.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of for isobutene. tetramethyl second
The method of alkene, with isobutene. as raw material, in fixed bed reactors, reaction temperature is 80 ~ 200 DEG C, and reaction pressure is in terms of absolute pressure
Being 0.2 ~ 0.8MPa, weight space velocity is 1 ~ 20 hour-1Under the conditions of, raw material and catalyst haptoreaction generate containing tetramethyl-ethylene
Effluent, wherein used catalyst is in terms of parts by weight, including following components: a) molybdenum oxide of 5 ~ 49 parts；B) 1 ~ 8 part of five oxygen
Change two phosphorus, c) alumina support of 50 ~ 94 parts.
In technique scheme, the preferred scope of reaction temperature is 100 ~ 150 DEG C；The preferred scope of reaction pressure is 0.4 ~
0.6MPa；The preferred scope of isobutene. weight space velocity is 2 ~ 10 hours-1；In terms of parts by weight the preferred scope of molybdenum oxide be 10 ~
30 parts, in terms of parts by weight, the preferred scope of phosphorus pentoxide is 1 ~ 4 part；Catalyst is through steam treatment, treatment conditions: temperature
Degree is 100～300 DEG C, and the process time is 1～8 hour, and the weight space velocity of water vapour is 1～20 hour-1；Can before catalyst reaction
Activated by alkene；The preferred version of activated olefins is 1-butylene and/or 2-butylene；The preferred version of activation condition is: activation
Temperature is 250～350 DEG C, and soak time is 0.5～4 hour, and the mass space velocity of alkene is 1～5h-1；Can lead to before catalyst reaction
Cross Hydrogen activation.
At catalyst before dismutation reaction, catalyst can be carried out steam treatment, treatment temperature is 100～300
DEG C, preferably scope is 150～200 DEG C, and the process time is 1～8 hour, and preferably scope is 2～6 hours, and the weight of water vapour is empty
Speed is 1～20 hour-1, preferably scope is 5～10 hours-1, steam treatment is conducive to the combination between phosphorus and aluminum, improves and lives
The disproportionation performance of property component.
Disproportionation catalyst in the present invention can use dipping, chemisorbed, chemical deposition, ion exchange, physical mixed etc.
Prepared by method, preferred version is addition alumina support in the aqueous solution containing active component and auxiliary agent, and wherein active component is molybdenum
Source, auxiliary agent is phosphorus-containing compound, adds field mountain valley with clumps of trees and bamboo powder after stirring a period of time, and kneading, extrusion prepare finished product.After drying at sky
In gas atmosphere, roasting obtains catalyst, and the temperature of roasting is 500～700 DEG C, and roasting time is 2～8 hours.
In the present invention, molybdenum source can be the one in molybdic acid, sodium molybdate, ammonium dimolybdate, ammonium tetramolybdate, and preferable molybdenum source is two
Ammonium molybdate.Phosphorus source includes phosphorous acid, such as phosphoric acid, phosphorous acid, phosphoric acid and salt thereof or its mixture, is suitable for preparation present invention catalysis
Agent system phosphate is selected from following material: diammonium phosphate, triammonium phosphate, ammonium dihydrogen phosphate, aluminum phosphate, dipotassium hydrogen phosphate,
Disodium hydrogen phosphate, magnesium phosphate or orthophosphoric acid and above-mentioned substance mixture, it is preferred to use diammonium phosphate or ammonium phosphate.
Catalyst can also be prepared by the following method: will be added to containing phosphorus source aqueous solution, is then passed through filter, is dried and roasting
Burn, it is characterised in that the method is to be joined by aluminium oxide containing in phosphorus source aqueous solution, control water and alumina weight than for (2～
5): 1, it is 1～10 in pH value, reacts 30～200 under the conditions of reaction temperature 50～200 DEG C and 0.2～1.2MPa reaction pressure
Minute, it being then passed through filter, be dried and roasting, obtain P Modification aluminium oxide, sintering temperature is 400～800 DEG C, and the time is 2～10
Hour；Being joined by P Modification aluminium oxide containing in the aqueous solution of molybdenum source, controlling water with molecular sieve ratio is (2～10): 1, instead
Answering temperature 50～100 DEG C, reaction pressure is to react 30～300 minutes under the conditions of 0.1～1.0MPa, be then passed through filter, washing,
Being dried and roasting, sintering temperature is 400～800 DEG C, and the time is 1～4 hour, obtains composite modified molecular sieve.
The catalyst prepared by above method, owing to using step load, improves active component molybdenum and auxiliary agent phosphorus
And the adhesion between carrier, in dismutation reaction, the disproportionation activity of catalyst is more preferably.The oxide of molybdenum can also and phosphorous oxides
Synergism, reduces the acidity of catalyst, the beneficially raising of target product selectivity.
Catalyst prepared by technique scheme is for olefin dismutation reaction, and the embodiment of the present invention is isobutene disproportionation reaction
Generate tetramethyl-ethylene.Reaction condition is as follows: in fixed bed reactors, and reaction temperature is 80 ~ 200 DEG C, and reaction pressure is with absolute pressure
Being calculated as 0.2 ~ 0.8MPa, raw material weight air speed is 1 ~ 20 hour-1.The fixed bed reactors wherein using internal diameter to be 1.5m are urged
Agent is evaluated, with the glass bead of 5mm or porcelain ball as reactor filler.Product composition Aglint 6820 gas chromatogram is carried out
Line analysis.Chromatographic column is the Plot-Al of 50m × 0.53mm2O3Capillary column, detector is hydrogen flame j detector (FID).
After catalysqt deactivation, reactor shutdowns regenerates, and under atmospheric pressure state, catalyst is first under at oxygen atmosphere 400
～600 DEG C of process 2～15h；400～600 DEG C process 2～8h the most in a nitrogen atmosphere, the volume space velocity 1000 of regeneration gas～
2000h-1, boosting after having regenerated and be cooled to reaction condition, regeneration gas is air or oxygen.
The computing formula of the isobutene conversion, tetramethyl-ethylene weight selectivities and the yield that use in the present invention is such as
Under:
Isobutene conversion: X=(1-CC4=)×100%
Tetramethyl-ethylene weight selectivities: S=C/ (1-CC4=)×100%
Tetramethyl-ethylene weight yield: Y=X × S=C × 100%
Wherein CC4=:Isobutene. weight percentage in product
C: in product, the gross weight percentage of tetramethyl-ethylene butylene is containing number
The present invention uses phosphate as the auxiliary agent of catalyst, and isobutene. can occur polyreaction in course of reaction, by
It is strong acid center in the active center of polymerization, therefore by the control of active center content can effectively be suppressed isobutene disproportionation
Polymerization in reaction, improves the selectivity of target product tetramethyl-ethylene.It is 80 ~ 200 DEG C in reaction temperature, reaction pressure
Being calculated as 0.2 ~ 0.8MPa with absolute pressure, raw material weight air speed is 1 ~ 20 hour-1Under conditions of, catalyst is contacted instead with isobutene.
Should, its target product tetramethyl-ethylene weight selectivities, up to 68%, contrasts its tetramethyl-ethylene weight selectivities of other catalyst
10% can be improved, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
By the solution containing 18.6 grams of diammonium phosphate and 940 grams of γ-Al2O3Mix homogeneously is put in blender, adds 10 grams
Sesbania powder adds 61.3 grams of ammonium dimolybdates after stirring 12 minutes, adds 2.5 kilograms of deionized waters, extrusion after mediating 0.5 hour
Molding, is dried the catalyst of extruded moulding 3 hours at 100 DEG C, 4 hours prepared finished catalysts of roasting at 550 DEG C, note
For SL-1.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 1.
[embodiment 2]
By the solution containing 37.2 grams of diammonium phosphate and 900 grams of γ-Al2O3Mix homogeneously is put in blender, adds 10 grams
Sesbania powder adds 98 grams of ammonium dimolybdates and 10 grams of ammonium metatungstates after stirring 12 minutes, adds 2.5 kilograms of deionized waters, mediates
Extruded moulding after 0.5 hour, is dried the catalyst of extruded moulding 3 hours at 100 DEG C, and at 550 DEG C, roasting prepares for 4 hours
Finished catalyst, is designated as SL-2.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 1.
[embodiment 3]
By the solution containing 55.8 grams of diammonium phosphate and 820 grams of γ-Al2O3Mix homogeneously is put in blender, adds 10 grams
Sesbania powder adds 183.9 grams of ammonium dimolybdates after stirring 12 minutes, adds 2.5 kilograms of deionized waters, extrusion after mediating 0.5 hour
Molding, is dried the catalyst of extruded moulding 3 hours at 100 DEG C, 4 hours prepared finished catalysts of roasting at 550 DEG C, note
For SL-3.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 1.
[embodiment 4]
Solution containing 18.6 diammonium phosphate and 500 grams of alumina catalyst support mix homogeneously are put in blender, adds 5 grams
Sesbania powder stir and add 600 grams of ammonium dimolybdates after 30 minutes, add 2.5 kilograms of deionized waters, extrusion one-tenth after mediating 1 hour
Type, is dried the catalyst of extruded moulding 5 hours at 100 DEG C, and at 500 DEG C, 5 hours prepared finished catalysts of roasting, are designated as
SL-4。
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 1.
[embodiment 5]
Solution containing 129.6 grams of ammonium dihydrogen phosphates and 820 grams of alumina catalyst support mix homogeneously are put in blender, adds
The sesbania powder of 10 grams adds 122.6 grams of ammonium dimolybdates after stirring 60 minutes, adds 1.5 kilograms of deionized waters, mediates 1.5 hours
Rear extruded moulding, is dried the catalyst of extruded moulding 3 hours at 120 DEG C, and at 570 DEG C, 3 hours prepared finished products of roasting are urged
Agent, is designated as SL-5.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 1.
[embodiment 6]
Solution containing 49.4 grams of ammonium dihydrogen phosphates and 660 grams of alumina catalyst support mix homogeneously are put in blender, adds 8
Gram sesbania powder stir and add 367.8 grams of ammonium heptamolybdates after 120 minutes, add 1.2 kilograms of deionized waters, after mediating 3 hours
Extruded moulding, is dried the catalyst of extruded moulding 6 hours at 80 DEG C, roasting prepared finished product catalysis in 2 hours at 600 DEG C
Agent, is designated as SL-6.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 1.
[embodiment 7]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first activates catalyst SL-1, activated gas
Being the 1-butylene of 99.9 weight %, activation temperature is 300 DEG C, and soak time is 2 hours, and the weight space velocity of 1-butylene is 6h-1；Live
Having changed rear feedstock and carried out dismutation reaction, calculated by mass fraction, raw material is the isobutene. of 99.9%, and reaction is to be in temperature
120 DEG C, pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of carry out, evaluation result such as table 1
Shown in.
[embodiment 8]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first activates catalyst SL-1, activated gas
Being 1-butylene and the 2-butylene of 50 weight % of 50 weight %, activation temperature is 250 DEG C, and soak time is 4 hours, the weight of 1-butylene
Amount air speed is 1h-1；Having activated rear feedstock and carried out dismutation reaction, calculated by mass fraction, raw material is the isobutene. of 99.9%,
Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of enter
OK, evaluation result is as shown in table 1.
[embodiment 9]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first activates catalyst SL-1, activated gas
Being the hydrogen of 99.9 weight %, activation temperature is 350 DEG C, and soak time is 0.5 hour, and the weight space velocity of hydrogen is 10h-1；Activation
After completing, feedstock carries out dismutation reaction, calculates by mass fraction, and raw material is the isobutene. of 99.9%, and reaction is to be 120 in temperature
DEG C, pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of carry out, evaluation result such as table 1 institute
Show.
[embodiment 10～13]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first catalyst SL-1 is carried out steam treatment, place
Reason condition is as shown in table 2, has processed rear feedstock and has carried out dismutation reaction, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene, reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 2.
[embodiment 14]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first catalyst SL-1 is carried out steam treatment, place
Reason condition is as shown in table 2, after having processed activates catalyst SL-1, and activated gas is the 1-butylene of 99.9 weight %, lives
Changing temperature is 300 DEG C, and soak time is 2 hours, and the weight space velocity of 1-butylene is 6h-1；Activate rear feedstock and carry out discrimination
Changing reaction, calculate by mass fraction, raw material is the isobutene. of 99.9%, and reaction is to be 120 DEG C in temperature, and pressure is calculated as with absolute pressure
0.6MPa, the weight space velocity of isobutene. is 4 hours-1Under conditions of carry out, evaluation result is as shown in table 2.
[embodiment 15]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first catalyst SL-1 is carried out Hydrogen activation, activation
Gas is the hydrogen of 99.9 weight %, and activation temperature is 350 DEG C, and soak time is 0.5 hour, and the weight space velocity of hydrogen is 10h-1；
Hydrogen activation carries out alkene activation to catalyst after completing again, and activated gas is the 1-butylene of 99.9 weight %, and activation temperature is
300 DEG C, soak time is 2 hours, and the weight space velocity of 1-butylene is 6h-1；Activate rear feedstock and carried out dismutation reaction, pressed
Mass fraction is calculated, and raw material is the isobutene. of 99.9%, and reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa, isobutyl with absolute pressure
The weight space velocity of alkene is 4 hours-1Under conditions of carry out, evaluation result is as shown in table 2.
[embodiment 16]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first catalyst SL-1 is carried out steam treatment, place
Reason condition is with embodiment 14, and steam treatment carries out Hydrogen activation to catalyst after completing, and activated gas is the hydrogen of 99.9 weight %
Gas, activation temperature is 350 DEG C, and soak time is 0.5 hour, and the weight space velocity of hydrogen is 10h-1；Hydrogen activation complete after raw material
Carrying out dismutation reaction, calculate by mass fraction, raw material is the isobutene. of 99.9%, and reaction is to be 120 DEG C in temperature, pressure with
Absolute pressure is calculated as 0.6MPa, and the weight space velocity of isobutene. is 4 hours-1Under conditions of carry out, evaluation result is as shown in table 2.
[embodiment 17]
The catalyst SL-1 that embodiment 1 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, first catalyst SL-1 is carried out steam treatment, place
Reason condition is with embodiment 14, and steam treatment carries out Hydrogen activation to catalyst after completing, and activated gas is the hydrogen of 99.9 weight %
Gas, activation temperature is 350 DEG C, and soak time is 0.5 hour, and the weight space velocity of hydrogen is 10h-1；Hydrogen activation is the most right after completing
Catalyst carries out alkene activation, and activated gas is the 1-butylene of 99.9 weight %, and activation temperature is 300 DEG C, and soak time is 2 little
Time, the weight space velocity of 1-butylene is 6h-1；Having activated rear feedstock and carried out dismutation reaction, calculated by mass fraction, raw material is
The isobutene. of 99.9%, reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 little
Time-1Under conditions of carry out, evaluation result is as shown in table 2.
[embodiment 18～22]
The catalyst SL-2 that embodiment 2 prepares is used for olefin dismutation reaction.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction condition is as shown in table 3, and evaluation result is as shown in table 3.
[comparative example 1]
By 940 grams of γ-Al2O3Put in blender with 10 grams of sesbania powder mix homogeneously, after stirring 12 minutes, add 61.3 grams
Ammonium dimolybdate, adds 2.5 kilograms of deionized waters, and extruded moulding after mediating 0.5 hour, by the catalyst of extruded moulding 100
Being dried 3 hours at DEG C, at 550 DEG C, 4 hours prepared finished catalysts of roasting, are designated as BJL-1.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 4.
[comparative example 2]
By 900 grams of γ-Al2O3Put in blender with 10 grams of sesbania powder mix homogeneously, after stirring 12 minutes, add 98 gram two
Ammonium molybdate and 10 grams of ammonium metatungstates, add 2.5 kilograms of deionized waters, and extruded moulding after mediating 0.5 hour, by extruded moulding
Catalyst is dried 3 hours at 100 DEG C, and at 550 DEG C, 4 hours prepared finished catalysts of roasting, are designated as BJL-2.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 4.
[comparative example 3]
By 820 grams of γ-Al2O3Put in blender with 1 gram of sesbania mix homogeneously, after stirring 12 minutes, add 183.9 gram two
Ammonium molybdate, adds 2.5 kilograms of deionized waters, and extruded moulding after mediating 0.5 hour, by the catalyst of extruded moulding at 100 DEG C
Under be dried 3 hours, at 550 DEG C, 4 hours prepared finished catalysts of roasting, are designated as BJL-3.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the isobutyl of 99.9%
Alkene.Reaction is to be 120 DEG C in temperature, and pressure is calculated as 0.6MPa with absolute pressure, and the weight space velocity of isobutene. is 4 hours-1Under conditions of
Carrying out, evaluation result is as shown in table 4.
Table 1
Table 2
Table 3
Table 4
Claims (9)
1. for a method for preparing tetramethylethylene through isobutene metathesis, with isobutene. as raw material, in fixed bed reactors, instead
Answering temperature is 80～200 DEG C, and reaction pressure is 0.2～0.8MPa, and raw material weight air speed is 1～20 hour-1Under the conditions of, raw material and
Catalyst haptoreaction generates the effluent containing tetramethyl-ethylene, and wherein used catalyst is in terms of parts by weight, including following group
Point: a) molybdenum oxide of 5～49 parts；B) 1～8 part of phosphorus pentoxide, c) alumina support of 50～94 parts；
Activated by alkene before catalyst reaction；Activation temperature is 200～400 DEG C, and soak time is 0.1～10 hour, alkene
Mass space velocity be 0.1～10h-1。
Method for preparing tetramethylethylene through isobutene metathesis the most according to claim 1, it is characterised in that reaction temperature
Being 100～150 DEG C, reaction pressure is 0.4～0.6MPa.
Method for preparing tetramethylethylene through isobutene metathesis the most according to claim 1, it is characterised in that raw material weight
Air speed is 2～10 hours-1。
Method for preparing tetramethylethylene through isobutene metathesis the most according to claim 1, it is characterised in that with catalyst
Parts by weight meter, the consumption of molybdenum oxide is 10～30 parts.
Method for preparing tetramethylethylene through isobutene metathesis the most according to claim 1, it is characterised in that with catalyst
Parts by weight meter, the consumption of phosphorus-containing compound is 1～4 part.
Method for preparing tetramethylethylene through isobutene metathesis the most according to claim 1, it is characterised in that catalyst makes
With front through steam treatment, treatment conditions: temperature is 100～300 DEG C, the process time is 1～8 hour, the weight of steam
Air speed is 1～20 hour-1。
Method for preparing tetramethylethylene through isobutene metathesis the most according to claim 1, it is characterised in that the alkene of activation
Hydrocarbon is 1-butylene and/or 2-butylene.
Method for preparing tetramethylethylene through isobutene metathesis the most according to claim 7, it is characterised in that activation temperature
Being 250～350 DEG C, soak time is 0.5～4 hour, and the mass space velocity of alkene is 1～5h-1。
9. according to the method for preparing tetramethylethylene through isobutene metathesis described in claim 1 or 6, it is characterised in that catalyst
By Hydrogen activation before reaction, activation temperature is 250～350 DEG C, and soak time is 2～5 hours, and hydrogen volume air speed is 0.5
～5h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310179945.XA CN104151123B (en) | 2013-05-16 | 2013-05-16 | Method for preparing tetramethylethylene through isobutene metathesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310179945.XA CN104151123B (en) | 2013-05-16 | 2013-05-16 | Method for preparing tetramethylethylene through isobutene metathesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104151123A CN104151123A (en) | 2014-11-19 |
| CN104151123B true CN104151123B (en) | 2016-12-28 |
Family
ID=51876789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310179945.XA Active CN104151123B (en) | 2013-05-16 | 2013-05-16 | Method for preparing tetramethylethylene through isobutene metathesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151123B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4542249A (en) * | 1984-05-04 | 1985-09-17 | Phillips Petroleum Company | Olefin conversions and catalysts |
| CN1033246A (en) * | 1987-11-18 | 1989-06-07 | 国际壳牌研究有限公司 | Catalyst system for olefin disproportionation and method of use thereof |
| CN102464551A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing tetramethyl ethylene by isobutene disproportionation reaction |
| CN102464552A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing 2, 3-dimethyl-2-butylene by isobutene disproportionation |
| CN103030514A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing 2,3-dimethyl-2-butene through isobutene disproportionation |
-
2013
- 2013-05-16 CN CN201310179945.XA patent/CN104151123B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4542249A (en) * | 1984-05-04 | 1985-09-17 | Phillips Petroleum Company | Olefin conversions and catalysts |
| CN1033246A (en) * | 1987-11-18 | 1989-06-07 | 国际壳牌研究有限公司 | Catalyst system for olefin disproportionation and method of use thereof |
| CN102464551A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing tetramethyl ethylene by isobutene disproportionation reaction |
| CN102464552A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing 2, 3-dimethyl-2-butylene by isobutene disproportionation |
| CN103030514A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing 2,3-dimethyl-2-butene through isobutene disproportionation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104151123A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2331488B1 (en) | Olefin isomerization and metathesis catalyst | |
| CN102070391B (en) | The method of comprehensive utilization mixed c 4 preparing isobutene | |
| KR102206883B1 (en) | Method for producing an olefin by catalytic conversion of at least one alcohol | |
| CN105367365A (en) | Integrated propylene production | |
| CN101679146A (en) | Propylene production | |
| CA2718763A1 (en) | Batch process and system for the production of olefins | |
| CN104684873A (en) | Propylene via metathesis with low or no ethylene | |
| JP5881856B2 (en) | Catalyst for producing ethylene and propylene from methanol and / or dimethyl ether, its production method and use | |
| CN103382147B (en) | Method for improving utilization value of mixed C4 | |
| EP2985077A1 (en) | Supported molybdenum or tungsten complexes, its preparation and use in olefin metathesis | |
| CN102372291A (en) | Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve | |
| JP2013501712A (en) | Method and system for producing isoprene | |
| CN106890672A (en) | A kind of methyl alcohol converts light olefin catalyst processed and its preparation method and application | |
| CN101428225A (en) | Nickel base catalyst for producing butylene-1 with butylenes-2 hydroisomerization containing a few butadiene | |
| CN104151123B (en) | Method for preparing tetramethylethylene through isobutene metathesis | |
| CN101165020B (en) | Method for increasing yield of propylene | |
| CN104109071B (en) | The method of cracked C 5 fraction propylene | |
| CN104649860B (en) | A kind of method of one-step method preparing propylene from methanol | |
| CN103626620B (en) | A kind of method of preparing butadiene and isoprene of being combined by hybrid C 4 | |
| CN113636903B (en) | Method for preparing triisobutene by oligomerization of isobutene | |
| CN108495710A (en) | The Catalyst And Method of propylene is produced by ethylene and butylene | |
| CN100496724C (en) | Solid phosphoric acid catalyst and methods of dimerizing olefin with the same | |
| CN106467450B (en) | Method for preparing isobutene | |
| CN106467449B (en) | Method for preparing isobutene | |
| CN103894225A (en) | Aluminum trichloride immobilized type catalyst as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |