CN106433761B - Multi-stage fluidized bed catalytic process for synthesizing alkylate by alkylating isobutane and butene - Google Patents
Multi-stage fluidized bed catalytic process for synthesizing alkylate by alkylating isobutane and butene Download PDFInfo
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- CN106433761B CN106433761B CN201510477150.6A CN201510477150A CN106433761B CN 106433761 B CN106433761 B CN 106433761B CN 201510477150 A CN201510477150 A CN 201510477150A CN 106433761 B CN106433761 B CN 106433761B
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- butene
- isobutane
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- fluidized bed
- catalytic process
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000001282 iso-butane Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 56
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 55
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000008569 process Effects 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 230000002152 alkylating effect Effects 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 238000009835 boiling Methods 0.000 claims abstract description 38
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 235000013847 iso-butane Nutrition 0.000 claims description 61
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 27
- 230000029936 alkylation Effects 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 11
- 239000011973 solid acid Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- CDNBBXKOCUDMCC-UHFFFAOYSA-N but-1-ene;2-methylpropane Chemical compound CCC=C.CC(C)C CDNBBXKOCUDMCC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006384 oligomerization reaction Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical class CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 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 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- -1 iso-butane alkane Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a multistage fluidized bed catalytic process for synthesizing alkylate by alkylating isobutane and butene, which comprises the following steps: sequentially passing the raw material isobutane through 2-8 sections of boiling bed reactors connected in series, dividing the raw material butene into corresponding parts according to the sections of the boiling bed reactors, and respectively inputting the parts into different boiling bed reactors; the raw material isobutane and the raw material butene are input from the bottom of each fluidized bed reactor and output from the upper part of each fluidized bed reactor, and are subjected to contact reaction in a catalyst bed layer in each fluidized bed reactor to prepare alkylate oil. The process can improve the isobutane-butene reaction material ratio at each section of the fluidized bed reactor, thereby improving the actual isobutane/butene reaction ratio on the catalyst in the alkylation reaction process, greatly reducing the occurrence of butene oligomerization side reaction, inhibiting the formation of macromolecular tar sediments, obviously improving the butene conversion rate and the product selectivity of the isobutane-butene alkylation reaction of the catalyst, and improving the reaction operation stability.
Description
Technical field
The invention belongs to the catalyst fields of petrochemical industry, and in particular to a kind of isobutane and butene alkylation synthesis of alkyl
The multistage boiling bed Catalytic processes of carburetion.
Background technology
Currently, social environmentally protective development proposes higher to the content limitation of sulfur in gasoline, aromatic hydrocarbons and additive etc.
Requirement.The octane number of petroleum refining gasoline is mainly derived from isoparaffin, alkene, aromatic hydrocarbons and the methyl for constituting gasoline at present
The antiknock dopes such as tertbutyl ether (MTBE), alcohols.But the burning of alkene and aromatic hydrocarbons can cause to have in the tail gas discharged
Evil substance；The leakage meeting polluted underground water resource of MTBE is led since its concentration at ppm grades will make drinking water become stench
Cause it disabled in some developed countries；Hybrid vapor when alcohols (such as ethyl alcohol) with gasoline because mixing is very high, level of application
It is restricted.Only alkylate oil aromatic-free, sulphur and alkene have the advantages that octane number is high, susceptibility is good, vapour pressure is low etc.,
It is referred to as cleaning alkyl gasoline.
Now in the application of the various techniques of petrochemical industry, isobutane and butene is alkylated reaction and generates higher octane
Value gasoline alkylate (main ingredient is trimethylpentane isomers) production technology is most important alkylation process industry
One of using.As a kind of cost-effective means providing premium blend component, iso-butane alkyl in petroleum refining industry
Change catalyst technology and obtains lasting research and development for a long time.Currently, hydrofluoric acid and the concentrated sulfuric acid are also widely used in this
The traditional industry catalyst of reaction.Although HF and H2SO4Formedness is all shown on activity, selectivity and catalyst life
Can, but HF and H in production process2SO4There is equipment corrosions by force, product and catalyst are not readily separated, easily cause environmental pollution
The shortcomings of serious with personal injury so that the commercial Application of isobutane alkylation is greatly limited with expanding production.So
There is an urgent need to the acidic catalysts of a kind of " close friend " for isobutane alkylation industry now to substitute existing liquid strong acid, and find
New catalysis material, exploitation new catalyst are then the fundamental ways for solving isobutane alkylation existing environment and etching problem.
Currently used for all there is prodigious defects on two kinds of liquid-phase catalysis reaction process of isobutane and butene alkylated reaction.Due to
H2SO4In the spent acid being discharged in process route H is used for containing water and heavier hydrocarbon, the 1/3 of production cost2SO4
Regeneration.And HF is a kind of liquid that high toxicity is volatile, boiling points near room temperature, therefore need that the next pre- protrusion-dispelling of expensive device is installed
Send out the danger of HF leakages.Some industrialized countries have even stopped issuing license to HF alkylation plants.Since iso-butane exists
Solubility in HF is higher, and HF catalysis shows the advantage of production high-octane rating alkylate oil, but dense H2SO4Unlike HF
Volatile, process safety ratio HF methods are relatively good.Currently, China is completed 20 sets of alkyl plant, actual processing energy
Power is asked up to 1,300,000 tons/year, but since alkyl plant generally existing such as acid corrosion, spent acid processing, safety operation etc. is a series of
Topic, so domestic alkyl plant is constantly in low-load operation operating status.Although being closed in liquid acid catalysis both at home and abroad
At in technique H can be effectively reduced using the measures such as addition additive and change process conditions2SO4Loss and HF volatilization
([1] Randolph B B, Hovis K W.REVAP：Reduced volatility alkylation for production
of high value alkylate blend stock.National Petrochemical&Refiners
Association Annual Meeting, Washington D.C., 2002；[2] Himes J F, Mehlberg R L,
Nowak F M.Advances in hydrofluoric acid catalyzed alkylation.National
Petrochemical＆Refiners Association Annual Meeting, San Antonio, 2003；[3]Davis J
R.Alkytech sulfuric acid alkylation management program.National
Petrochemical＆Refiners Association Annual Meeting, San Antonio, 2004；[4]Rock K
L, Vogt T.Two new alkylation advances.National Petrochemical＆Refiners
Association Annual Meeting, San Antonio, 2007.], however still cannot thoroughly solve a large amount of of spent acid
The problems such as generation and security risk, and these measures can also increase construction or operating cost to a certain extent, therefore use green
The inexorable trend of the solid acid catalyst substitution liquid acid catalyst alkylation process development of color.
CN1125640A discloses a kind of alkylated solid heteropoly acid salt catalyzer of isobutane and butene, has selected by phosphorus
The alkali metal (Cs, K) and ammonium (NH that four kinds of tungsten, phosphorus molybdenum, silicon tungsten, silicon molybdenum heteropoly acids synthesize4 +, N (C2H5)4 +) salt as catalyst use
Alkane component accounts for 95% or more in the alkylated reaction of catalyzing iso-butane alkane and butylene, alkylate oil, in terms of olefin feed weight most
Good oil yield is more than 150%, and it does not have the strong corrosive and toxic of sulfuric acid and hydrofluoric acid；But there is long-term for the catalyst
The poor problem of stability in use, constrains its industrial applications.
CN1277893A discloses a kind of modification for being used in iso-butane/butene alkylation and producing high-knock rating gasoline
Beta-zeolite catalyst uses β zeolites for parent, is leached with metal salt after conventional dealuminzation, then promoted with sulfate, or use chlorination
Titanium loads, and modified β zeolites roasting is made；The catalyst prepared using this method can make activity and the choosing of alkylated reaction
Selecting property is significantly improved.But due to zeolite solid acid catalyst, its acid quantity is few compared with liquid acid catalyst, and zeolite pore
Road opening size is smaller, which still has reactivity and decline comparatively fast, and trimethylpentane isomery in product alkylate oil
The low problem of body component content.
Sulfonated phenylethylene hydrogen form cation acidic resins have uniform acid strength, stronger acid and preferable stabilization
Property, it has been used as solid acid resin catalyst to be widely used in various esterifications, etherificate, alkylation of phenol, alkene instead of sulfuric acid at present
Hydrocarbon hydration etc. is in various acid catalyzed reactions, have product postprocessing it is simple, it is small to equipment extent of corrosion, be convenient for continuous production etc.
Advantage.There are many disclosed patents for preparation and application about storng-acid cation exchange resin acidic catalyst.
CN1389297A discloses the preparation method of the macroporous cation exchange resin catalyst of highly acid；CN1555924A is also disclosed that
A kind of high-capacity resin catalyst and preparation method thereof.But common styrene-divinylbenzene cation exchange resin
The pore volume of itself and specific surface area are small, the sour amount of hole surface is smaller, cause its as solid acid catalyst Reaction-diffusion terms by
The problem of limitation, to make it heterogeneous catalysis application in reactivity with selectively it is relatively low.
The Nafion perfluorinated sulfonic resins of Dupont companies of U.S. exploitation are copolymerized by perfluorinated sulfonic acid ether and tetrafluoroethene
The solid super-strong acid being prepared is applicable to the direct alkylation catalytic reaction of iso-butane butylene.But due to Nafion trees
Very low (the 0.02m of surface area of fat2/ g), need to be carried on porous material just has higher catalytic activity.Wei Shen etc.
[Shen W,Gua Y,Xuh L.Alkylation of isobutane/1-butene on methyl-modified
Nafion/SBA-15materials.Applied Catalysis A:General,2010,377:1-8.] Nafion is passed through
Dip loading has obtained surface hydrophobic, acid stronger organic and inorganic on the SBA-15 that trimethylethoxysilane synthesizes
Compound solid-acid material.The results show that under same sour load capacity, catalyzing iso-butane alkane is with butene alkylated effect better than negative
Carrying heteropolyacid and molecular sieve catalyst.But the manufacturing cost of both Nafion resins and mesoporous material is all higher, and load system
It is easy to block the ducts SBA-15 during standby, there is operations to be difficult to control, prepares the shortcomings that poor repeatability, limits its industry
Change the possibility of application.
CN1167011A discloses the preparation method of high thermal stability sulfonic acid type cation exchange resin catalyst,
CN1569334A also discloses that more similar Thermostable strong acid cation resin catalyst and preparation method thereof.By in phenyl ring
The upper high temperature resistance for introducing the electron-withdrawing groups such as F, Cl, Br and improving polystyrene highly acidic resin catalyst, but resin catalysis
Still relatively low (the 30-50m of agent specific surface area2/ g), cause its reactivity relatively low, and easily fouling and inactivate very fast；On the other hand,
The electron-withdrawing groups such as F, Cl, Br are introduced on phenyl ring is directly fluorinated mode of operation and condition not easy-regulating, it is also difficult to carry out work
Industry application.
Analysis on to existing cationic acid resin catalyst preparation method and its performance is as it can be seen that the sulphur of business at present
Though changing styrene resin catalyst has larger acid amount, restricts resin solid acid substitution liquid acid and realize industrial applications
Problem is the Kong Rong little of resin catalyst, the relatively low (30-50m of specific surface area2/ g), the not high enough disadvantage of acid strength leads to it
Reactivity is relatively low, reaction selectivity is poor.And cannot still it meet as isobutane and butene alkylated reaction heterogeneous catalyst
The requirement applied.
Therefore isobutane and butene alkylation synthesis of alkyl carburetion is total in existing commercial plant and patent literature
With in the single-stage autoclave or fixed-bed catalytic technique of charging, the alkylated reacting material ratio of isobutane and butene is relatively low, easily
In butene dimerization and trimerization side reaction occurs, reduce butylene utilization rate and alkylate oil yield.On the other hand, butene oligomerization pair
Reaction, which generates heavy, leads to catalyst bed coking and deactivation, reduces catalyst service life.
Invention content
To solve the above problems, the object of the present invention is to provide a kind of isobutane and butenes to be alkylated synthesis of alkyl carburetion
The butene conversion and selectivity of product of iso-butane butene alkylation can be improved in multistage boiling bed Catalytic processes, this method,
And improve reaction operation stability.
In order to achieve the above objectives, the present invention provides the multistage boilings that a kind of isobutane and butene is alkylated synthesis of alkyl carburetion
A catalytic process is risen, this approach includes the following steps：
Raw material iso-butane is passed sequentially through into concatenated 2-8 sections of fluidized bed reactor, is loaded in the fluidized bed reactor
There is solid acid resin catalyst bed；
Raw material butylene is divided into corresponding number according to the hop count of fluidized bed reactor, and it is anti-to input different ebullated beds respectively
Answer device；
The raw material iso-butane is exported with the raw material butylene by the bottom input top of each fluidized bed reactor, and
Alkylate oil is made in catalyst bed haptoreaction in fluidized bed reactor；
In fluidized bed reactor, the molar ratio of isobutane and butene is 3:1-50:1.
Multistage boiling bed catalytic process provided by the invention is the multi-segment fluidized bed reactor by using series winding,
Solid acid resin catalyst bed is filled in fluidized bed reactor, raw material iso-butane is all from the of multi-segment fluidized bed reactor
One section of bottom enters, and raw material butylene merotomize according to the hop count of fluidized bed reactor after (amount of each section can be according to reality
Border situation distribution), it is fed respectively from the bottom of corresponding fluidized bed reactor.Since raw material isobutane and butene is anti-by ebullated bed
It answers the lower part of device to input top outflow, makes the solid acid resin catalyst in each fluidized bed reactor in boiling fluidized state.
In above-mentioned multistage boiling bed catalytic process, it is preferable that the solid acid resin catalyst is macropore benzene second
Olefin sulfonic acid resin.
In above-mentioned multistage boiling bed catalytic process, it is preferable that the acid amount of the macropore styrene sulfonic acid resin
For 3.0-4.5mmol/g.
In above-mentioned multistage boiling bed catalytic process, it is preferable that the macropore styrene sulfonic acid resin is breathed out for sieve
A-35, A-15 of company or domestic D-08.
In above-mentioned multistage boiling bed catalytic process, it is preferable that the hop count of the fluidized bed reactor is 3-5 sections.
In above-mentioned multistage boiling bed catalytic process, it is preferable that the raw material iso-butane and the raw material butylene
Molar ratio is 1:1-15:1 (referring to the total moles ratio of two kinds of materials of isobutane and butene).
In above-mentioned multistage boiling bed catalytic process, it is preferable that the raw material iso-butane and the raw material butylene
Molar ratio is 2:1-10:1.
In above-mentioned multistage boiling bed catalytic process, it is preferable that at each catalyst bed, isobutane and butene
Molar ratio is 4:1-30:1.
In above-mentioned multistage boiling bed catalytic process, it is preferable that isobutane and butene is anti-in catalyst bed contact
Seasonable temperature is 50-80 DEG C, pressure 2-20atm；Further preferably 65-75 DEG C, 3-10atm.
In above-mentioned multistage boiling bed catalytic process, it is preferable that overall reaction air speed WHSV is 1.0-4.0h-1, into one
Step is preferably 2.0-3.0h-1。
The multistage boiling bed catalysis reaction work of synthesis of alkyl carburetion is alkylated using isobutane and butene provided by the invention
Process, can be greatly reduced the generation of butene oligomerization side reaction, and inhibit the formation of macromolecular tar deposits, to aobvious
The butene conversion and selectivity of product of the iso-butane butene alkylation for improving catalyst are write, and improves reaction operation
Stability；It can achieve good technique effect with important application value.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
A kind of multistage boiling bed Catalytic processes of isobutane and butene alkylation synthesis of alkyl carburetion are present embodiments provided,
The technique includes the following steps：
The macropore styrene sulfonic acid that filling acid amount is 3.8 (mmol/g) respectively in 6 sections of fluidized bed reactors of series winding
Resin catalyst Luo Ha company A-3550g；
With high-pressure pump by raw material iso-butane all from the bottom input of first segment fluidized bed reactor, and raw material butylene is put down
Six parts are divided into, a butylene is inputted respectively to every section of fluidized bed reactor bottom with high-pressure pump；Reaction product is boiled from the 6th section
Rise the top outflow of a reactor.
The total iso-butane butylene material ratio 3/1 (mol/mol) of reaction raw materials, the iso-butane butene reaction of every section of bed catalyst
Material ratio 18/1 (mol/mol)；Controlling reaction temperature is 65 DEG C, pressure 6atm, and overall reaction air speed WHSV is 3.0h-1Under the conditions of
It is alkylated reaction 100h；
It is formed toward gas chromatographic analysis reaction product using online capillary, butene conversion 99.6wt%, alkane is calculated
Base carburetion yield is calculated as in 193wt% or more, C8 hydrocarbon trimethylpentane MTP contents as 77.4wt% with butylene.
The calculation formula of butene conversion is：(reaction raw materials butene content-reaction product butene content)/reaction raw materials fourth
Alkene content；
The calculation formula of alkylate oil yield is：Reaction product alkylate oil content/(reaction raw materials butene content-reaction
Product butene content).
Embodiment 2
A kind of multistage boiling bed Catalytic processes of isobutane and butene alkylation synthesis of alkyl carburetion are present embodiments provided,
The technique includes the following steps：
The macropore styrene sulfonic acid that filling acid amount is 3.0 (mmol/g) respectively in 3 sections of fluidized bed reactors of series winding
The domestic China's reason D-0850g of resin catalyst；
With high-pressure pump by raw material iso-butane all from the bottom input of first segment fluidized bed reactor, and raw material butylene is put down
Three parts are divided into, a butylene is inputted respectively to every section of fluidized bed reactor bottom with high-pressure pump；Reaction product is boiled from third section
Rise the top outflow of a reactor.
The total iso-butane butylene material ratio 1/1 (mol/mol) of reaction raw materials, the iso-butane butene reaction of every section of bed catalyst
Material ratio 3/1 (mol/mol)；Controlling reaction temperature is 80 DEG C, pressure 20atm, and overall reaction air speed WHSV is 1.0h-1Under the conditions of
It is alkylated reaction 160h；
It is formed toward gas chromatographic analysis reaction product using online capillary, butene conversion 99.2wt%, alkane is calculated
Base carburetion yield is calculated as in 194wt% or more, C8 hydrocarbon trimethylpentane MTP contents as 76.1wt% with butylene.
Embodiment 3
A kind of multistage boiling bed Catalytic processes of isobutane and butene alkylation synthesis of alkyl carburetion are present embodiments provided,
The technique includes the following steps：
The macropore styrene sulfonic acid that filling acid amount is 4.5 (mmol/g) respectively in 2 sections of fluidized bed reactors of series winding
Resin catalyst Luo Ha company A-3550g；
With high-pressure pump by raw material iso-butane all from the bottom input of first segment fluidized bed reactor, and raw material butylene is divided
At two parts, every section of fluidized bed reactor bottom inputs a butylene respectively；Reaction product is upper from second segment fluidized bed reactor
It flows out in portion.
The total iso-butane butylene material ratio 2/1 (mol/mol) of reaction raw materials, the iso-butane butene reaction of every section of bed catalyst
Material ratio 4/1 (mol/mol)；Controlling reaction temperature is 70 DEG C, pressure 10atm, and overall reaction air speed WHSV is 2.0h-1Under the conditions of
It is alkylated reaction 200h；
It is formed toward gas chromatographic analysis reaction product using online capillary, butene conversion 99.5wt%, alkane is calculated
Base carburetion yield is calculated as in 191wt% or more, C8 hydrocarbon trimethylpentane MTP contents as 77.3wt% with butylene.
Embodiment 4
A kind of multistage boiling bed Catalytic processes of isobutane and butene alkylation synthesis of alkyl carburetion are present embodiments provided,
The technique includes the following steps：
The macropore styrene sulfonic acid that filling acid amount is 3.5 (mmol/g) respectively in 8 sections of fluidized bed reactors of series winding
Resin catalyst Luo Ha company A-1550g；
With high-pressure pump by raw material iso-butane all from the bottom input of first segment fluidized bed reactor, and raw material butylene is divided
At eight parts, a butylene is inputted respectively to every section of fluidized bed reactor bottom with high-pressure pump；Reaction product is from the 8th section of ebullated bed
It flows out on the top of reactor.
The total iso-butane butylene material ratio 6/1 (mol/mol) of reaction raw materials, the iso-butane butene reaction of every section of bed catalyst
Material ratio 48/1 (mol/mol)；Controlling reaction temperature is 50 DEG C, pressure 2atm, and overall reaction air speed WHSV is 4.0h-1Under the conditions of
It is alkylated reaction 80h；
It is formed toward gas chromatographic analysis reaction product using online capillary, butene conversion 99.3wt%, alkane is calculated
Base carburetion yield is calculated as in 192wt% or more, C8 hydrocarbon trimethylpentane MTP contents as 76.8wt% with butylene.
Embodiment 5
A kind of multistage boiling bed Catalytic processes of isobutane and butene alkylation synthesis of alkyl carburetion are present embodiments provided,
The technique includes the following steps：
The macropore styrene sulfonic acid that filling acid amount is 4.1 (mmol/g) respectively in 4 sections of fluidized bed reactors of series winding
The domestic China's reason D-0850g piecewise uniforms filling of resin catalyst；
With high-pressure pump by raw material iso-butane all from the bottom input of first segment fluidized bed reactor, and raw material butylene is divided
At four parts, a butylene is inputted respectively to every section of fluidized bed reactor bottom with high-pressure pump；Reaction product is from the 4th section of ebullated bed
It flows out on the top of reactor.
The total iso-butane butylene material ratio 5/1 (mol/mol) of reaction raw materials, the iso-butane butene reaction of every section of bed catalyst
Material ratio 20/1 (mol/mol)；Controlling reaction temperature is 60 DEG C, pressure 3atm, and overall reaction air speed WHSV is 2.0h-1Under the conditions of
It is alkylated reaction 60h；
It is formed toward gas chromatographic analysis reaction product using online capillary, butene conversion 99.4wt%, alkane is calculated
Base carburetion yield is calculated as in 195wt% or more, C8 hydrocarbon trimethylpentane MTP contents as 76.7wt% with butylene.
Embodiment 6
A kind of multistage boiling bed Catalytic processes of isobutane and butene alkylation synthesis of alkyl carburetion are present embodiments provided,
The technique includes the following steps：
The macropore styrene sulfonic acid that filling acid amount is 4.1 (mmol/g) respectively in 5 sections of fluidized bed reactors of series winding
Resin catalyst Luo Ha company A-3550g；
With high-pressure pump by raw material iso-butane all from the bottom input of first segment fluidized bed reactor, and raw material butylene is divided
At five parts, a butylene is inputted respectively to every section of fluidized bed reactor bottom with high-pressure pump；Reaction product is from the 5th section of ebullated bed
It flows out on the top of reactor.
The total iso-butane butylene material ratio 5/1 (mol/mol) of reaction raw materials, the iso-butane butene reaction of every section of bed catalyst
Material ratio 25/1 (mol/mol)；Controlling reaction temperature is 75 DEG C, pressure 12atm, and overall reaction air speed WHSV is 3.2h-1Condition
Under be alkylated reaction 150h；
It is formed toward gas chromatographic analysis reaction product using online capillary, butene conversion 99.1wt%, alkane is calculated
Base carburetion yield is calculated as in 197wt% or more, C8 hydrocarbon trimethylpentane MTP contents as 77.0wt% with butylene.
From the test result in above-described embodiment 1-6 as it can be seen that using isobutane and butene alkyl chemical combination provided by the invention
It is reacted under the conditions of lower reaction temperature and higher reaction velocity at the multistage boiling bed catalytic process of alkylate oil
50-200h, average butene conversion have reached 99wt% or more, alkylate oil yield and have been calculated as 190wt% or more, C8 hydrocarbon with butylene
Middle trimethylpentane MTP contents 76wt% or more.It is catalyzed reaction process technology phase with isobutane and butene alkylation is currently used for
Than being used for the butene alkylated synthesis of alkyl carburetion of iso-butane using the method for the present invention, the good product selectivity of acquisition, butylene turn
Rate and alkylate oil high income and good reaction operation stability, have preferable application value and Technical Economy.
Claims (11)
1. a kind of multistage boiling bed catalytic process of isobutane and butene alkylation synthesis of alkyl carburetion, this method include with
Lower step：
Raw material iso-butane is passed sequentially through into concatenated 2-8 sections of fluidized bed reactor, is filled in the fluidized bed reactor solid
Body acid resin catalyst bed；
Raw material butylene is divided into corresponding number according to the hop count of fluidized bed reactor, and inputs different ebullating bed reactors respectively
Device；
The raw material iso-butane is exported with the raw material butylene by the bottom input top of each fluidized bed reactor, and is being boiled
Alkylate oil is made in catalyst bed haptoreaction in bed reactor；
In fluidized bed reactor, the molar ratio of isobutane and butene is 3:1-50:1；
The molar ratio of the raw material iso-butane and the raw material butylene is 1:1-15:1.
2. multistage boiling bed catalytic process according to claim 1, wherein the solid acid resin catalyst is big
Hole styrene sulfonic acid resin.
3. multistage boiling bed catalytic process according to claim 2, wherein the macropore styrene sulfonic acid resin
Acid amount be 3.0-4.5mmol/g.
4. multistage boiling bed catalytic process according to claim 2 or 3, wherein the macropore styrene sulfonic acid
Resin is A-35, A-15 or domestic D-08 of Luo Ha companies.
5. multistage boiling bed catalytic process according to claim 1, wherein the hop count of the fluidized bed reactor is
3-5。
6. multistage boiling bed catalytic process according to claim 1, wherein the raw material iso-butane and the raw material
The molar ratio of butylene is 2:1-10:1.
7. multistage boiling bed catalytic process according to claim 1, wherein in fluidized bed reactor, iso-butane
Molar ratio with butylene is 4:1-30:1.
8. multistage boiling bed catalytic process according to claim 1, wherein isobutane and butene is in catalyst bed
Temperature when haptoreaction is 50-80 DEG C, pressure 2-20atm.
9. multistage boiling bed catalytic process according to claim 1, wherein isobutane and butene is in catalyst bed
Temperature when haptoreaction is 65-75 DEG C, pressure 3-10atm.
10. multistage boiling bed catalytic process according to claim 1, wherein overall reaction air speed WHSV is 1.0-
4.0h-1。
11. multistage boiling bed catalytic process according to claim 1, wherein overall reaction air speed WHSV is 2.0-
3.0h-1。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073421A (en) * | 1991-10-22 | 1993-06-23 | 罗姆和哈斯公司 | Isoalkane-olefin alkylation process |
| CN1326430A (en) * | 1998-10-05 | 2001-12-12 | 美孚石油公司 | Fluid-bed aromatics alkylation |
| US20130165724A1 (en) * | 2011-07-27 | 2013-06-27 | Lu Han | Fluid Bed Reactor with Staged Baffles |
-
2015
- 2015-08-06 CN CN201510477150.6A patent/CN106433761B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073421A (en) * | 1991-10-22 | 1993-06-23 | 罗姆和哈斯公司 | Isoalkane-olefin alkylation process |
| CN1326430A (en) * | 1998-10-05 | 2001-12-12 | 美孚石油公司 | Fluid-bed aromatics alkylation |
| US20130165724A1 (en) * | 2011-07-27 | 2013-06-27 | Lu Han | Fluid Bed Reactor with Staged Baffles |
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