CN106365942A - Mixed C4 conversion method - Google Patents
Mixed C4 conversion method Download PDFInfo
- Publication number
- CN106365942A CN106365942A CN201510435645.2A CN201510435645A CN106365942A CN 106365942 A CN106365942 A CN 106365942A CN 201510435645 A CN201510435645 A CN 201510435645A CN 106365942 A CN106365942 A CN 106365942A
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- China
- Prior art keywords
- mixing carbon
- unit
- carbon
- reaction
- hydrocarbon
- Prior art date
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- Granted
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 76
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 68
- 230000003197 catalytic effect Effects 0.000 claims abstract description 52
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 claims abstract description 40
- 238000006266 etherification reaction Methods 0.000 claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 26
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 69
- 150000002430 hydrocarbons Chemical class 0.000 claims description 69
- 239000004215 Carbon black (E152) Substances 0.000 claims description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 63
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000003054 catalyst Substances 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 31
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 27
- 230000009466 transformation Effects 0.000 claims description 19
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 17
- 150000001298 alcohols Chemical class 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
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- 239000000047 product Substances 0.000 abstract description 44
- -1 carbon olefin Chemical group 0.000 abstract description 19
- 150000001993 dienes Chemical class 0.000 abstract description 19
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- 238000001354 calcination Methods 0.000 description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 235000013847 iso-butane Nutrition 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
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- 206010013786 Dry skin Diseases 0.000 description 5
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- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
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- 238000005899 aromatization reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
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- 238000004821 distillation Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 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 2
- 241000196324 Embryophyta Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000006837 decompression Effects 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
- 238000007598 dipping method Methods 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
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- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for preparing a high-octane gasoline component and butadiene from mixed C4, which is a method for producing butadiene and the high-octane gasoline component by mainly carrying out oxidative dehydrogenation, etherification and catalytic dehydrogenation combined processes on the mixed C4 according to the composition characteristics that the contents of n-butane, isobutane and olefin in the mixed C4 are relatively rich. The method has the characteristics of overcoming the defect that diolefins seriously influence the conversion rate of tertiary carbon olefin, the yield of high-octane gasoline and the content of etherification products in the gasoline, producing a certain amount of high-value diolefins as byproducts, and improving the economic benefit and market competitiveness of the process.
Description
Technical field
The present invention relates to a kind of work producing butadiene and high octane gasoline component by mixing carbon four conversion
Process.
Background technology
Enter 12, with the oil refining of 20,000,000 tons/year of CNPC's Guangdong petrochemical industry, 10,000,000 tons of Kunming/
Year oil refining, Sichuan petrochemical industry Integrated Refinery And Petrochemical engineering, 800,000 tons/year of ethylene of Fushun petrochemical industry, Daqing petrochemical 120
The propulsion of the projects such as ten thousand tons/year of expansion of ethylene, the refining capacity of CNPC and ethylene production capacity also will enter one
Step expands, and the yield of the catalytic cracking c4 of refinery's by-product and cracking c4 resource is also being significantly increased.C4 provides
Source, in addition to part is used for producing mtbe, alkylate oil, polymerized monomer, is burnt mostly as domestic fuel.
And c4 hydrocarbon and tops are not only cheap, and in cost of transportation height, transportation, loss is big, to refinery
For belong to low-value product.
Developing rapidly with Chinese national economy, being continuously increased, to vehicle fuel gasoline of automobile pollution
Demand increasing.Meanwhile, increasingly strict to gasoline quality standard also with environmental requirement, automobile-used
Gasoline quality standard develops to low sulfur content, low olefin-content, low-steam pressure and high-octane direction.
Market has pole to volume increase premium-type gasoline with to low-sulfur, low olefin-content, high octane value gasoline blending component
Big demand, the technological development of this aspect also becomes the hot issue of domestic each research unit and enterprises pay attention.
Butadiene is elastomeric primary raw material, accounts for the 71% of total raw material, butadiene demand in 2015
It is up to 3,500,000 tons.Chinese butadiene source is more single, mainly uses carbon four extraction process, is filled by ethylene
Put production, by 21,000,000 tons of calculating of ethylene ability in 2015, butadiene total resources is 284~2,940,000
Ton, butadiene will appear from serious breach.Another important sources of butadiene are butylene oxidation-dehydrogenation technology.Fourth
Alkene oxidative dehydrogenation with positive structure butylene as raw material, domestic n-butene dehydrogenation being total to of relevant unit at home
Under making great efforts, experienced ternary molybdenum series catalyst, hexa-atomic molybdenum series catalyst, h-198 ferrum system and b-o2 ferrum
Series catalysts, also by initial deflector apron fluid bed development, two-stage nitration finally is axially adiabatic fixing for reaction bed
Bed.Industrialized production proves h-198 Fe-series catalyst and deflector apron fluid bed group technology, b-o2 ferrum
Series catalysts and the insulation fix bed group technology of two sections of axial directions can make domestic n-butene oxidative dehydrogenation device
Production cost and environmental pollution are greatly lowered, and overall economic efficiency reaches same time advanced level.
But from the eighties in 20th century, with constantly newly-built, the butadiene of domestic large-scale ethylene plant
Production technology progressively replaced by the less expensive carbon of cost four extraction process, numerous n-butene oxidative dehydrogenation dresses
Put and gradually stop production, therefore domestic n-butene oxidative dehydrogenation technology could not further be developed.But it is long-range next
See, affected by ethylene cracker raw material lighting, extraction process increase newly butadiene production capacity will be increasingly difficult to
Meet the demand to butadiene for the following downstream synthetic rubber.From the point of view of production cost, n-butene oxidative dehydrogenation system
The production cost of butadiene is higher than traditional extraction process by 30%~40%.
On the other hand, with increasing oil refining apparatus and ethylene unit newly-built and enlarging, domestic oil refining and
The expansion further of ethylene production capacity, the catalytically cracked C four of refinery's by-product and cracking c_4 etc. mix carbon four resource
Yield also will be significantly increased.Carbon four resource remove part be used for producing mtbe, alkylate oil, aromatization carburetion,
Outside polymerized monomer, burn mostly as domestic fuel.In this part carbon four resource, except normal butane, different
Outside butane, containing quite abundant n-butene and isobutene., it is the extraordinary raw material producing butadiene.
Phillips company develops normal butane two step method dehydrogenating technology at first and produces butadiene, and the first step is reacted
Using chromium Al catalysts, by normal butane dehydrogenation, n-butene is dehydrogenated to fourth in the presence of steam by second step again
Diene.This method raw material only has normal butane, for using produced mixing carbon in oil refining and chemical process
For four, less applicable.
Basf company in order to improve the product yield of normal butane dehydrogenation butadiene, in phillips two step method
Update on the basis of technique, add oxygen to second step dehydrogenation systems, make dehydrogenation reaction and oxidation reaction
It is combined together, thus increasing substantially the conversion ratio of n-butene and the selectivity of butadiene, its technique stream
Cheng Wei: the raw material containing normal butane is introduced the first dehydrogenation zone, and the catalytic dehydrogenation of normal butane non-oxidizable ground is
First product gas flow of 1-butylene, 2-butylene and butadiene.First product gas flow is introduced the second dehydrogenation zone,
And be butadiene by 1-butylene and the ground dehydrogenation of 2-butylene oxidisability, to obtain containing butadiene, normal butane etc. the
Two product gas flow, then reclaim butadiene from the second product gas flow.The non-oxidizable catalytic dehydrogenation of normal butane
Plate-type reactor is carried out with autothermal catalysis dehydrogenation, this reactor includes one or more continuously urging
Agent bed, dehydrogenation is platinum group catalyst.N-butene oxidative dehydrogenation is l, and the catalyst of 3- butadiene is
Molybdenum-bismuth-oxygen poly-metal deoxide system.Although after introducing oxygen, the product yield of two step method dehydrogenating technology has
Larger raising, but this technique productions step is many, high cost, and steam consumption is very big.
Italian snamprogetti spa company adopts its original tubular reactor and cartridge reactor skill
Art, develops the det technique of the Tertiary olefin etherificate in catalytic light gasoline, specifically includes that light gasoline divides
From tower, selective hydrogenation reaction device, 2 methyltertiarvbutyl ether reactors, depentanizer, tame knockout tower, mpp
Adsorber and non-Tertiary olefin skeletal isomerization reactor.
The tame technological process of production that IFP (ifp) develops includes purification of raw materials, etherificate
Reaction and Methanol Recovery 3 part.Except that etherification reaction employs a main reactor, and (expanded bed is anti-
Answer device) and an end reaction device (catalytic rectifying tower) be used in series, the 90% of wherein total material is swollen
Carry out in swollen bed reactor.
The catalytic light gasoline etherification technology that Arco chemical technology company (arco) develops, is mainly used in giving birth to
Produce mtbe coproduction tame.In Etherification of Light FCC Gasoline technique, etherification reaction adopts tandem fixed bed adiabatic anti-
Answer device.Its technological process is divided into purification of raw materials, etherification reaction and 3 unit processes of Methanol Recovery.C5 is former
Two fixed bed adiabatic reactions that material is connected with methanol mixed, entrance after washing, selection weighted BMO spaces
In device, reacted in the presence of ion-exchange resin catalyst.
During producing butadiene using two step dehydridings, n-butene and normal butane do main contributions, isobutyl
Alkene and iso-butane conversion ratio are relatively low.And during catalytic dehydrogenation, iso-butane is converted into turning of isobutene.
Rate is higher.Tertiary olefin in logistics can be generated in the presence of catalyst accordingly using etherification technology
Ether compound, Tertiary olefin conversion ratio, more than 95%, isobutene conversion is high-octane ether
Class compound, as gasoline blend component.Different from n-butene and n-butane feedstock, in mixing carbon four, no
Only abundant normal butane, the also suitable n-butene of content, isobutene., iso-butane, the present invention is by two steps
The technique of butadiene is produced in dehydrogenation and etherification technology combines, and exploitation is a kind of to utilize mixing carbon four component next life
Produce the process of butadiene and high octane gasoline component, the added value of mixing carbon four can be improved further.
Content of the invention
Present invention aims to positive iso-butane, positive isoolefine hydrocarbon content are relatively all richer in mixing carbon four
Rich compositing characteristic, provides a kind of mixing carbon four mainly to combine through oxidative dehydrogenation, etherificate, catalytic dehydrogenation
Technical process, the method producing butadiene and high octane gasoline component.
A kind of mixing carbon four method for transformation, is characterised by that conversion process at least comprises the steps: that the first step is mixed
Close carbon four raw material, the logistics containing oxidant and water or water vapour enters oxidative dehydrogenation unit, in filling oxidation
In the reactor of dehydrogenation react after, enter separative element i, by reacted logistics be divided into butadiene,
Other C-4-fractions and other components;Second step is by the other C-4-fractions isolated in the first step and alcohols thing
Streaming enters to be etherified unit, carries out etherification reaction in the reactor equipped with catalyst for etherification, and product enters divides
From unit ii, reacted logistics is divided into carbon more than five component, C_4 hydrocarbon and other component;3rd step will
Isolate C_4 hydrocarbon in second step and send into catalytic dehydrogenation unit with hydrogen, anti-equipped with catalytic dehydrogenation catalyst
Answer and in device, carry out alkane catalytic dehydrogenating reaction, and the logistics after catalytic dehydrogenation is separated through separative element iii
After going out on-condensible gas, send into oxidative dehydrogenation unit together with mixing carbon four raw material.
In the present invention, mixing carbon four raw material refers to refine oil the C_4 hydrocarbon with generation in chemical process, such as carbon after ether
4th, the separation component of catalytically cracked C four, cracking c_4 or light gasoline.Wherein C_4 hydrocarbon quality
Content is not less than 95%, preferably not below 99%, and C 4 olefin mass content is not less than 40%, preferably not
Less than 50%, the mass content of n-butene and normal butane and be not less than 35%, preferably not below 40%.Can
To be raw material or the mixing of separate sources raw material in same source.
In the present invention, the catalyst of oxidative dehydrogenation unit does not also specially require, and can meet n-butene conversion not
Less than 70%, preferably not below 75% requirement.The not specified percentage ratio of the present invention is matter
Amount %.Oxydehydrogenation catalyst can be the main work loading specific ratios using some resistant to elevated temperatures framework materials
Property component and help active component to complete.Wherein, resistant to elevated temperatures framing structure can be metal gauze, many
Empty material all in one piece or aluminium oxide of different shapes, silicon dioxide, zirconium oxide, cordierite, titanium oxide, rich alumina minium
Pillar, stable aluminium oxide, stable zirconium oxide etc. or two kinds of above exotic material or two
Plant above mixture.The mode of loading of active component can for micro- wet impregnated with method, chemical vapour deposition technique,
Coprecipitation etc..Main active component can be 3%~8% lanthanide element or lanthanide element
Oxide, or being mutually mixed for several materials above, can be specifically samarium, cerium, praseodymium, terbium, and its
One or several combination in oxide;Can also be 0.2%~1% platinum group and combinations thereof,
Can be specifically ruthenium, one of palladium, osmium, iridium or platinum or several.Preferably also comprise in catalyst
The metal of 0.01%~0.07% viii race, the metal-oxide of viii race or combinations thereof, tool
Body is ferrum, ferrum oxide, nickel, nickel oxide, palladium, Palladium monoxide, platinum, platinum oxide, sail, vanadium oxide, chromium,
Chromium oxide, manganese, one of manganese oxide etc. or several combinations.Less than 0.1% alkali can also be added
Earth metal and rare earth element are as helping active component.Oxydehydrogenation catalyst is preferably coprecipitation method preparation
There is spinelle or the ferrite of hexahedron structure and the catalyst of alpha-ferric oxide structure simultaneously.Ferrite
In metal ion can be, zinc, barium, magnesium, calcium, strontium, nickel, one of copper or several.Relatively
A kind of Oxydehydrogenation catalyst of the spinelle-alpha-ferric oxide structure of employing coprecipitation method preparation recommended
In, spinelle content 45-60%, the content 2.8%~4.4% of zinc ferrite, other ferrous acid salt contents and not high
In 3%.
In the present invention, the reaction condition of oxidative dehydrogenation unit is to be slightly different according to different catalyst, but
It is well: temperature is 280 DEG C~410 DEG C, preferably 310 DEG C~395 DEG C, pressure 0~100kpa, preferably 0~
40kpa, volume space velocity 10~500h-1, preferably 60~400h-1.The not specified air speed of the present invention is equal
For volume space velocity during liquid.
In the present invention, the logistics containing oxidant of oxidative dehydrogenation unit can be oxygen, oxygen rich air, air etc.
Containing oxygen molecule or contain oxidizing strong oxygen atom material stream, preferred air in the present invention, oxygen rich air and
Oxygen.Particularly preferably oxygen rich air.Oxygen rich air between 32%~45% for the special recommendation oxygen content.Wherein,
With oxymeter in logistics containing oxidant, the alkene of all hydrocarbon materials in oxygen and entrance oxidative dehydrogenation unit
Hydrocarbon mol ratio is 0.1~1.0:1, preferably 0.3~0.85:1.In the fill process of oxidative dehydrogenation unit, add
The water of certain ratio or vapor, lead to temperature with the coking and beds preventing catalyst due to coking
Degree rises too fast problem.In water or steam oxidation dehydrogenation unit, the mass ratio of all hydrocarbon materials can be
0.5~30:1, preferably 5~20:1.
In the present invention reactor of oxidative dehydrogenation unit can for fixed bed reactors, fluidized-bed reactor,
Moving-burden bed reactor, trickle bed reactor or catalystic rectifying reactor, fixed bed reaction tube bank,
Can also be above reactor series connection and or parallel connection.Preferred reactor is two or multiple stage fixed bed reaction
Device or the parallel way of fluidized-bed reactor, facilitate the regeneration of catalyst and the continuous of technical process.
In separative element i in the present invention, separation method can be extraction, rectification or extracting rectifying,
Azeotropic distillation, membrance separation, chemical absorbing etc..Can be obtained using the ripe isolation technics of Technical comparing
Qualified 1,3-butadiene product, and make the content of butadiene in other C-4-fractions of separating not
It is more than not higher than 0.3%, preferably not higher than 0.1%.
It is not particularly limited catalyst for etherification it is desirable to the conversion ratio of isobutene. is not low in etherificate unit in the present invention
In 95%.
Alcohols logistics in etherificate unit in the present invention refers to the low-carbon alcohols that carbon atom number is not more than 4, especially
Recommend methanol, ethanol, preferably methanol.
When in the present invention, raw material enters etherification reaction unit, alcohols is etherified all hydrocarbon materials of unit with entering
In isobutene. mol ratio be 0.8~1.5:1, preferably 1.1~1.3:1.
The reaction condition being etherified unit in the present invention is: 30~100 DEG C, preferably 45~80 DEG C, pressure is
0.1~2.0mpa, preferably 0.5~1.5mpa, volume space velocity is 0.1~5h-1, preferably 1~2h-1.
In the present invention, methyltertiarvbutyl ether reactor is not particularly limited, can be fixed bed, moving bed suspension bed, catalysis
One of distillation reactor etc. or several combinations.It is desirable that being catalytic distillation technology, tertiary carbon can be made
Alkene fully converts, and in separative element, the C-4-fraction of separating methanol tower top output sends into catalytic dehydrogenation unit, tower
The as high octane gasoline component of kettle output, the methanol of recovery can also be recycled to methyltertiarvbutyl ether reactor entrance to be made
With.
In separative element ii in the present invention, separation method is not limited, and can divide for rectification, extraction, film
From etc., but compare and recommend rectification.Require in carbon four logistics isolate ethers, the quality of carbon four component
Content is not less than 97%, preferably not below 99%.
It is not particularly limited dehydrogenation it is desirable to alkene in catalytic dehydrogenation product in catalytic dehydrogenation unit of the present invention
Hydrocarbon content is not less than 35%, is preferably such that olefin(e) centent more than 45%.
In the present invention, the reaction condition of catalytic dehydrogenation unit is preferably: 480~700 DEG C, pressure 0.01~
3mpa, liquid volume air speed is 0.1~10h-1.The reaction condition of special recommendation is: 560~650 DEG C, pressure
Power 0.4~1.2mpa, liquid volume air speed is 2~7h-1.
Entering hydrogen and C_4 hydrocarbon mol ratio in catalytic dehydrogenation unit in the present invention is 0.01~1:1, preferably
0.1~0.5:1.
The catalytic dehydrogenating reaction device being related in the present invention is fixed bed reactors, can be a reactor list
Solely use, two processes interval realizations are regenerated by reaction-catalyst it is also possible to two or more reactor
Used in parallel be circulated operation, multiple reactors can also be divided in parallel and or series combination use.When one
Catalyst in individual or several reactor due to carbon distribution serious inactivation, by switching material import and export, urge by inactivation
Agent regeneration Posterior circle uses, and realizes reaction, the continuous operation of regenerative system.
The dry gas that on-condensible gas after catalytic dehydrogenation unit in the present invention, separative element ii separate can
To direct cycle to catalytic dehydrogenation supplies of unit entrance, recycle.
In addition, the segregation apparatuss of on-condensible gas can be included in separative element, such as flash tank, absorption/parsing
Tower, chiller and compressor etc..
The present invention more specifically embodiment is: is not less than 95% using C_4 hydrocarbon mass content, preferably not
Less than 99%, C 4 olefin mass content is not less than 40%, preferably not below 50%, n-butene and positive fourth
The mass content of alkane and be not less than 35%, preferably not below 40% mixing carbon four raw material.It is 280 in temperature
DEG C~410 DEG C, pressure 0~100kpa, volume space velocity 10~500h-1, oxygen with enter oxidative dehydrogenation list
The olefin molar ratio of all hydrocarbon materials of unit is 0.1~1:1, water or water vapour with enter oxidative dehydrogenation unit
The mass ratio of all hydrocarbon materials be under the process conditions of 0.5~30:1, with oxygen content 32%~
Oxygen-enriched stream mixing between 45% carries out oxidative dehydrogenation, after product isolates butadiene, with alcohol
Class logistics enters etherificate unit, and alcohols with the isobutene. mol ratio in the hydrocarbon material entering methyltertiarvbutyl ether reactor is
0.8~1.5:1, preferably 1.1~1.3:1, in 30~100 DEG C of temperature, preferably 45~80 DEG C, pressure is
0.1~2.0mpa, preferably 0.5~1.5mpa, volume space velocity is 0.1~5h-1, preferably 1~2h-1
Under conditions of carry out etherification reaction after, after isolating ether compound in product and other components, remain
Remaining C_4 hydrocarbon enters catalytic dehydrogenation unit, and in 480~700 DEG C of temperature, pressure 0.01~3mpa, volume is empty
Speed is 0.1~10h-1, hydrogen with enter catalytic dehydrogenation unit all hydrocarbon materials mol ratio be 0.01~
After carrying out catalytic dehydrogenating reaction under conditions of 1:1, enter oxidative dehydrogenation unit together with raw material mixing carbon four.
During mixing carbon four modification utilizes, overcoming isomerization technique, it produced advantages of the present invention
Unfriendly to environment in journey, high temperature aromatization technology dry gas production rate is high by 20%, technical process easily
The shortcomings of economic benefit can be subject to no small loss, during etherification technology continues deeper into research and utilization,
Produce diene units and alkadienes separative element by increasing oxidative dehydrogenation, both overcome the serious shadow of alkadienes
While ringing conversion ratio, the ether compound yield that monoolefine is etherified, the diene of a certain amount of high value of by-product
Hydrocarbon, thus improve economic benefit and the market competitiveness of this technique, the also utilization low-carbon (LC) for more becoming more meticulous
Alkanes provide another technique.In addition, in oxidative dehydrogenation process, due to the generation of side reaction,
A small amount of ketone and aldehyde can be produced.The amount of aldehyde and ketone generation is too high, directly affects alkadienes optionally simultaneously,
Process washing aldehyde and the waste water process of ketone generation also can increase process costs.In the present invention, oxygen-enriched by controlling
In air-flow, oxygen content enters reaction system material total amount to control, and to control oxygen atom in reaction system, alkene
The contact with catalyst for the hydrocarbon, controls reaction time from still further aspect.This method not only can guarantee that list
Alkene is fully converted into alkadienes, and effectively controls the generation of alcohols and aldehydes, improves two
The yield of alkene and selectivity.
Brief description
Fig. 1 is a kind of process flow diagram of the application present invention.
In figure: r1- oxidative dehydrogenation reactor, r2- methyltertiarvbutyl ether reactor, r3- catalytic dehydrogenating reaction device, t1,
T2, t3- are reactor r1, r2, r3 piece-rate system i, ii below, iii.
Specific embodiment
Below by embodiment in detail the present invention is described in detail.Table 1, table 2 by embodiment employing mixing carbon four raw material
Property, mixing carbon four a is catalyzed workshop mixing carbon four for Lanzhou Petrochemical Company, and mixing carbon four b refines for grand celebration
Change company one urges mixing carbon four again.Methanol adopts the methanol that commercially available Cangzhou Zheng Yuan Chemical Co., Ltd. produces, its
The mass content of middle methanol is 99.5%.Ethanol adopts the nothing that commercially available Yixing City Qiu Yun Chemical Co., Ltd. produces
The mass content of water-ethanol, wherein ethanol is 99.5%.
Table 1 mixes the composition (w%) of carbon four a
Table 2 mixing carbon four b composition (w%)
Component | ω % | Component | ω % |
Propane | 0.00 | Isobutene. | 12.45 |
Propylene | 0.00 | Cis-butene-2 | 12.79 |
Iso-butane | 34.29 | Isopentane | 0.06 |
Normal butane | 10.38 | 1,3- butadiene | 0.07 |
Trans-butene-2 | 17.33 | 2- methyl-2-butene | 0.02 |
1-butylene | 12.63 | 1- amylene | 0.04 |
All using technique as shown in Figure 1, in embodiment, catalytic dehydrogenating reaction device pressurizes embodiment for 200ml
Two reactor cycles of fixed bed reactors use, and oxidative dehydrogenation unit adopts the suspension bed reaction of 100ml
Device, etherification reaction system adopts catalytic distillation reaction unit, and pre- methyltertiarvbutyl ether reactor is 200ml fixed bed,
In reactive distillation column, loaded catalyst is 150ml.Analysis sample is the instantaneous sample after reacting 3 hours.Point
The rectifying column being 18 using theoretical cam curve in unit i (t1).Adopt in separative element ii (t2)
After cyclone separator dehydration, flash distillation removes on-condensible gas, and extraction isolates alkadienes.Separative element iii
(t3) rectifying column being 10 using number of theoretical plate.
Prepare in the raw material that catalyst is adopted in embodiment, sesbania powder is technical grade, other is commercially availableization
Learn pure reagent.
Water is deionized-distilled water.
Oxygen-enriched stream is by technical grade pure oxygen and air mixed configuration.
In embodiment, the content of alkene, the yield of alkadienes, the yield of aromatization products, arene content
Computational methods are as follows:
In the quality/catalytic dehydrogenation product of produced butylene, amylene in the content of alkene=catalytic dehydrogenation product
Quality * 100 of all hydro carbons
The mass yield of alcohols=alcohols quality produced by oxidative dehydrogenation unit and/entrance oxidative dehydrogenation unit
Quality * 100 of middle hydrocarbon material
The mass yield of ketone=ketone quality produced by oxidative dehydrogenation unit and/entrance oxidative dehydrogenation unit
Quality * 100 of middle hydrocarbon material
The mass yield of alkadienes=alkadienes quality produced by oxidative dehydrogenation unit/entrance oxidative dehydrogenation list
Quality * 100 of hydrocarbon material in unit
Quality after yield=etherificate all product removal on-condensible gas of etherification product/entrance etherificate unit hydrocarbon
Quality * 100 of class material
Embodiment 1
Olefin oxidation dehydrogenation adopts the preparation method system of embodiment 2 in patent cn102671714a
Standby, concrete preparation method is as follows: 17 grams of magnesium nitrate hexahydrates is dissolved in 20ml distilled water, then
Add 20 grams of zirconium oxides, above-mentioned mixed solution be evaporated be dried 12 hours afterwards in Muffle furnace at 80 DEG C,
The solid sample of heating gained 3 hours in air atmosphere at 550 DEG C, then use metavanadic acid ammonia spirit to soak
Stain sample.Metavanadic acid ammonia spirit is by steaming 5 grams of metavanadic acid ammonia and 10.6 grams of dissolving oxalic acid a small amount of
Prepare in distilled water.It is being dried 12 hours at 80 DEG C through the sample of metavanadic acid ammonia solution dipping, Ran Hou
In Muffle furnace, heat the solid sample 3 hours of gained in the air atmosphere at 550 DEG C, final sizing is
40~80 mesh are stand-by.Catalyst for etherification adopts the kc-116 type resin catalyst that Kai Rui chemical company produces,
Its particle size range >=99% (0.355~1.250mm), wet true density 1150~1250g/l, total exchange capacity
≥1.7mmol/ml[h+], mechanical strength >=98% (H type).Catalytic dehydrogenation catalyst adopts Haitai company
Htpb-dh dehydrogenation, wherein with al2o3For carrier with pt and cl as active component, wherein pt
Mass content be 1%, chlorine mass content be 2%, specific surface area be 200m2/ g, pore volume 0.5ml/g,
A diameter of 1.59mm, heap density 0.6g/cm3.Raw material a enters oxidative dehydrogenation with empty gas and water through preheating
In reactor, at 340 DEG C, atmospheric pressure, air speed 400h-1, enter all hydrocarbons of oxidation deacidification unit
Alkene in material: oxygen=1:0.68 (mol ratio), enter all hydrocarbon materials of oxidative dehydrogenation unit: water
Reacted under the process conditions of=1:12 (mass ratio).In product, the mass yield of alkadienes is
55.4%, the mass yield of alcohols is 0.52%, and the mass yield of ketone is 0.45%.Product is passed through
Separative element i, after isolating butadiene, by other C-4-fractions enter methyltertiarvbutyl ether reactor in, etherificate anti-
The condition is answered to be: 45 DEG C of reaction temperature, volume space velocity 2h-1, reaction pressure 1.5mpa, wherein methanol with enter
The mol ratio entering isobutene. in hydrocarbon material in methyltertiarvbutyl ether reactor is 1.2:1.In product, ethers chemical combination
The mass yield of thing is 49.2%.After separative element ii isolates ether compound, C_4 hydrocarbon enters and urges
In fluidized dehydrogenation reactor, in hydrogen with all hydrocarbon material mol ratios entering catalytic deoxidation unit it is
0.25:1, in 480 DEG C of reaction temperature, volume space velocity 0.1h-1, it is catalyzed under conditions of reaction pressure 0.01mpa
Dehydrogenation, it is 37.1% that reaction obtains olefin(e) centent in dehydrogenation product.
Embodiment 2
Olefin oxidation dehydrogenation adopts the preparation of catalyst in embodiment 1 in patent cn99106660.x
Method, its concrete preparation method is as follows: by the manganese dioxide powder of 43.5g with 1000ml water in same appearance
In device, agitating heating, after 10 minutes, adds 1.09 grams of antimony trioxide powder, system is heated to after 80 DEG C
Then temperature is heated to 90 DEG C and is stirred for 4 hours by stirring 2 hours, when System forming pastel,
It is dried 14 hours at 120 DEG C, makes powder, molding, final sizing is that 40~80 mesh are stand-by.Etherificate is urged
Agent adopts the d005-ii resin catalyst that Dandong Mingzhu Special Type Resin Co., Ltd. produces.Its particle size range
0.315~1.25mm, wet true density 1180~1200g/l, total exchange capacity >=5.2mmol/g [h+], machine
Tool intensity >=95% (H type).Catalytic dehydrogenation catalyst adopts the side of embodiment 4 in cn101940922a
Prepared by method.It concretely comprises the following steps: first weighs 117.5 grams of chromium oxide, is dissolved in deionized water and being sufficiently stirred for,
Being configured to weight concentration is 47% oxidation chromium solution.It is reconfigured at the potassium nitrate that weight concentration is 3.86% water-soluble
Liquid.Then by 55.0 grams of boehmites, 2.2 grams of bentonite, the oxidation chromium solution preparing with 7.59 grams
It is sufficiently mixed, mediate, be extruded into bead.Then it is dried 3 hours at 120 DEG C, then in 500 DEG C of constant temperature
3 hours, in 620 DEG C of constant temperature 2 hours, finally 760 DEG C of roastings 4 hours under 20% water and 80% air.
Take 11.39 grams of the oxidation chromium solution preparing again, roasting sample is impregnated 20 minutes, at 120 DEG C
It is dried 3 hours, in 550 DEG C of constant temperature calcinings 5 hours.The Alkitrate preparing is taken to impregnate again,
120 DEG C of dryings 3 hours, standby in 620 DEG C of constant temperature calcinings 6 hours.Raw material b with oxygenous 45% richness
Oxygen stream, water enter in oxidative dehydrogenation reactor through preheating, at 350 DEG C, pressure 100kpa, and volume
Air speed 10h-1, enter the alkene in the hydrocarbon material of oxidation unit: oxygen=1:0.3 (mol ratio), enter oxidation
The hydrocarbon material of unit: reacted under the process conditions of water=1:30 (mass ratio).In product, diene
The mass yield of hydrocarbon is 49.2%, and the mass yield of alcohols is 0.47%, and the mass yield of ketone is 0.23%.
Product, through separative element i, isolates butadiene, and other C-4-fractions enter in methyltertiarvbutyl ether reactor,
The reaction condition of etherificate is: 80 DEG C of reaction temperature, volume space velocity 3.0h-1, reaction pressure 1.0mpa, its
Middle methanol is 1.1:1 with the mol ratio entering isobutene. in hydrocarbon material in methyltertiarvbutyl ether reactor.In product,
The mass yield of ether compound is 44.8%.After separative element ii isolates ether compound, carbon four
Hydrocarbon enter catalytic dehydrogenating reaction device in, hydrogen with enter catalytic deoxidation unit all hydrocarbon material mol ratios
For 0.1:1, in 700 DEG C of reaction temperature, volume space velocity 1.0h-1, reaction pressure 0.15mpa reacted,
It is 51.6% that reaction obtains olefin(e) centent in dehydrogenation product.
Embodiment 3
Olefin oxidation dehydrogenation adopts the method for preparation example 2 in patent 200780013916.9 to be obtained,
It specifically comprises the following steps that and 69 grams of ammonium molybdate is dissolved in stirring in 500ml distilled water, then by 108.1
Gram bismuth nitrate be added in 5.3% salpeter solution and stir to after be completely dissolved, be added drop-wise to ammonium molybdate solution
In.Then Deca ammonia makes the ph to 1.5 of above-mentioned solution, and after stirring 1 hour, decompression sucking filtration obtains solid
Body sample, then at 100 DEG C, solid sample is dried after 26 hours, at 475 DEG C in Muffle furnace,
Calcining 24 hours, last crushing and screening is that 20~80 mesh are stand-by.Catalyst for etherification adopts Nankai University's chemical industry
The nkc-9 cation exchange resin catalyst that factory produces.Its particle size range >=95% (0.4~1.25mm),
Specific surface area 77m2/ g, pore volume 0.27ml/g, total exchange capacity >=4.7mmol/g [h+].Dehydrogenation
Using the method preparation using embodiment 1 in patent cn 101618319.By 2.24 grams of calcium oxide and 3.1
Gram Polyethylene Glycol is dissolved in 120ml deionized water, 240 DEG C of hydrothermal treatment consists 24 hours, and 600 DEG C of calcinations 5 are little
Shi Hou, is used appropriate dehydrated alcohol to mix homogeneously with 7.2 grams of chromic nitrates, 6 grams of aluminium sesquioxide, is dried
Grind uniformly after 12 hours, standby after calcination 3 hours at 550 DEG C.With oxygenous 35% oxygen rich air
Stream, water enter in oxidative dehydrogenation reactor through preheating, at 380 DEG C, 50kpa, volume space velocity 60h-1,
Enter the alkene in the hydrocarbon material of oxidation unit: oxygen=1:0.1 (mol ratio), enter the hydro carbons of oxidation unit
Material: reacted under the process conditions of water=1:5 (mass ratio).In product, the mass yield of alkadienes
For 56.1%, the mass yield of alcohols is 0.39%, and the mass yield of ketone is 0.18%.Product warp
Cross separative element i, isolate butadiene, other carbon four components enter in methyltertiarvbutyl ether reactor, the reaction of etherificate
Condition is: 65 DEG C of reaction temperature, volume space velocity 4h-1, reaction pressure 0.5mpa, wherein methanol and entrance
In hydrocarbon material in methyltertiarvbutyl ether reactor, the mol ratio of isobutene. is 1.3:1.In product, ether compound
Mass yield be 58.8%.After separative element ii isolates ether compound, C_4 hydrocarbon enters catalysis
In dehydrogenation reactor, hydrogen is 0.01:1 with all hydrocarbon material mol ratios entering catalytic deoxidation unit,
570 DEG C of reaction temperature, volume space velocity 3.0h-1, reacted under conditions of reaction pressure 1.7mpa, reaction
Obtaining olefin(e) centent in dehydrogenation product is 54.9%.
Embodiment 4
Olefin oxidation dehydrogenation adopts the method system preparing embodiment 2 in patent 200880014941.3
, it specifically comprises the following steps that and for 14.2 grams of zinc chloride and 56.1 grams of ferric chloride hexahydrates to be dissolved in 800ml
In distilled water, it is stirred well to after being completely dissolved, the sodium hydrate aqueous solution of Deca 3m adjusts above-mentioned solution
Ph value to 8, after being then stirred at room temperature 12 hours, decompression sucking filtration obtains solid sample.By solid-like
Product are dried 16 hours at 175 DEG C, calcine 12 hours at 650 DEG C, and last crushing and screening is 20~65
Mesh is stand-by.The macropore strong acid that catalyst for etherification is produced using Jiangsu AudioCodes petrochemistry Technology Co., Ltd.
Resin catalyst, its granularity is 0.315-1.25mm, bulk density 0.77-0.85g/ml, and specific surface area is big
In 20-70m2/ g, aperture is more than 20-50nm, and pore volume is more than 0.3-0.5cc/g.Dehydrogenation adopts
The method preparation of embodiment 4 in cn101940922a.It concretely comprises the following steps: first weighs 117.5 grams of oxygen
Change chromium, be dissolved in deionized water and being sufficiently stirred for, being configured to weight concentration is 47% oxidation chromium solution.Join again
Put the Alkitrate that weight concentration is 3.86%.Then by 55.0 grams of boehmites, 2.2 grams of swellings
Soil, the oxidation chromium solution being prepared with 7.59 grams is sufficiently mixed, and mediates, is extruded into bead.Then again 120
It is dried at DEG C 3 hours, then in 500 DEG C of constant temperature 3 hours, in 620 DEG C of constant temperature 2 hours, finally 20%
Water and lower 760 DEG C of roastings of 80% air 4 hours.Take 11.39 grams of the oxidation chromium solution preparing again, will roast
Burned sample impregnates 20 minutes, in 120 DEG C of dryings 3 hours, in 550 DEG C of constant temperature calcinings 5 hours.
The Alkitrate preparing is taken to impregnate, in 120 DEG C of dryings 3 hours, in 620 DEG C of constant temperature calcinings 6 again
Hour is standby.Raw material b enters oxidative dehydrogenation with oxygenous 40% oxygen-enriched stream, water through preheating
In device, at 390 DEG C, 20kpa, volume space velocity 500h-1, enter the alkene in the hydrocarbon material of oxidation unit
Hydrocarbon: oxygen=1:0.8 (mol ratio), enter the hydrocarbon material of oxidation unit: the process conditions of water=1:16 (mass ratio)
Under reacted.In product, the mass yield of alkadienes is 46.7%, and the mass yield of alcohols is
0.41%, the mass yield of ketone is 0.20%.Product, through separative element i, isolates butadiene,
Other C-4-fractions enter in methyltertiarvbutyl ether reactor, and the reaction condition of etherificate is: 75 DEG C of reaction temperature, volume
Air speed 5h-1, isobutyl in hydrocarbon material in reaction pressure 1.2mpa, wherein methanol and entrance methyltertiarvbutyl ether reactor
The mol ratio of alkene is 1.5:1.In product, the mass yield of ether compound is 50.5%.Through undue
Isolate after ether compound from unit ii, C_4 hydrocarbon enters in catalytic dehydrogenating reaction device, hydrogen and entrance
All hydrocarbon material mol ratios of catalytic deoxidation unit are 0.3:1, in 600 DEG C of reaction temperature, volume space velocity
5.0h-1, reacted under reaction pressure 1.1mpa, it is 64.0% that reaction obtains olefin(e) centent in dehydrogenation product.
Embodiment 5
Olefin oxidation dehydrogenation adopts method in embodiment 4 in cn96113127 to be obtained, concrete steps
As follows: by 177 grams of fe (no3)3·9h2O, 43.3 grams of zn (no3)2·6h2O, 43 grams of ca (no3)2·4h2O,
1.5 grams of co (no3)2·6h2O is dissolved in the distilled water of 500ml, and the quick ammonia stirring lower instillation 20% sinks
Form sediment, in precipitation process, add 1 gram of sesbania powder.When ph value is to 8.5 in solution, terminates ammonia and instill.
Precipitate is in 80 DEG C of heat ageings 1 hour, aging 30 minutes at 55 DEG C, filters, uses 1000ml every time
Water washing, altogether twice.Filter cake, in 110 DEG C of dryings 12 hours, is calcined 14 hours at 650 DEG C, is finally sieved
It is divided into 40~80 mesh stand-by.Catalyst for etherification adopts the etherified resin catalysis that Kai Rui Chemical Co., Ltd. produces
Agent, its particle size range 0.335~1.25mm, wet true density 0.75~0.85g/ml, total exchange capacity >=5.2
Mmol/g, mechanical strength >=95%.Dehydrogenation adopts embodiment 9 in patent cn96121452.x
Method preparation.Weigh 17 grams of cr (no3)3·9h2O, 1.1 grams of cu (no3)2·3h2O, 80.8 grams
al(no3)3·9h2O, prepares catalyst with coprecipitation, and 10% koh (or naoh) selected by precipitant
Solution, nitrate is dissolved in distilled water, adds precipitant while stirring so as to form gel completely, and
Ph value is 8.5~9, aging 3 hours, filters, and at 110 DEG C, is dried 20 hours, roasts at 650 DEG C
Burn 7 hours, rear standby after crushing and screening.Raw material a is passed through in advance with oxygenous 32% oxygen-enriched stream, water
Heat enters in oxidative dehydrogenation reactor, at 280 DEG C, 10kpa, volume space velocity 300h-1, enter oxidation single
Alkene in the hydrocarbon material of unit: oxygen=1:0.55 (mol ratio), enter the hydrocarbon material of oxidation unit: water
Reacted under the process conditions of=1:10 (mass ratio).In product, the mass yield of alkadienes is
55.6%, the mass yield of alcohols is 0.43%, and the mass yield of ketone is 0.21%.Product is passed through
Separative element i, after isolating butadiene, other C-4-fractions enter in methyltertiarvbutyl ether reactor, the reaction of etherificate
Condition is: 55 DEG C of reaction temperature, volume space velocity 0.1h-1, reaction pressure 2.0mpa, wherein ethanol with enter
Entering isobutene. mol ratio in hydrocarbon material in methyltertiarvbutyl ether reactor is 1.2:1.In product, ether compound
Mass yield be 48.5%.After separative element ii isolates ether compound, C_4 hydrocarbon enters catalysis
In dehydrogenation reactor, hydrogen is 0.15:1 with all hydrocarbon material mol ratios entering catalytic deoxidation unit,
650 DEG C of reaction temperature, volume space velocity 8.0h-1, reacted under conditions of reaction pressure 2.4mpa, reaction
Obtaining olefin(e) centent in dehydrogenation product is 35.6%.
Embodiment 6
Olefin oxidation dehydrogenation adopts the preparation method preparation of embodiment 1 in patent cn103055890,
Specifically comprise the following steps that and first the zinc powder of 280 grams of iron powder and 80.3 grams is added to 1000 milliliters of 1m's
In salpeter solution, to be dissolved completely after, add 97.1 grams of manganese nitrates and 3.3 grams of magnesium nitrates, be completely dissolved
Afterwards, under conditions of 60 DEG C of solution temperature, the ammonia of Deca 20% is simultaneously sufficiently stirred for, to ph value 7.5
Afterwards, solution temperature continues to keep 60 DEG C, continues aging 60 minutes of stirring, filters serosity and washs to ph
Value in 7.0~9.0 values, then by after filter cake extrusion, 200 DEG C of dryings 12 hours, 500 DEG C of calcinings 48 are little
Shi Hou, by short for strip catalyst broken be 2~3 millimeters stand-by.Catalyst for etherification buys petrochemical industry academy of science
The rze-3 zeolite catalyst for etherification of research and development, profile is that diameter 8mm is spherical, bulk density 0.71g/cm3,
Specific surface area 487m2/ g, pore volume 0.464ml/g, average pore size 175nm, intensity > 20n.Dehydrogenation is urged
Agent prepares catalyst using the step of catalyst preparation in embodiment 1 in patent cn 101623633a.
Zsm-5 molecular screen primary powder is placed in the sncl of 0.16m first2·2h210hr is impregnated in 80 DEG C in o solution,
The load capacity making the sn in catalyst reaches 4wt%, then 6hr is dried at 120 DEG C.Dried
Sample roasting 4hr under 550 DEG C of air atmosphere.Powder after roasting is in the h of 0.03m2ptcl6·6h2o
Impregnate 4hr in solution at 80 DEG C, make catalyst that pt content be 20wt% to be finally obtained, then 120
6hr is dried, roasting 4hr at 550 DEG C at DEG C.Standby in 550 DEG C of hydrogen reducing 12hr afterwards.With pure oxygen
Gas and water enters in oxidative dehydrogenation reactor through preheating, at 340 DEG C, 70kpa, volume space velocity 250h-1,
Enter the alkene in the hydrocarbon material of oxidation unit: oxygen=1:0.1 (mol ratio), enter the hydrocarbon of oxidation unit
Material: reacted under the process conditions of water=1:0.5 (mass ratio).In product, the quality of alkadienes is received
Rate is 41.7%, and the mass yield of alcohols is 0.82%, and the mass yield of ketone is 0.66%.Product
Through separative element i, isolate butadiene, other carbon four components enter in methyltertiarvbutyl ether reactor, etherification reaction
Condition is: 30 DEG C of reaction temperature, volume space velocity 0.5h-1, reaction pressure 1.7mpa, wherein methanol with enter
The mol ratio entering isobutene. in hydrocarbon material in methyltertiarvbutyl ether reactor is 0.95:1.In product, ethers
The mass yield of compound is 42.5%.After separative element ii isolates ether compound, C_4 hydrocarbon enters
In catalytic dehydrogenating reaction device, hydrogen is 0.5:1 with all hydrocarbon material mol ratios entering catalytic deoxidation unit,
In 550 DEG C of reaction temperature, volume space velocity 10.0h-1, reacted under conditions of reaction pressure 3.0mpa,
It is 44.7% that reaction obtains olefin(e) centent in dehydrogenation product.
Comparative example
Catalyst for etherification buys the rze-3 zeolite catalyst for etherification of petrochemical industry academy of science research and development, and profile is
Diameter 8mm is spherical, bulk density 0.71g/cm3, specific surface area 487m2/ g, pore volume 0.464ml/g,
Average pore size 175nm, intensity > 20n.Dehydrogenation adopts in patent cn 101623633a to be implemented
In example 1, the step of catalyst preparation prepares catalyst.Zsm-5 molecular screen primary powder first is placed in 0.16m's
sncl2·2h2In 80 DEG C of dipping 10hr so that the load capacity of sn in catalyst reaches 4wt% in o solution,
Then 6hr is dried at 120 DEG C.Dried sample roasting 4hr under 550 DEG C of air atmosphere.After roasting
Powder 0.03m h2ptcl6·6h2Impregnate 4hr at 80 DEG C in o solution, make finally to be obtained pt
Content is the catalyst of 20wt%, then 6hr is dried at 120 DEG C, roasting 4hr at 550 DEG C.Exist afterwards
550 DEG C of hydrogen reducing 12hr are standby.Raw material b and methanol mixed enter in methyltertiarvbutyl ether reactor, etherification reaction bar
Part is: 73 DEG C of reaction temperature, volume space velocity 1.4h-1, reaction pressure 1.7mpa, wherein methanol and entrance
In hydrocarbon material in methyltertiarvbutyl ether reactor, the mol ratio of iso-butane is 0.95:1.Through separative element, isolate
Ether compound, its yield is 34.1%.Hydrogen and the institute entering catalytic deoxidation unit in dehydrogenation reactor
Hydrocarbon material mol ratio is had to be 0.5:1, in 550 DEG C of reaction temperature, volume space velocity 10.0h-1, reaction pressure
Reacted under conditions of 3.0mpa, it is 42.5% that reaction obtains olefin(e) centent in dehydrogenation product.
Certainly, the present invention also can have other various embodiments, without departing substantially from present invention spirit and its essence
In the case of, those of ordinary skill in the art can make various corresponding changes according to the present invention and become
Shape, but these corresponding changes and deformation all should belong to the protection domain of the claims in the present invention.
Claims (17)
1. a kind of mixing carbon four method for transformation is it is characterised in that conversion process at least comprises the steps: the
One step mixing carbon four raw material, the logistics containing oxidant and water or water vapour enter oxidative dehydrogenation unit, in dress
After filling out reaction in the reactor of Oxydehydrogenation catalyst, enter separative element i, reacted logistics is divided into
Butadiene, other C-4-fraction and other components;Second step is by the other C-4-fractions isolated in the first step
Send into etherificate unit with alcohols logistics, carry out etherification reaction in the reactor equipped with catalyst for etherification, reaction is produced
Thing enters separative element ii, and reacted logistics is divided into carbon more than five component, C_4 hydrocarbon and other component;
3rd step sends into catalytic dehydrogenation unit by isolating C_4 hydrocarbon in second step with hydrogen, is urging equipped with catalytic dehydrogenation
Carry out alkane catalytic dehydrogenating reaction in the reactor of agent, and by the logistics after catalytic dehydrogenation through separative element
After iii isolates on-condensible gas, send into oxidative dehydrogenation unit together with mixing carbon four raw material.
2. mixing carbon four method for transformation according to claim 1 is it is characterised in that mix carbon four raw material
Refer to refine oil the C_4 hydrocarbon with generation in chemical process, carbon four, catalytically cracked C four, cracking preferably after ether
Carbon four and or light gasoline separation component;Or C_4 hydrocarbon mass content is not less than 95% in mixing carbon four,
In preferably not below 99%, or mixing carbon four, alkene mass content is not less than 40%, preferably not below 50%,
Or the mass content of n-butene and normal butane and be not less than 35%, preferably not below 40% in mixing carbon four.
3. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit
N-butene conversion be not less than 70%, preferably not below 75%.
4. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit
Reaction condition be: temperature be 280 DEG C~410 DEG C, pressure be 0~100kpa, volume space velocity be 10~
500h-1, preferred reaction condition is: temperature is 310 DEG C~395 DEG C, and pressure is 0~40kpa, volume
Air speed is 60~400h-1.
5. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit
Oxidant be material stream containing oxygen molecule or containing oxidizing strong oxygen atom, preferably air, oxygen-enriched
Gas or oxygen.
6. mixing carbon four method for transformation according to claim 1 is it is characterised in that containing oxidant
With oxymeter in logistics, oxygen with the olefin molar ratio entering all hydrocarbon materials in oxidative dehydrogenation unit is
0.1~1.0:1, preferably 0.3~0.85:1.
7. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit
Vapor is 0.5~30 with butylene mass ratio in all hydrocarbon materials of entrance oxidative dehydrogenation unit, preferably
5~20.
8. mixing carbon four method for transformation according to claim 1 is it is characterised in that separative element i divides
The content separating out butadiene in the C-4-fraction after butadiene is not higher than 0.3%, and preferably not higher than 0.1%.
9. mixing carbon four method for transformation according to claim 1 is it is characterised in that etherification reaction unit
Middle isobutene conversion is not less than 92%.
10. mixing carbon four method for transformation according to claim 1 is it is characterised in that etherification reaction unit
Middle alcohols logistics refers to low-carbon alcohols, special recommendation methanol, ethanol.
11. mixing carbon four method for transformation according to claim 1 are it is characterised in that enter etherification reaction
In unit, alcohols with enter etherification reaction unit all hydrocarbon materials in isobutene. mol ratio be 0.8~
1.5:1, preferably 1.1~1.3:1.
12. according to claim 1 mixing carbon four method for transformation it is characterised in that etherification reaction anti-
The condition is answered to be: temperature is 30~100 DEG C, pressure is 0.1~2.0mpa, volume space velocity is 0.1~5h-1;
Preferably temperature is 45~80 DEG C, and pressure is 0.5~1.5mpa, and volume space velocity is 1~2h-1.
13. mixing carbon four method for transformation according to claim 1 are it is characterised in that separated unit ii
Isolate in the C_4 hydrocarbon after carbon five and above component, the mass content of C_4 hydrocarbon class is not less than 97%,
It is not less than 99% well.
14. mixing carbon four method for transformation according to claim 1 are it is characterised in that catalytic dehydrogenation unit
In middle catalytic dehydrogenation product, olefin(e) centent is not less than 35%, is preferably such that olefin(e) centent more than 45%.
15. mixing carbon four method for transformation according to claim 1 are it is characterised in that catalytic dehydrogenation unit
Reaction condition be preferably: temperature be 480~700 DEG C, pressure be 0.01~3mpa, liquid volume air speed
For 0.1~10h-1;Preferably temperature is 560~650 DEG C, and pressure is 0.4~1.2mpa, and liquid volume is empty
Speed is 2~7h-1.
16. mixing carbon four method for transformation according to claim 1 are it is characterised in that enter catalytic dehydrogenation
In unit, hydrogen is 0.01~1:1 with the mol ratio of all hydrocarbon materials entering catalytic dehydrogenation unit,
It is well 0.1~0.5:1.
17. mixing carbon four method for transformation according to claim 1 are it is characterised in that catalytic dehydrogenation unit
In catalytic dehydrogenating reaction device be two or more fixed bed reactors used in parallel.
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CN101555197A (en) * | 2008-04-11 | 2009-10-14 | 中国石油化工股份有限公司 | Comprehensive use method of mixed C-4 |
CN103193581A (en) * | 2013-04-15 | 2013-07-10 | 华东理工大学 | Device and method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4 |
US20140081062A1 (en) * | 2012-09-20 | 2014-03-20 | Basf Se | Process for the Preparation of Butadiene with Removal of Oxygen from C4-Hydrocarbon Streams |
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CN101119949A (en) * | 2005-01-17 | 2008-02-06 | 巴斯福股份公司 | Method for producing butadiene from n-butane |
CN101555197A (en) * | 2008-04-11 | 2009-10-14 | 中国石油化工股份有限公司 | Comprehensive use method of mixed C-4 |
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