CN105732271A - Front hydrogenation method of trace acetylene in methanol-to-olefin device - Google Patents
Front hydrogenation method of trace acetylene in methanol-to-olefin device Download PDFInfo
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- CN105732271A CN105732271A CN201410771840.8A CN201410771840A CN105732271A CN 105732271 A CN105732271 A CN 105732271A CN 201410771840 A CN201410771840 A CN 201410771840A CN 105732271 A CN105732271 A CN 105732271A
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- hydroxyl
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- bipyridyl
- precursor
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 68
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 106
- 238000002360 preparation method Methods 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 4
- 229910002668 Pd-Cu Inorganic materials 0.000 claims abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 88
- 229910052593 corundum Inorganic materials 0.000 claims description 47
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 47
- 239000002243 precursor Substances 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- MWPGSUYGVCNVKP-UHFFFAOYSA-N 2-pyridin-2-ylpyridin-3-ol Chemical group OC1=CC=CN=C1C1=CC=CC=N1 MWPGSUYGVCNVKP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 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 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005755 formation reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 23
- 239000005977 Ethylene Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000047 product Substances 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 229920002521 macromolecule Polymers 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- -1 ethylene, propylene Chemical group 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 102000002322 Egg Proteins Human genes 0.000 description 5
- 108010000912 Egg Proteins Proteins 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 210000003278 egg shell Anatomy 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- DDHGHUCXYQKHDF-UHFFFAOYSA-N 3-hydroxy-2-pyridin-2-yl-1H-pyridin-4-one Chemical group OC1=CC=NC(C=2N=CC=CC=2)=C1O DDHGHUCXYQKHDF-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- WZGWWPARMFQTAY-UHFFFAOYSA-N ethene;methanol Chemical group OC.C=C WZGWWPARMFQTAY-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010187 selection method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NPOJSRFZNPCHGN-UHFFFAOYSA-N 5-(6-oxo-1h-pyridin-3-yl)-1h-pyridin-2-one Chemical group C1=NC(O)=CC=C1C1=CC=C(O)N=C1 NPOJSRFZNPCHGN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 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
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 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
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 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
- 238000007614 solvation Methods 0.000 description 1
- 238000005507 spraying 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a front hydrogenation method of trace acetylene in a methanol-to-olefin device, wherein an adiabatic bed reactor for hydrogenation is positioned in front of a demethanizer or a deethanizer, and the method is characterized in that: the fixed bed reactor is filled with a Pd-Cu catalyst, and the catalyst is combined with a bipyridyl derivative with hydroxyl through a carrier in the preparation process, and the hydroxyl bipyridyl derivative combined with the carrier and an active component form a metal complex; by adopting the hydrogenation method, the selectivity of the hydrogenation reaction is greatly superior to that of the traditional hydrogenation method, and the loss of ethylene is reduced; the hydrogenation activity is excellent, the content of the outlet acetylene is obviously lower than that of other two hydrogenation methods, the purity of ethylene is improved, so that the performance of a polymer-grade ethylene product can be well improved, and simultaneously, the reduction of green oil ensures that the active center of the catalyst is not covered by-products, the activity and the selectivity of the catalyst are well maintained, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to a kind of front-end hydrogenation method of trace acetylene in a kind of selection method of hydrotreating, particularly methanol-to-olefins device.
Background technology
The low-carbon alkene such as ethylene, propylene is important basic chemical raw materials, and along with the demand of low-carbon alkene is day by day risen by the development of the development of Chinese national economy, particularly modern chemical industry, imbalance between supply and demand also will become increasingly conspicuous.Up to now, the important channel of the low-carbon alkene such as preparing ethylene, propylene, remain by Petroleum, the catalytic cracking of light diesel fuel (being all from oil), cracking, as raw material resources such as the Petroleum of ethylene production raw material, light diesel fuels, be faced with increasingly severe short situation.It addition, crude oil in China import volume has accounted for about the half of processing total amount in recent years, the at a relatively high percentage of import will be maintained with the polyolefin products that ethylene, propylene are raw material.Therefore, development non-oil resource carrys out the technology of preparing low-carbon olefins and day by day causes the attention of people.
Methanol ethylene, the MTO technique of propylene and the MTP technique of preparing propylene from methanol are Chemical Engineering Technologies important at present.The methanol that this technology synthesizes with coal or natural gas, for raw material, produces low-carbon alkene, is the development non-oil resource core technology that produces the product such as ethylene, propylene.
MTO technology is the committed step in coal-based alkene industrial chain, its technological process is mainly under suitable operating condition, with methanol for raw material, choose suitable catalyst (ZSM-5 zeolite catalyst, SAPO-34 molecular sieve etc.), in fixing bed and vulcanization bed reactor, pass through preparing low-carbon olefin through methanol dehydration.Difference according to purpose product, MTO technology is divided into methanol ethylene, propylene (methanol-to-olefin, MTO), preparing propylene from methanol (methanol-to-propylene, MTP).The representative technology of MTO technique has AP Oil company (UOP) and the UOP/HydroMTO technology of Hydro company (NorskHydro) joint development, the DMTO technology of Dalian Inst of Chemicophysics, Chinese Academy of Sciences's autonomous innovation research and development；The representative technology of MTP technique has the FMTP technology of LurgiMTP technology that LURGI (Lurgi) develops and the independent research of Tsing-Hua University of China.
The whole reaction of methanol-to-olefins can be divided into two stages: water smoking, cracking reaction stage
1. the water smoking
2CH3OH→CH3OCH3+H2O+Q
2. the cracking reaction stage
The catalytic cracking reaction that this course of reaction is mainly dehydration reaction product dimethyl ether and a small amount of unconverted material benzenemethanol carries out, including:
Primary response (generation alkene):
nCH3OH→CnH2n+nH2O+Q
nCH3OH→2CnH2n+nH2O+Q
N=2 and 3 (mainly), 4,5 and 6 (secondary)
Any of the above olefin product is gaseous state.
Side reaction (generates alkane, aromatic hydrocarbons, oxycarbide coking):
(n+1)CH3OH→CnH2n+2+C+(n+1)H2O+Q
(2n+1)CH3OH→2CnH2n+2+CO+2nH2O+Q
(3n+1)CH3OH→3CnH2n+2+CO2+(3n-1)H2O+Q
N=1,2,3,4,5 ... ...
nCH3OCH3→CnH2n-6+3H2+nH2O+Q
N=6,7,8 ... ...
Above product has gaseous state (CO, H2、H2O、CO2、CH4In alkane, aromatic hydrocarbons etc.) and solid-state (macromolecule hydrocarbon and coke) point.
Methanol, after dehydration, cracking, separation, still contains the acetylene of 5～100ppm in the ethylene feed of deethanizer overhead, it affects the polymerization process of ethylene, and causes product quality to decline, it is necessary to by selecting method of hydrotreating to be removed.In ethylene feed, the polymerization process of ethylene is had extremely important impact by the hydrogenation that selects of trace acetylene, except ensureing that hydrogenation has enough activity, have good in alkynes performance when low acetylene content, ensure that the acetylene content of reactor outlet is up to standard, outside the hydrogen content of reactor outlet is up to standard, also require that selectivity of catalyst is excellent, it is possible to make the generation ethane that ethylene is the least possible, it is ensured that hydrogenation process does not bring the loss of device ethylene.
The separative element of methanol-to-olefins device, the order separation process of current commonly used Lummus company.The refining adoptable front-end hydrogenation of ethylene, two kinds of techniques of back end hydrogenation.Hydrogenation reactor is front-end hydrogenation before being positioned at separative element, and hydrogenation reactor is back end hydrogenation after being positioned at separative element.The commonly used back end hydrogenation technique of current methanol-to-olefins device, carries out hydrofinishing elimination acetylene by the isolated ethylene of pyrolysis product, and propylene does not set hydrofining reactor, and isolated carbon four blending ingredients carries out selective hydrogenation and removing butadiene.But this technique exists drawback, adopting first to separate and ethylene, propylene are refined respectively again, plant energy consumption is of a relatively high.Therefore, it is proposed to before separative element, arrange refining reaction device, the front-end hydrogenation process route separated again after elimination acetylene, contribute to reducing plant energy consumption, improve device economic benefit.
For front-end hydrogenation technique, in methanol-to-olefins device ethylene feed, the selection hydrogenation of trace acetylene is main adopts single hop reactor process.The volume content of each material is as follows: acetylene 5～100ppm, CO1～10ppm, and hydrogen adopts the hydrogen itself contained in material, H2Content is generally 1.2%～2.5%.Reaction pressure 1.5～2.5MPa, air speed 2000～10000h-1, inlet temperature 25 DEG C～50 DEG C.Reactor content composition is complex, and particular make-up is by table 1.
Table 1 methanol-to-olefins device front-end hydrogenation technique acetylene hydrogenation reactor entrance material forms
| Component | Compositing range (v%) | Composition citing (v%) |
| H2 | 1.2～2.5 | 1.72 |
| N2 | 0.5～1.0 | 0.72 |
| O2 | 0.005～0.015 | 0.01 |
| CO | 0.60～1.0 | 0.85 |
| CO2 | 0.20～0.60 | 0.38 |
| H2S | 0～0.0008 | 0.0001 |
| CH4 | 6～10 | 8.09 |
| C2H2 | 0～0.01 | 0.0005 |
| C2H6 | 1～2 | 1.64 |
| C2H4 | 40～60 | 51.10 |
| C3H8 | 1.5～3 | 2.06 |
| C3H6 | 15～40 | 20.91 |
| C3H4 | 0～0.01 | 0.001 |
| C4 | 3～6 | 4.49 |
| C5+ | 6～10 | 8.03 |
Alkynes and diolefin hydrogenate catalyst are (US4762956) by noble metal such as palladium load being obtained in the Inorganic material carrier of porous.In order to increase selectivity of catalyst, reduce the catalysqt deactivation that the green oil produced by oligomerization when being hydrogenated with causes, prior art have employed that to add such as group ib element in the catalyst be the method for co-catalysis component: Pd-Au (US4490481), Pd-Ag (US4404124), Pd-Cu (US3912789), or adding alkali metal or alkaline-earth metal (US5488024) etc., carrier used has aluminium oxide, silicon dioxide (US5856262), the loyal cordierite of honeycomb (CN1176291) etc..
US5856262 reports with the modified silicon oxide of potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) for carrier, and the method for preparation low in acidity palladium catalyst, at air speed 3000h-1, inlet temperature 35 DEG C, entrance acetylene molar fraction 0.71%, when hydrogen alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity reaches 56%.Patent US4404124, with aluminium oxide for carrier, adds promoter silver and palladium effect, is prepared for the C2 hydrogenation catalyst of function admirable.This catalyst has minimizing ethane growing amount, it is suppressed that is adsorbed on the acetylene on catalyst surface and carries out partial hydrogenation dimerization reaction, it is suppressed that 1,3-butadiene generates, and reduces green oil and generates, improves ethylene selectivity, reduce the feature of oxygenatedchemicals growing amount, be applied widely in ethylene industry.But, above-mentioned catalyst all adopts infusion process to prepare, and by the restriction of preparation method, metal dispersity is only about 30%, and catalyst performance there is also many deficiencies, still has necessity of improvement further.
CN101745389A discloses a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene, belong to the synthesis of oil (natural gas) chemical products and new catalytic material technical field, relate to a kind of egg-shell catalyst that preparation of ethylene through selective hydrogenation of acetylene is had superior catalytic performance.It is characterized in that with aluminium oxide (Al2O3) bead is carrier, adopt infusion process to prepare the loaded catalyst that active component palladium be eggshell type and is distributed, and adopt Ag to eggshell type Pd/Al2O3Catalyst is modified.Pd load capacity is 0.01～0.1wt%, Ag and Pd atomic ratio is 1～5.The invention have the advantages that, a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene provided, can when high conversion of alkyne, especially close to 100% conversion of alkyne time, it is achieved high ethylene selectivity.
Traditional Pd-Ag bimetallic selective hydrogenation catalyst is all adopt aqueous impregnation method to prepare.When adopting sub-dip method, what a kind of component can be more is enriched in carrier surface, and another kind of component is enriched in outer surface, and only part metals atom interpenetrates, and defines alloy structure.When adopting total immersion method, owing to the presoma of two metal ion species and the interaction of carrier are different, and surface tension and solvation, it is hardly formed the uniform load of two kinds of components, also can only partly form alloy structure.When this catalyst is applied to C 2 fraction selective hydrogenation, often better at initial reaction stage selectivity, with the prolongation of the time of operation, selectivity constantly declines, and generally runs 3～6 months and is accomplished by regeneration, and economic loss is bigger.
CN201110086174.0 by adsorbing specific macromolecular compound on carrier, macromolecule wrapped layer is formed at carrier surface certain thickness, with with the compound of function base and high molecular weight reactive, can with the function base of active component complexation so as to have, on carrier surface function base, complex reaction is there is, it is ensured that active component is in order and high degree of dispersion by active component.Adopt this patented method, the specific macromolecular compound of carrier adsorption, carry out chemisorbed by the hydroxyl of aluminium oxide and macromolecule, the amount of carrier adsorption macromolecular compound is subjected to the hydroxyl value quantitative limitation of aluminium oxide；Not strong with the complexing of Pd through the macromolecule of functionalization, activity component load quantity does not reach requirement sometimes, goes back residual fraction active component in impregnation liquid, causes catalyst cost to improve；Adopt the method to prepare C2 hydrogenation catalyst and there is also the shortcoming that technological process is complicated.
Select in hydrogenation process at the trace acetylene that air speed is higher, particularly in the front-end hydrogenation technical process that CO content is higher, catalyst activity is required higher by hydrogenation operating mode, and with Pd be active component, Ag be auxiliary agent bimetal supported catalyst for the type device, there is reaction temperature height, activity can not better meet matching requirements, it is easy to shortcoming leakage alkynes occur, need to select more suitable auxiliary agent to prepare catalyst, to meet the hydrogenation requirements of device.
Summary of the invention
It is an object of the invention to provide a kind of front-end hydrogenation method of trace acetylene in methanol-to-olefins device.By selecting active component high degree of dispersion, there is the Pd-Cu catalyst of height alloy structure, improve hydrogenation selectivity, improve ethylene increment, improve plant running stability and economic benefit.
The inventors discovered that, when the catalyst adopting the preparation method of the present invention to prepare, the Pd in catalyst is separated by Cu, the spacing making active center widens, and catalyst selectivity improves, and therefore the surface coking rate of catalyst is greatly reduced, catalyst on-stream cycle time extends, and economic benefits are obvious.
The invention provides a kind of front-end hydrogenation method of trace acetylene in methanol-to-olefins device.Before adiabatic reactor reactor for being hydrogenated with is positioned at domethanizing column or dethanizer, from the carbon one at the bottom of drying tower tower, carbon two and carbon 3 material in methanol-to-olefins device, enter adiabatic reactor reactor to carry out selecting hydrogenation, it is characterised in that: equipped with Pd-Cu series catalysts in adiabatic reactor reactor, with Al2O3Or Al2O3Being carrier with other hopcalite, with the quality of catalyst for 100%, wherein Pd content 0.015～0.050%, Cu content is 0.02～0.3%, and the specific surface area of catalyst is 20～60m2/ g, pore volume is 0.15～0.70mL/g；This catalyst, in preparation process, is combined with hydroxyl-bipyridyl by carrier, and the hydroxyl bipyridyl on carrier forms metal complex with active component；Reaction condition is: adiabatic reactor reactor inlet temperature 30 DEG C～50 DEG C, reaction pressure 1.5～2.5MPa, air speed 5000～15000h-1。
The feature of the Pd-Cu series catalysts used in the present invention is: this catalyst is by the employing PdCu-hydroxyl-bipyridyl/Al of the present invention2O3Prepared by the method for precursor.
The catalyst preparation process recommended, at least includes: load on carrier by hydroxyl dipyridyl derivatives, and the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or nitrilo and Pd, Cu forms complex ion.
The hydroxyl dipyridyl derivatives of the present invention, preferably hydroxyl 2,2,-dipyridyl derivatives, hydroxyl 3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives, can there is good complex reaction with Pd, Cu in two nitrilo at hydroxyl unnecessary after being combined with aluminium oxide and ortho position because of it.
The present invention is the selection method of hydrotreating of trace acetylene in methanol-to-olefins device, and in entrance raw material, composition is mainly ethylene, propylene, and reactor inlet material forms in Table 1.Reactor inlet temperature 30 DEG C～50 DEG C, reaction pressure 1.5～2.5MPa, air speed 5000～10000h-1。
Defining the catalyst type of use in the present invention, such catalyst selectivity and traditional catalyst have bigger difference.
Principles of the invention is: in selective hydrogenation reaction, along with the catalyst activity component Pd, the Cu that use form alloy, the quantity of the hydrogen that caltalyst phase is adsorbed is greatly reduced, and the trend of acetylene generation deep hydrogenation is substantially reduced, and catalyst selectivity significantly improves.
The acquisition of this catalyst preferably includes following steps: by the organic solution of hydroxyl dipyridyl derivatives, impregnates carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution impregnation hydroxyl-bipyridyl/Al of preparation Pd, Cu2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdCu-hydroxyl-bipyridyl/Al2O3Precursor.At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
Carrier of the present invention is preferably aluminium oxide, or mainly contains Al2O3, wherein also doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.Described aluminium oxide is γ, δ, θ, alpha-crystal form or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation.
In the present invention, carrier can be spherical, cylindrical, annular, bar shaped, cloverleaf pattern, Herba Galii Bungei shape etc..
Catalyst preparing of the present invention can adopt procedure below to implement, and this process can be divided into 3 steps to carry out.
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
The organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, makes solution be absorbed, at 20 DEG C～60 DEG C temperature, react 2～24h, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；Hydroxyl dipyridyl derivatives organic solution volume is preferably equal to or greater than the 80% of carrier cumulative volume.
B.PdCu-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed-cation solution of preparation Pd, Cu, with step A gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, takes out solid particle after cooling, dry at 60 DEG C～150 DEG C, obtains PdCu-hydroxyl-bipyridyl/Al2O3Precursor.The volume of the mixed-cation solution of Pd, Cu is hydroxyl-bipyridyl/Al preferably2O3The 60%～200% of precursor cumulative volume；The ratio of the molal quantity of best Cu and the molal quantity of Pd is 0.4～5, it is desirable to regulating pH value is 1.0～4.0.
C. the preparation of catalyst
PdCu-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdCu-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
When catalyst uses, the catalyst that above method can be prepared, use H in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
In step, hydroxyl dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives, hydroxyl 3,3 ,-dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives.May insure that Al2O3While it is produced extensive chemical absorption, two nitrilo that unnecessary hydroxyl is adjacent with bipyridyl combine with active component Pd, Cu.With molar basis, the molal quantity of hydroxyl-bipyridyl/(Pd+Cu) is 3～100.
Adding solvent in step to make hydroxyl-bipyridyl be completely dissolved, to be conducive to macromolecule absorption on carrier, solvent can be ethanol and ether.The addition of solvent is how many, mainly to control institute's solubilizer and macromolecule can be made to be completely dissolved.
In stepb, the solution of palladium-copper can be the soluble salt solutions of palladium, copper, as being Pd (NO3)2、CuNO3Mixed solution.In described mixed solution, palladium, mantoquita consumption are can make Pd, Cu content of final catalyst.
In step C, roasting preferably carries out in having oxygen atmosphere, sintering temperature of the present invention preferably 350 DEG C～500 DEG C.
When catalyst uses, the catalyst that above method can be prepared, use H in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
The present inventors have additionally discovered that, when adopting the method to carry out selective hydrogenation reaction, the activity of catalyst reaction, selectivity are all significantly improved, and catalyst stability strengthens.
Meanwhile, the inventive method prepares palladium-copper catalyst, and its alloy structure is more suitably applied to the working condition that catalyst activity requirement is higher.The trace acetylene that in, raw material higher in air speed, CO content is higher selects, in hydrogenation process, have reaction temperature low, the advantage that hydrogenation activity is good.
Accompanying drawing illustrates:
Accompanying drawing 1 is the C2 hydrogenation process chart of a kind of methanol-to-olefins adopting predepropanization technique of the application present invention.
In figure: 1 DME reactor；2 MTP reactors；3 pre-chillings separate；4 chillings separate；5 level Four compressions；6 level Four separate；7 drying towers；8-acetylene hydrogenation reactor；9 domethanizing columns；10 dethanizers.
Detailed description of the invention
Embodiment 1
Weighing Φ 4.2mm, specific surface area is 23.0m2Spherical α-the Al of/g, pore volume 0.36mL/g, bulk density 0.87g/mL2O3Carrier 500g.
By 87.72g4,4-dihydroxy-2,2-bipyridyl is dissolved in 700mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 2h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 60 DEG C of dry 10h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.44gPd (NO3)2、2.59gCu(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 1.5, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 2h, pours out residual liquid, obtain PdAg-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=30).After 120 DEG C of dry 4h at 550 DEG C of temperature roasting 2h in air atmosphere, obtain (Pd-Cu)/Al2O3Catalyst.
Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature reduce, obtain loaded catalyst S-1.Recording this catalyst Pd content is 0.036%, and Cu content is 0.18%.
Comparative example 1
Weighing Φ 4.2mm, specific surface area is 23.0m2Spherical α-the Al of/g, pore volume 0.36mL/g, bulk density 0.87g/mL2O3Carrier 500g.
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC8.9g is dissolved completely in 800mLTHF (oxolane), in above-mentioned carrier impregnation to above-mentioned solution, after standing 2h, PVC will be made to be adsorbed in Al2O3Surface, drying for standby.Obtain PVC/Al2O3。
Add 119.28g dicyandiamide and 4.0gNa2CO3, add above-mentioned preparation PVC/Al2O3Backflow 1h, is cooled to room temperature, with deionized water wash to neutral, and 60 DEG C of dry 10h, obtain functionalized PVC/Al2O3。
B, Pd-Cu-high-molecular complex/Al2O3The preparation of presoma
Weigh 0.44gPd (NO3)2、2.59gCu(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 1.5, is configured to mixed solution, takes the functionalized-PVC/Al prepared2O3Presoma, adds it to Pd (NO3)2、Cu(NO3)2Mixed solution in, stir 30min, pour out residual liquid, by above-mentioned product deionized water wash to neutral, 120 DEG C of dry 4h obtain (Pd-Cu)-PVC/Al2O3Presoma.
C, catalyst preparation
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h in air atmosphere, obtain oxidation state (Pd-Cu)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst D-1.Recording this catalyst Pd content is 0.036%, and Cu content is 0.18%.
Adopting the C2 hydrogenation technique of methanol-to-olefins, its process chart as shown in Figure 1, adopts 500mL evaluating apparatus, and working condition is in Table 1, and raw material forms in Table 2.
Table 1 micro anti-evaluation parameter
Table 2 raw material forms
| Component | Compositing range (%) | Component | Compositing range (%) |
| H2 | 1.2～2.5 | C2H2 | 0～0.01 |
| N2 | 0.5～1.0 | C2H6 | 1～2 |
| O2 | 0.005～0.015 | C2H4 | 40～60 |
| CO | 0.60～1.0 | C3H8 | 1.5～3 |
| CO2 | 0.20～0.60 | C3H6 | 15～40 |
| H2S | 0～0.0008 | C3H4 | 0～0.01 |
| CH4 | 6～10 | C4 | 3～6 |
| C2H2 | 0～0.01 | C5+ | 6～10 |
Table 3 catalyst 1000h performance meansigma methods
Embodiment 2
Weighing Φ 4.0mm, high 4.0mm, specific surface area is 58.0m2/ g, pore volume is 0.44mL/g, and bulk density is cylindrical vector 500g, the Al of 0.75g/mL2O3Mixing crystal formation for δ and θ.
By 18.46g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 8h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 90 DEG C of dry 8h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.59gPd (NO3)2、2.59gCu(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 2.0, is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and remaining solid dry 8h at 110 DEG C obtains PdCu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=30).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst S-2.Recording this catalyst Pd content is 0.048%, and Cu content is 0.096%.
Comparative example 2
Weighing Φ 4.0mm, high 4.0mm, specific surface area is 58.0m2/ g, pore volume is 0.44mL/g, and bulk density is cylindrical vector 500g, the Al of 0.75g/mL2O3Mixing crystal formation for δ and θ.
A, functionalized polystyrene acrylonitrile (SAN)/Al2O3Preparation
Weighing SAN resin 2.2g, be dissolved in 600mLDMF (dimethylformamide) solvent, under room temperature, stirring makes SAN resin be completely dissolved, add in this solution and above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred for, dry after separating solvent, obtain SAN/Al2O3。
By SAN/Al obtained above2O3, joining in 1000mL deionized water, add 57.6g ethylenediamine, backflow 4h, after cooling, take out product, washing, to neutral, dry and obtains functionalized-SAN/Al2O3。
B、(Pd-Cu)-SAN/Al2O3The preparation of presoma
Weigh 0.59gPd (NO3)2、2.59gCu(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 2.0, is configured to mixed solution, takes the functionalized-SAN/Al prepared2O3Presoma, by functionalized-SAN/Al2O3Join Pd (NO3)2、Cu(NO3)2Mixed solution in, stir 5min, pour out residual liquid, by above-mentioned product deionized water wash to neutral, obtain (Pd-Cu)-SAN/Al after drying2O3Presoma.
C, catalyst preparation
By the presoma of above-mentioned preparation, at 500 DEG C of roasting 4h of air atmosphere, obtain Pd-Cu/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst D-2.Recording this catalyst Pd content is 0.048%, and Cu content is 0.096%.
Adopting the C2 hydrogenation technique of methanol-to-olefins, its process chart as shown in Figure 1, adopts 500mL evaluating apparatus, and working condition is in Table 4, and raw material forms in Table 2.
Table 4 micro anti-evaluation parameter
Table 5 catalyst 1000h performance meansigma methods
Embodiment 3
Weighing Φ 3.0mm, specific surface area is 40.0m2/ g, pore volume is 0.18mL/g, and heap is than the tooth ball type carrier 500g, wherein θ-Al for 0.78g/mL2O3460g, titanium oxide 40g.
By 80.62g6,6'-dihydroxy-3,3'-bipyridyl is dissolved in 700mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 12h, make 6,6'-dihydroxy-3,3'-bipyridyl loads to after on alumina support completely, 120 DEG C of dry 4h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.41gPd (NO3)2,0.74gCu(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 3.2, is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and remaining solid is dry 4h at 120 DEG C, obtains PdCu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=85).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst S-3.Recording this catalyst Pd content is 0.034%, and Cu content is 0.05%.
Comparative example 3
Catalyst preparing
Weighing Φ 3.0mm, specific surface area is 40.0m2/ g, pore volume is 0.18mL/g, and heap is than the tooth ball type carrier 500g, wherein θ-Al for 0.78g/mL2O3460g, titanium oxide 40g.
Weigh 0.41gPd (NO3)2, 0.74gCu (NO3)2Being dissolved in the 400mL deionized water containing appropriate nitric acid, adjusting pH is 3.2, is configured to mixed solution, by concussion after this solution spraying to above-mentioned carrier 0.5 hour, after drying, in air atmosphere, 450 DEG C of roasting 6h obtained (Pd-Cu)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst D-3.Recording this catalyst Pd content is 0.034%, and Cu content is 0.05%.
Adopting the C2 hydrogenation technique of methanol-to-olefins, its process chart as shown in Figure 1, adopts 500mL evaluating apparatus, and working condition is in Table 6, and raw material forms in Table 2.
Table 6 micro anti-evaluation parameter
Table 7 catalyst 500h performance meansigma methods
Embodiment 4
Weighing Φ 4.2mm, high 4.2mm, specific surface area is 54.0m2/ g, pore volume is 0.48mL/g, and bulk density is cylindrical vector 500g, the Al of 0.74g/mL2O3Mixing crystal formation for δ and θ.
By 93.06g4,4-dihydroxy-2,2-bipyridyl is dissolved in 600mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 10h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 100 DEG C of dry 6h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.54gPd (NO3)2、4.24gCu(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 2.8, is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, and remaining solid dry 10h at 90 DEG C obtains PdCu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=20).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst S-4.Recording this catalyst Pd content is 0.044%, and Cu content is 0.29%.
Comparative example 4
Weighing Φ 4.2mm, high 4.2mm, specific surface area is 54.0m2/ g, pore volume is 0.48mL/g, and bulk density is cylindrical vector 500g, the Al of 0.74g/mL2O3Mixing crystal formation for δ and θ.
By 93.06g4,4-dihydroxy-2,2-bipyridyl is dissolved in 600mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 10h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 100 DEG C of dry 6h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2、AgNO3Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 2.8, is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, and remaining solid dry 10h at 90 DEG C obtains PdAg-hydroxyl-bipyridyl/Al2O3Precursor.
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst D-4.Recording this catalyst Pd content is 0.044%, and Ag content is 0.29%.
Adopting the C2 hydrogenation technique of methanol-to-olefins, its process chart as shown in Figure 1, adopts 500mL evaluating apparatus, and working condition is in Table 8, and raw material forms in Table 2.
Table 8 micro anti-evaluation parameter
Table 9 catalyst 500h performance meansigma methods
Can be seen that, compared with adopting tradition preparation catalyst, with when active component content is identical, with organic polymer grafted functional group load on a catalyst support, again by this carrier impregnation activity Pd, the solution of Cu obtains the method for organic polymer metal complex to be prepared catalyst and compares, have employed the method for hydrotreating of the present invention, the activity of hydrogenation reaction and selectivity are significantly better than traditional method of hydrotreating, outlet acetylene content is significantly lower than other two kinds of method of hydrotreating, Ethylene purity improves, such that it is able to improve the performance of polymer grade ethylene product very well, the reduction of green oil simultaneously, the active center making catalyst is not covered by by-product, catalyst activity and selectivity are able to good maintenance, catalyst extends service life.
Claims (13)
1. the front-end hydrogenation method of trace acetylene in a methanol-to-olefins device, before adiabatic reactor reactor for being hydrogenated with is positioned at domethanizing column or dethanizer, from the carbon one at the bottom of drying tower tower, carbon two and carbon 3 material in methanol-to-olefins device, enter adiabatic reactor reactor to carry out selecting hydrogenation, it is characterized in that: equipped with Pd-Cu series catalysts in adiabatic reactor reactor, with Al2O3Or Al2O3Being carrier with other hopcalite, with the quality of catalyst for 100%, wherein Pd content 0.015～0.050%, Cu content is 0.02～0.3%, and the specific surface area of catalyst is 20～60m2/ g, pore volume is 0.15～0.70mL/g；This catalyst, in preparation process, is combined with hydroxyl dipyridyl derivatives by carrier, and hydroxyl dipyridyl derivatives forms metal complex with active component；Reaction condition is: adiabatic reactor reactor inlet temperature 30 DEG C～50 DEG C, reaction pressure 1.5～2.5MPa, air speed 5000～15000h-1。
2. front-end hydrogenation method according to claim 1, it is characterized in that catalyst preparation process, at least including: load on carrier by hydroxyl dipyridyl derivatives, the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or nitrilo and Pd, Cu forms complex ion.
3. the front-end hydrogenation method of trace acetylene in a kind of methanol-to-olefins device according to claim 2, it is characterized in that hydroxyl dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives or hydroxyl 3,3,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.
4. front-end hydrogenation method according to claim 1, it is characterised in that the acquisition of catalyst comprises the steps: the organic solution with hydroxyl dipyridyl derivatives, impregnates carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution impregnation hydroxyl-bipyridyl/Al of preparation Pd, Cu2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdCu-hydroxyl-bipyridyl/Al2O3Precursor.At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
5. front-end hydrogenation method according to claim 1, it is characterised in that carrier mainly contains Al2O3, wherein also doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide；Described Al2O3For γ, δ, θ, α or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation.
6. front-end hydrogenation method according to claim 1, it is characterised in that carrier is spherical, cylinder, annular, bar shaped, cloverleaf pattern or Herba Galii Bungei shape.
7. according to the arbitrary described front-end hydrogenation method of claim 1-6, it is characterised in that the preparation method of catalyst comprises the steps:
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
The organic solution of hydroxyl dipyridyl derivatives mixes with carrier, reacts 2～24h, take out solid particle at 20 DEG C～60 DEG C temperature, dry at 60 DEG C～150 DEG C, obtains hydroxyl-bipyridyl/Al2O3Precursor；
B.PdCu-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed-cation solution of preparation Pd, Cu, with step A gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, takes out solid particle, dry at 60 DEG C～150 DEG C, obtains PdCu-hydroxyl-bipyridyl/Al2O3Precursor；
C. the preparation of catalyst
PdCu-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdCu-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
8. front-end hydrogenation method according to claim 7, it is characterised in that in step A, the molal quantity of hydroxyl-bipyridyl/(Pd+Cu) is 1～100:1.
9. front-end hydrogenation method according to claim 7, it is characterised in that in stepb, the mixed solution that mixed-cation solution is Palladous nitrate. and copper nitrate of Pd, Cu.
10. front-end hydrogenation method according to claim 7, it is characterised in that in stepb, the ratio of the molal quantity of Cu and the molal quantity of Pd is 0.4～11:1.
11. front-end hydrogenation method according to claim 7, it is characterised in that in stepb, the mixed-cation solution ph regulating Pd, Cu is 1.5～4.0.
12. front-end hydrogenation method according to claim 1, it is characterised in that adiabatic reactor reactor reaction bed number is single hop bed.
13. front-end hydrogenation method according to claim 1, it is characterised in that hydrogen and acetylene volume ratio are 2～6:1.
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