CN106362795A - Method of improving reaction performance in preparation of higher alcohols (C<6+> alcohol) through synthetic gas one-step method by means of bifunctional catalyst combination system - Google Patents
Method of improving reaction performance in preparation of higher alcohols (C<6+> alcohol) through synthetic gas one-step method by means of bifunctional catalyst combination system Download PDFInfo
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- CN106362795A CN106362795A CN201610728588.1A CN201610728588A CN106362795A CN 106362795 A CN106362795 A CN 106362795A CN 201610728588 A CN201610728588 A CN 201610728588A CN 106362795 A CN106362795 A CN 106362795A
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- Prior art keywords
- catalyst
- reaction
- higher alcohols
- alcohol
- combined system
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 88
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- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 65
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
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- 239000010703 silicon Substances 0.000 claims abstract description 22
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- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002210 silicon-based material Substances 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 31
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- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 3
- 239000003345 natural gas Substances 0.000 abstract description 3
- 229910017061 Fe Co Inorganic materials 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 41
- 230000015572 biosynthetic process Effects 0.000 description 39
- 229910052799 carbon Inorganic materials 0.000 description 28
- 239000002585 base Substances 0.000 description 19
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- 239000000047 product Substances 0.000 description 17
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 14
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- 238000011065 in-situ storage Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
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- 230000015556 catabolic process Effects 0.000 description 7
- 230000009514 concussion Effects 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
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- 229910021641 deionized water Inorganic materials 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 230000008859 change Effects 0.000 description 5
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- 239000003102 growth factor Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
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- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
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- 150000001299 aldehydes Chemical class 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
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- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 2
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- 239000000956 alloy Substances 0.000 description 1
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- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- YVYBDVDCJNLVEI-UHFFFAOYSA-N oxalic acid;rhodium Chemical compound [Rh].OC(=O)C(O)=O.OC(=O)C(O)=O.OC(=O)C(O)=O YVYBDVDCJNLVEI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method of improving reaction performance in preparation of higher alcohols (C<6+> alcohol) through a synthetic gas one-step method by means of a bifunctional catalyst combination system. The bifunctional catalyst combination system includes a catalyst A and a catalyst B, wherein the catalyst A is a Cu-Fe-Co based catalyst supported by a polymer/mesoporous silicon composite material, and the catalyst B is a Cu-Zn-Fe based catalyst supported by an acid-modified attapulgite/cerium-zirconium solid solution composite material. The bifunctional catalyst combination system is packed in a two-stage reaction zone in the material feeding direction according to the sequence of A//B or B//A in an upper-lower layer manner, or is packed in a three-stage reaction zone in the material feeding direction according to the sequence of A//B or B//A in an equal-volume multi-layer manner. The bifunctional catalyst combination system has mild reaction conditions, simple preparation process and convenient operations, and can be used for producing the higher alcohols from the raw materials such as coal, biomass, natural gas and the like through the synthetic gas one-step method. The method has excellent industrialization application prospect.
Description
Technical field
The invention belongs to bifunctional catalyst combined system technical field is and in particular to a kind of bifunctional catalyst assembly
It is to prepare higher alcohols (c for improving one-step method from syngas6+Alcohol) reactivity worth method.
Background technology
Preparing MAS for raw material through synthesis gas circuit line using coal, biomass and natural gas has become c1Chemical multiphase
One of main research of catalytic field.The catalyst system being adopted mainly has modified methanol synthetic catalyst, modified expense
Support (f-t) synthetic catalyst, rh base catalyst and modified mo base catalyst (sulfide and oxide) etc., product is mainly low-carbon (LC)
Alcohol.In conventional fixed bed reactors, low-carbon alcohols selectivity and yield all relatively low it is difficult to meet industrialization demand.For this reason, being directed to
C in higher alcohols synthesis1→c2With difference and the thermodynamics feature of subsequent step reaction rate, passed through suitable using double sections of bed reactors
When bed combination can obtain preferably co conversion ratio and c2+The selectivity of alcohol.Beretta etc. synthesis isobutanol during,
Using cs-cu/zno/cr2o3‖cs-zno/cr2o3Dual bed catalytic agent obtains compared with monolayer bed cs-cu/zno/cr2o3Catalyst
Higher isobutanol yield, the reaction temperature of two kinds of beds be respectively 325 DEG C and 405 DEG C [j.chem.soc.,
chem.commun.1995,2525-2526】.United States Patent (USP) us 5096688 discloses one kind by overlying catalyst coo-maox-
zno-mbox(maFor ti, al, mn, mg, mbFor alkali metal li, na, k, rb, cs) and the conjunction of lower-layer modified low-temp low-pressure cu base methanol
Become double section bed reactors of catalyst combination loading, synthesis gas is converted into first in 232～343 DEG C under overlying catalyst effect
Alcohol, c2+Alcohol, the unsaturated organic oxygen-containing compound (as carboxylic acid, aldehyde, ketone, ester) containing 2 or more c atom, water and hydro carbons by-product
Thing, the unsaturated oxygenatedchemicalss in this mix products so that lower catalyst agent effect under by hydrogenation formed alcohols, water is then
It is eliminated by water gas shift reaction, promote c2+Alcohol selectivity and the raising of low-carbon alcohols purity.
Compared with low-carbon alcohols, higher alcohols (c6+Alcohol) there is higher carbon number and added value.Generally c6～c10Alcohol claims
For plasticizer alcohol, c12+Alcohol is referred to as detergent alcohol, and they are synthetic surfactant, detergent, plasticizer and other are multiple fine
Chemical products want raw material.External high-carbon alcohol production started from for 18th century, was mainly produced by animal oil.The development of 19 beginnings of the century
N-alkane oxidizing process produces higher alcohols.The forties in 20th century, Germany is succeeded with oxo process legal system higher alcohols.1961
The U.S. develops Ziegler legal system alcohol variation route.Higher alcohols mainly crack gained alkene with non-renewable petroleum resources at present is former
Material, the carbongl group synthesis reaction through rh base or co base catalyst produces, but technique is typically more complicated.China had started in the sixties
The production of small-scale.The eighties, the domestic high-carbon alcohol production built up with natural oil, synthetic fatty acid, alkene as raw material
Device, and progressively developed with ethylene and paraffin for the method for Material synthesis higher alcohols.However, China's higher alcohols industrial foundation is thin
Weak, backward in technique, yield poorly, and the huge market demand leads to import volume to increase year by year, this imbalance between supply and demand seriously constrains down
The development of trip related industry.
In recent years, the concern that higher alcohols gradually cause Chinese scholars is directly prepared by synthesis gas, the catalysis being adopted
Agent system mainly have Chinese patent cn 102266790a, cn 102266778b, cn 101310856b, cn 103586060b and
Co base catalyst disclosed in United States Patent (USP) us 7670985, Chinese patent cn 102319575b, cn 103433046a, cn
Cu-fe, cu-co and cu-co-fe base catalyst disclosed in 102500374b, cn 105085185a.Additionally, some have special
The catalyst of structure, such as three-dimensional ordered macroporous cu-fe base catalyst (chemcatchem, 2014,6 (2): 473-478),
Cocumn ternary metal nuclear shell structure nano catalyst (journal of the american chemical society,
2013,135 (19): 7114-7117) and cu@(cuco-alloy)/al2o3Nuclear shell structure nano catalyst (green
Chemistry, 2015,17 (3): 1525-1534) also applied.Polymer/mesoporous silicon composite loads cu-fe-co
Base catalyst also has good synthesis gas and prepares higher alcohols performance, and reaction condition is gentle, and method for preparing catalyst is simple and property
Can be stable, but also exist that alcohol selectivity is relatively low, the higher problem of other by-product selectivitys.
From thermodynamic analysis, exothermic reaction is belonged to by the reaction that synthesis gas directly prepares mixed alcohol, temperature is more low more favourable
In the synthesis of alcohol, but low temperature is unfavorable for the conversion of co, and co2Selectivity is higher, and the timely transfer of reaction heat is catalyzed for maintaining
Agent activity is most important；Reverse water-gas-shift reaction belongs to the endothermic reaction, and temperature is more high more is conducive to co2Conversion and alcohol carbon
Chain increases, but high temperature is unfavorable for the synthesis of alcohol, and is also easy to produce the by-products such as hydro carbons.In addition to reaction heat, each product (inclusion water) phase
The impact of heating is also very big.Therefore, the impact to selectivity of product for the selection of reaction temperature is larger.Using mixing alcohol synthesis reaction
Coupling effect and reverse water-gas-shift reaction between, transfer and byproduct of reaction convert in time in time to make reaction heat, can be effective
Adjust catalyst activity and selectivity of product, and improve catalyst stability.Patent cn 103613483b, is loaded by upper strata
Cu-fe-co base modification f-t synthetic catalyst cuafebcocmd/sio2Cu/zno/al with lower floor's filling2o3/mxoyModified first
The combination of alcohol synthetic catalyst, makes synthesis gas be converted into co in the presence of overlying catalyst2, water, methanol, c2+Alcohol, other not
The complete synthesis gas of saturation organic oxygen-containing compound (as carboxylic acid, aldehyde, ketone, ester) and hydro carbons by-product, products therefrom and unreacted enters
Enter lower catalyst agent, part co therein2Pass through hydrogenation with unsaturated oxygenatedchemicalss and form alcohols, water is then become by water gas
Change reaction to be eliminated, thus promoting the conversion of higher alcohols synthesis byproduct in process thing, effectively increase reactivity and
The yield of low-carbon alcohols and selectivity.But this layering loading catalyst is mainly for the preparation of c1～c5Low-carbon alcohols.Up to the present,
Bifunctional catalyst combined system be applied to one-step method from syngas prepare in the reaction system of higher alcohols have not been reported.
Content of the invention
It is an object of the invention to provide a kind of bifunctional catalyst combined system is used for improving one-step method from syngas preparation
Higher alcohols (c6+Alcohol) reactivity worth method, this bifunctional catalyst combined system achieves the timely of reaction heat in course of reaction
Transfer and the timely conversion of byproduct of reaction, make the industrial prospect that one-step method from syngas prepares higher alcohols get a promotion.
In order to realize foregoing invention purpose, technical scheme is as follows:
It is an object of the invention to provide a kind of bifunctional catalyst combined system is used for improving one-step method from syngas preparation height
Carbon alcohol (c6+Alcohol) reactivity worth method, raw material of synthetic gas is introduced fixed bed hydrogenation reactor, by bifunctional catalyst group
Zoarium system bed, reaction under the conditions of thermal coupling generates higher alcohols；
Described bifunctional catalyst combined system bed is made up of catalyst a and catalyst b, and described catalyst a is polymerization
Thing/mesoporous silicon composite loads cu-fe-co base catalyst, and described catalyst b is sour attapulgite modified/cerium zirconium sosoloid
Composite loads cu-zn-fe base catalyst；
Described fixed bed hydrogenation reactor comprises more than two sections of reaction zone, the bifunctional catalyst group in two-stage reaction area
The order levels filling of a//b or b//a, the double-function catalyzing in more than three sections reaction zones are pressed along feed stream direction by fit system
Agent combined system presses the order equal volume multilamellar filling of a//b or b//a along feed stream direction；
The admission space of described catalyst a and described catalyst b is than for 1/9～9/1.
Catalyst a mainly provides the c-o that synthesis gas is prepared needed for higher alcohols to insert into alcohol and c-c chain growth active sites, urges
Agent b mainly provides by-product co2Active sites needed for conversion, realize effective modulation of h/c ratio in synthesis gas, provide by-product simultaneously
In thing, aldehyde, ketone, acid are hydrogenated into active sites needed for alcohol, and to improve higher alcohols selectivity, this bifunctional catalyst combined system is realized
The timely transfer of reaction heat and the timely conversion of byproduct of reaction in course of reaction, improve polymer/mesoporous silicon composite wood
The reactivity of material load cu-fe-co base catalyst and higher alcohols selectivity.
The polymer that catalyst a is prepared for emulsion polymerization in situ/mesoporous silicon composite (pm/ms) loads cu-fe-co
Base catalyst, catalyst b be coprecipitation or sol-gel process or solution combustion method preparation acid attapulgite modified/cerium
Zirconium solid solution composite (atp-czo) loads cu-zn-fe base catalyst.Two kinds of catalyst granules are 20-100 mesh, preferably
60-80 mesh, and uniformly mix with isopyknic 40-60 mesh quartz sand respectively, by silica wool by bifunctional catalyst separately.
Preferably, the expression formula of described catalyst a is cua1feb1coc1m1d1/ pm-ms, wherein m1 are selected from la, zr or k
More than one, a1, b1, c1 and d1 are respectively cu, fe, co and m1 and account for the mass fraction of catalyst, and a1=10～30%, b1
=10～30%, c1=1～10%, d1=1～5%；Described polymer pm is by monomer methyl acrylate or methyl methacrylate
Polymerization is formed for ester or both mixing (mixing quality than for 1/4～4/1), and is expressed as pma or pmma or pmma＆pma；
Described mesoporous silicon ms divides selected from mcm-41 molecular sieve, mcm-48 molecular sieve, mcm-50 molecular sieve, sba-15 molecular sieve, sba-16
One of sub- sieve, msu-j molecular sieve, msu-h molecular sieve or hexagonal mesoporous silicon or two kinds；Described mesoporous silicon and described polymer
The mass ratio of monomer is 0.005～0.4.
The preparation method of catalyst a, comprises the steps:
(1) in terms of mass fraction, successively by 40～80 parts of polymer monomers, 0.1～0.5 part of initiator, 0.4～16 part of Jie
Hole silicon, 0.1～0.5 part of buffer agent, 60～120 parts of water, 0.2～1.0 portion of anion surfactant and 0.2～1.0 part of emulsifying
Agent is added in reaction vessel, at room temperature after ultrasonic wave concussion 20～60min, polyreaction occurs in 60～80 DEG C of water-baths
2～5h, is cooled to less than 50 DEG C, filters, and collects condensation product, the emulsion mass fraction obtaining is 5～30% demulsifier water
Solution breakdown of emulsion obtains solid product, rinses and dries, pulverized 100 mesh standard sieves obtain the carrier polymer of described catalyst a/
Mesoporous silicon composite；
(2) by active component cu, fe, the nitrate of co or acetate or oxalates or citrate and auxiliary agent la,
The chloride of at least one of zr, k or nitrate or acetate or oxalates are configured to metal ion total concentration together and are
The mixed aqueous solution of 0.5～5.0mol/l, or contain less than 30% ethanol or the mixed aqueous solution of ethylene glycol and above-mentioned substance, to
Wherein add carrier polymer/mesoporous silicon composite powder, and dipping 2～12h is stirred at room temperature, then dry, pulverize
After put in Muffle furnace, in 300～600 DEG C of roasting 2～8h, that is, polymer/mesoporous silicon load cu-fe-co base catalyst is obtained；
Described polymer monomer is that (mixing quality ratio is for 1/ for acrylic acid methyl ester. or methyl methacrylate or both mixing
4～4/1)；
Described initiator is selected from Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, azodiisobutyronitrile or dibenzoyl peroxide
One of；
Described mesoporous silicon ms be selected from mcm-41 molecular sieve, mcm-48 molecular sieve, mcm-50 molecular sieve, sba-15 molecular sieve,
The mixing of one of sba-16 molecular sieve, msu-j molecular sieve, msu-h molecular sieve or hexagonal mesoporous silicon (hms) or two kinds is (mixed
Closing mass ratio is 1/4～4/1)；
Preferably, described mesoporous silicon ms is selected from mcm-41 molecular sieve, sba-15 molecular sieve or hexagonal mesoporous silicon (hms)
One or two mixing (mixing quality than for 1/4～4/1), wherein mcm-41 is prepared with reference to United States Patent (USP) us 5102643,
Sba-15 is prepared with reference to Chinese patent zl 01126509.4, and hms reference literature (Chen Junhua. the synthesis of hexagonal mesoporous silicon hms, change
Property and performance study [d]. Nanjing: Nanjing Forestry University, 2009) preparation；
Described buffer agent is selected from one of sodium bicarbonate, potassium bicarbonate or ammonium hydrogen carbonate；
Described anion surfactant is selected from dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, lauryl sulphate acid
One of ammonium, Brij 35 sodium sulfate or sodium lauryl sulphate；
Described emulsifying agent is selected from alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or polyoxyethylene carboxylate
A kind of；
Described demulsifier is selected from one of sodium chloride, calcium chloride, aluminum chloride, iron chloride or aluminum sulfate.
Preferably, the expression formula of described catalyst b is cua2znb2fec2m2d2/ pal-czo, wherein m2 be selected from co, mn, rh,
One or more of k, mol ratio a2/b2/c2/d2 of cu, zn, fe and m2 be 1/ (0.5～1)/(0.05～1)/(0.01～
0.3) mass fraction that, carrier pal-czo accounts for described catalyst b is 20～75%.
The preparation method of catalyst b, comprises the steps:
(1) attapulgite modified by Pressure hydrometallurgical process preparation acid
By the solid mass ratio 3～8:1 of liquid, by concentration be 4～20% sulfuric acid solution and attapulgite mixing, mix homogeneously
Afterwards, closed reaction vessel, is warming up to 100～150 DEG C of constant temperature stirring reaction 0.5～3h, terminates rear blowing, quiet heavy rear upper strata slurry
Filtered, Cake Wash, to neutral, is dried, the acquisition acid that pulverizes and sieves is attapulgite modified；
(2) by coprecipitation or sol-gel process or solution combustion method preparation pal-czo carrier
During coprecipitation preparation pal-czo carrier, cerium salt, zirconates and sour modified attapulgite powder end are dissolved in the water,
Ultrasonic disperse 1～5h obtains mixed solution while stirring, carries out in being simultaneously added dropwise respectively to container with ammonia at 25～80 DEG C
Co-precipitation, maintains reaction system ph=8.0～10.0, after being added dropwise to complete, continues at the same temperature to stir aging 1～5h, mistake
Filter, washing precipitate to neutral, dry by filter cake, and in 400～800 DEG C of roasting 3～7h, pulverizes and sieves acquisition attapulgite/cerium
Zirconium solid solution composite；
During sol-gel process preparation pal-czo carrier, cerium salt, zirconates are dissolved in the water, add ethanol and citric acid,
Magnetic agitation 1～5h forms colloidal sol, is proportionally added into sour modified attapulgite powder end, continues magnetic agitation 1 in gained colloidal sol
～5h, solvent evaporated in 60～90 DEG C of water-baths, gained gel is dried in an oven, and in 400～800 DEG C of roasting 3～7h, powder
The broken acquisition attapulgite/cerium zirconium sosoloid composite that sieves；
During solution combustion method preparation pal-czo carrier, cerium salt, zirconates are dissolved in the water, add ethylene glycol to stir,
Add sour modified attapulgite powder end, ultrasonic disperse 1～5h while stirring in resulting solution, resulting solution is placed directly within Muffle
With 1.0～5.0 DEG C/min ramp to 400～800 DEG C of roasting 3～7h in stove, the acquisition attapulgite/cerium zirconium that pulverizes and sieves is solid
Solution composite；
(3) by infusion process preparation pal-czo load cu-zn-fe base catalyst, will active component cu, zn, fe and auxiliary agent
The nitrate of at least one of co, mn, rh, k or acetate or oxalates or citrate are configured to metal ion total concentration
Mixed aqueous solution for 0.5～5.0mol/l, is added thereto to attapulgite/cerium zirconium sosoloid composite powder and in room temperature
Lower stirring dipping 3～24h, then dries, puts in Muffle furnace after pulverizing, in 300～500 DEG C of roasting 2～6h；
Above-mentioned cerium salt is selected from cerous nitrate or ammonium ceric nitrate, and zirconates is selected from zirconium nitrate, zirconyl nitrate or zirconium oxychloride
Kind；
The ethanol adding in above-mentioned sol-gel process preparation process is 0.5～4:1 with the mass ratio of aqueous solvent, interpolation
Citric acid molal quantity is 1～2:1 with the ratio of cerium, the molal quantity sum of zirconium ion；
The ethylene glycol adding in above-mentioned solution combustion method preparation process is 0.5～2:1 with the volume ratio of aqueous solvent；
In above-mentioned attapulgite/cerium zirconium sosoloid composite, the attapulgite modified mass ratio with cerium zirconium sosoloid of acid
For 2～5:1；Cerium zirconium sosoloid consist of cexzr1-xo2, 0.05≤x≤0.95.
Preferably, the volume ratio of described catalyst a and described catalyst b is 5/5～9/1, and described reaction zone is 2～5 sections.
Preferably, described bifunctional catalyst combined system carries out reduction activation process before the reaction, and reducing condition is: also
Former temperature is 300～500 DEG C, and reduction pressure is 0.5～4.0mpa, and reduction air speed is 1000～5000h-1, also Primordial Qi is h2.
Preferably, the thermal coupling reaction condition of described bifunctional catalyst combined system is: reaction temperature is 180～280
DEG C, reaction pressure is 4.0～7.0mpa, and reaction velocity is 2000～6000h-1, reaction gas h2The mol ratio of/co be 1.0～
3.0.
The invention has the beneficial effects as follows:
(1) pass through to adjust the filling order of two kinds of catalyst and filling ratio in this bifunctional catalyst combined system, real
Effective conversion of existing byproduct of reaction, it is possible to achieve effective modulation of alcohol product carbochain growth factor α, improves reactivity, alcohol
Space-time yield and higher alcohols selectivity；
(2) there is between catalyst in this bifunctional catalyst combined system good " thermal coupling effect " and " product turns
Change coupling effect ", be conducive to improving catalyst stability and extend catalyst life；
(3) reaction condition of this bifunctional catalyst combined system is gentle, and preparation process is simple, easy to operate, can apply
In higher alcohols are prepared for raw material through one-step method from syngas by coal, biomass, natural gas etc., before there are preferable industrial applications
Scape.
Brief description
Fig. 1 is by catalyst a cu in the embodiment of the present invention 130fe10co10k1/ pmma-sba-15 and catalyst
b——cu1zn0.5fe0.15mn0.05k0.05/atp-ce0.75zr0.25o2Through different volumes ratio (1/9～9/1) filling constituted double
Function catalyst combination system b//a catalyzes and synthesizes gas one-step method at a temperature of differential responses and prepares higher alcohols gained alcohol product
Carbochain growth factor α.
Specific embodiment
With reference to instantiation, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright, rather than limit protection scope of the present invention.Technical staff makes according to the present invention in actual applications improvement and tune
Whole, still fall within protection scope of the present invention.
The equipment using except special instruction, the present invention and reagent are the art routine commercial products.
The bifunctional catalyst combined system that the present invention provides is used for improving one-step method from syngas prepares higher alcohols (c6+Alcohol)
The method of reactivity worth, first in 300～500 DEG C of temperature, pressure 0.5～4.0mpa, air speed 1000～5000h-1Under conditions of,
Using h2Reduction activation process is carried out to bifunctional catalyst combined system, then in 180～280 DEG C of temperature, pressure 4.0～
7.0mpa, air speed 2000～6000h-1Under conditions of, make h2/ co mol ratio be 1.0～3.0 synthesis gas with reduction after double work(
The contact of catalyst combination system can carry out higher alcohols synthesis.
Bifunctional catalyst combined system of the present invention is made up of catalyst a and catalyst b, fills in and comprises 2～5
In the fixed bed hydrogenation reactor of section reaction zone, when for two-stage reaction area, material is entered on this bifunctional catalyst combined system edge
The order levels filling of a//b or b//a, when for more than three sections reaction zones, this bifunctional catalyst assembly are pressed in stream direction
System along feed stream direction press a//b//a//... or b//a//b//... order equal volume multilamellar load.Catalyst a and urging
The admission space of agent b is than for 1/9～9/1, preferably 5/5～9/1.
In the application, polymer/mesoporous silicon composite that catalyst a is prepared for emulsion polymerization in situ loads cu-fe-
Co base catalyst, catalyst b is the atp-czo load cu- of coprecipitation or sol-gel process or solution combustion method preparation
Zn-fe base catalyst.
Unless otherwise defined or described herein, all specialties used in the present invention are skilled with art technology with scientific words
Same meaning familiar to personnel institute.
Analysis method during evaluating catalyst is as follows:
Unstripped gas and tail gas form by the agilent 7890a gas with four valve six post, double tcd+fid tri- detector system
Chromatograph completes, a road tcd analysis h2, another road tcd analysis o2、n2, co and co2, fid is then used for analyzing gaseous hydrocarbon
Class；After reaction terminates, collect product liquid, extract and separate is carried out using hexamethylene, aqueous phase and oil phase are all using agilent7890
Gas chromatograph off-line analysiss, fid detector, ffap chromatographic column (30m × 0.25mm × 0.25 μm).
According to the content of component each in reaction end gas, with the conversion ratio of the molal quantity calculating carbon monoxide of carbon atom and respectively
The selectivity of product, computing formula is as follows:
CO conversion (mol%): cco=[n (co)in- n (co)out]×100/[n(co)in]
Carbon dioxide selectivity (mol%): sco2=n (co2)×100/[n(co)in- n (co)out]
Methane selectively (mol%): sch4=n (ch4)×100/[n(co)in- n (co)out]
Alcohol selectivity (mol%): sroh=n (roh) × 100/ [n (co)in- n (co)out]
c2+Hydrocarbon-selective (mol%): shc2+=n (hc2+)×100/[n(co)in- n (co)out]
The selectivity (mol%) of other oxygenatedchemicalss: shoc=100-sco2- sch4- sroh- shc2+
Alcohol space-time yield (g ml-1(cat.)·h-1): styroh=m (roh)/[v (catalyst) × t]
Wherein: n (co)inWith n (co)outIt is respectively the molal quantity of co in gas after reacting front and reacting；n(co2)、n
(ch4), n (roh) and n (hc2+) be respectively react after carbon dioxide in gas, methane, total alcohol and c2+The molal quantity of hydrocarbon；m(roh)
It is respectively total alcohol quality and catalyst volume with v (catalyst)；T is the response time.
The following is and the present invention is further illustrated, but content not thereby limiting the invention.
Embodiment 1～6 illustrates bifunctional catalyst combined system and its preparation of the present invention.
Embodiment 1
Prepare sba-15 molecular sieve with reference to patent zl 01126509.4；Pmma-sba- is prepared using emulsion polymerization in situ
15 composites: successively by 60g methyl methacrylate (mma) monomer, 0.2g Ammonium persulfate., 0.6gsba-15 (> 200 mesh),
0.2g sodium bicarbonate, 90g water, 1.0g dodecyl sodium sulfate and 0.5g alkylphenol polyoxyethylene op-10 are added to and are connected with
In agitator, condensing tube, the four-hole boiling flask of thermometer, at room temperature after ultrasonic wave concussion 20min, occur poly- in 75 DEG C of water-baths
Close reaction 3h, be cooled to less than 50 DEG C, filtered with 100 mesh standard sieves, the emulsion mass fraction obtaining is 10% aluminum sulfate
Aqueous solution breakdown of emulsion obtains solid product, and deionized water is rinsed for several times repeatedly, dries, pulverized 100 mesh in vacuum drying oven
Standard screen obtains pmma-sba-15.
Using preparation catalyst: by cu, fe, co, k in catalyst mass fraction be respectively 30wt%,
10wt%, 10wt%, 1wt%, weigh copper nitrate, ferric nitrate, cobalt nitrate and potassium nitrate, are configured to total concentration of metal ions and are
The mixed aqueous solution of 0.5mol/l, the pmma-sba-15 powder of above-mentioned preparation is added in this mixed solution and stirs at room temperature
Mix dipping 5h, then drying, 400 DEG C of roasting 4h, prepared catalyst a cu30fe10co10k1/pmma-sba-15.
Prepare sour attapulgite modified atp with reference to embodiment 3 in patent cn 104815664a；With reference to patent
In cn104815664a, embodiment 1 adopts coprecipitation to prepare atp-ce0.75zr0.25o2Composite.Urged using infusion process preparation
Agent: the mol ratio according to cu/zn/fe/mn/k in catalyst is 1/0.5/0.15/0.05/0.05 and their total load amount
For 60wt%, the metal ion total concentration prepared containing copper nitrate, zinc acetate, ferric nitrate, manganese nitrate and potassium nitrate is 2.0mol/l
Mixed aqueous solution, be added thereto to atp-ce0.75zr0.25o2Powder is simultaneously stirred at room temperature dipping 3h, then dries, 500 DEG C
Roasting 3h, prepared catalyst b cu1zn0.5fe0.15mn0.05k0.05/atp-ce0.75zr0.25o2.
3:1 bilayer fills in the reaction zone of fixed bed hydrogenation reactor to catalyst a and catalyst b by volume, constitutes double
Function catalyst combination system a//b.In 500 DEG C, 1.0mpa and 1000h-1Under the conditions of be passed through h2This bifunctional catalyst is combined
After reduction system activation 6h, it is cooled to 80 DEG C, in t=250 DEG C, p=6.0mpa, ghsv=5000h-1Thermal coupling under the conditions of logical
Enter h2The synthesis gas of/co=2.0 evaluates the higher alcohols synthesis performance of this bifunctional catalyst combined system, reaction result such as table 1
Shown.
Embodiment 2
Respectively refer to patent zl 01126509.4 and us 5102643 preparation sba-15 molecular sieve and mcm-41 molecular sieve.
Pmma＆pma-sba-15＆mcm-41 composite is prepared using emulsion polymerization in situ: successively by 36g acrylic acid methyl ester. (ma)
With 12g methyl methacrylate (mma) monomer, 0.5g potassium peroxydisulfate, 6.4gsba-15 (> 200 mesh) and 1.6gmcm-41 (> 200
Mesh), 0.5g potassium bicarbonate, 100g water, 0.5g ammonium lauryl sulfate and 0.3g fatty alcohol-polyoxyethylene ether oe-6 be added to even
It is connected in the four-hole boiling flask of agitator, condensing tube, thermometer, at room temperature after ultrasonic wave concussion 60min, send out in 80 DEG C of water-baths
Raw polyreaction 4h, is cooled to less than 50 DEG C, is filtered with 100 mesh standard sieves, the emulsion mass fraction obtaining is 20% chlorine
Change aluminum water solution breakdown of emulsion and obtain solid product, and deionized water is rinsed for several times repeatedly, dry in vacuum drying oven, pulverized
100 mesh standard sieves obtain pmma＆pma-sba-15＆mcm-41 composite.
Using preparation catalyst: by cu, fe, co, la, k in catalyst mass fraction be respectively 30wt%,
30wt%, 1wt%, 2wt%, 3wt%, weigh cupric oxalate, ferric oxalate, cobalt oxalate, Lanthanum (III) nitrate and potassium chloride, are configured to total metal
Ion concentration is the mixed aqueous solution of 3.0mol/l, and the pmma＆pma-sba-15＆mcm-41 powder of above-mentioned preparation is added this to mix
Close in solution and stir at room temperature and impregnate 12h, then drying, 600 DEG C of roasting 2h, prepared catalyst a
cu30fe30co1la2k3/pmma&pma-sba-15&mcm-41.
Prepare sour attapulgite modified atp with reference to embodiment 2 in patent cn 104815664a.Using sol-gel legal system
Standby atp-ce0.05zr0.95o2Composite: by atp/cexzr1-xo2(mass ratio)=5/1 and cerium zirconium sosoloid structural formula
ce0.05zr0.95o2(ce/zr mol ratio=1/19), weighs ce (nh4)2(no3)6With zr (no3)4·5h2O is dissolved in suitable quantity of water
In, obtain the cerium zirconium precursor water solution that concentration is 2.0mol/l, (mass ratio with above-mentioned aqueous solvent is to be added thereto to ethanol
0.5:1) with citric acid (ratio with the molal quantity sum of ce, zr ion is 2:1), magnetic agitation 1h forms colloidal sol, molten to gained
Add atp powder in glue, continue magnetic agitation 5h, solvent evaporated in 90 DEG C of water-baths, gained gel is dried, and at 800 DEG C
Lower roasting 3h, pulverized 100 mesh standard sieves and obtained atp-ce0.05zr0.95o2Composite.Using preparation catalyst: root
Mol ratio according to cu/zn/fe/co/mn in catalyst is 1/0.8/0.05/0.05/0.15 and their total load amount is
50wt%, the metal ion total concentration prepared containing Schweinfurt green, zinc oxalate, ferric nitrate, cobalt nitrate and manganese acetate is 1.0mol/l's
Mixed aqueous solution, is added thereto to atp-ce0.05zr0.95o2Powder is simultaneously stirred at room temperature dipping 12h, then dries, 400 DEG C
Roasting 6h, prepared catalyst b cu1zn0.8fe0.05co0.05mn0.15/atp-ce0.05zr0.95o2.
1:1 bilayer fills in the reaction zone of fixed bed hydrogenation reactor to catalyst a and catalyst b by volume, constitutes double
Function catalyst combination system b//a.In 400 DEG C, 2.0mpa and 3000h-1Under the conditions of be passed through h2This bifunctional catalyst is combined
After reduction system activation 3h, it is cooled to 80 DEG C, in t=220 DEG C, p=6.0mpa, ghsv=5000h-1Thermal coupling under the conditions of logical
Enter h2The synthesis gas of/co=2.5 evaluates the higher alcohols synthesis performance of this bifunctional catalyst combined system, reaction result such as table 1
Shown.
Embodiment 3
Prepare mcm-41 molecular sieve with reference to patent us 5102643.Pmma-mcm-41 is prepared using emulsion polymerization in situ
Composite: successively by 40g methyl methacrylate (mma) monomer, 0.1g azodiisobutyronitrile, 0.2gmcm-41 (> 200
Mesh), 0.1g sodium bicarbonate, 60g water, 0.2g Brij 35 sodium sulfate and 0.2g polyoxyethylene carboxylate
Lae-4 is added in the four-hole boiling flask being connected with agitator, condensing tube, thermometer, at room temperature after ultrasonic wave concussion 30min,
There is polyreaction 5h in 60 DEG C of water-baths, be cooled to less than 50 DEG C, filtered with 100 mesh standard sieves, the emulsion quality obtaining
Fraction is that 5% ferric chloride in aqueous solution breakdown of emulsion obtains solid product, and deionized water is rinsed for several times repeatedly, in vacuum drying oven
Dry, pulverized 100 mesh standard sieves and obtain pmma-mcm-41.Using preparation catalyst: by cu in catalyst, fe,
The mass fraction of co, zr, k is respectively 10wt%, 20wt%, 5wt%, 2wt%, 1wt% and weighs Schweinfurt green, Ferrous acetate, vinegar
Sour cobalt, zirconium oxychloride and potassium acetate, are configured to the mixed aqueous solution containing 20% ethanol that total concentration of metal ions is 5.0mol/l,
The pmma-mcm-41 powder of above-mentioned preparation is added in this mixed solution and stirring dipping 6h at room temperature, then dry, 600
DEG C roasting 8h, prepared catalyst a cu10fe20co5zr2k1/pmma-mcm-41.
Prepare sour attapulgite modified atp with reference to patent cn 104815664a embodiment 4.Using solution combustion method preparation
atp-ce0.95zr0.05o2Composite: by atp/cexzr1-xo2(mass ratio)=3/1 and cerium zirconium sosoloid structural formula
ce0.95zr0.05o2(ce/zr mol ratio=19/1) weighs ce (no3)3·6h2O and zro (no3)2·2h2O is dissolved in suitable quantity of water
In, obtain the cerium zirconium precursor water solution that concentration is 1.0mol/l, be added thereto to the ethylene glycol (volume ratio with above-mentioned aqueous solvent
For 2:1) stir, be subsequently adding atp powder, while stirring ultrasonic disperse 5h, resulting solution be placed directly within Muffle furnace with
1.0 DEG C/min ramp, to 800 DEG C of roasting 3h, was pulverized 100 mesh standard sieves and was obtained atp-ce0.95zr0.05o2Composite.
Using preparation catalyst: the mol ratio according to cu/zn/fe/rh/mn/k in catalyst is 1/1/0.5/0.1/0.1/
0.1 and their total load amount be 25wt%, prepare containing Schweinfurt green, zinc nitrate, ferric oxalate, rhodium nitrate, manganese nitrate and citric acid
The metal ion total concentration of potassium is the mixed aqueous solution of 5.0mol/l, is added thereto to atp-ce0.95zr0.05o2Powder in room
Temperature lower stirring dipping 24h, then drying, 300 DEG C of roasting 6h, prepared catalyst b cu1zn1fe0.5rh0.1mn0.1k0.1/atp-
ce0.95zr0.05o2.
5:1 divides five layers of reaction zone filling in fixed bed hydrogenation reactor to catalyst a and catalyst b by volume, constitutes
Bifunctional catalyst combined system b//a//b//a//b.In 300 DEG C, 4.0mpa and 1200h-1Under the conditions of be passed through h2To this pair of work(
After energy catalyst combination system reduction activation 5h, it is cooled to 80 DEG C, in t=280 DEG C, p=4.0mpa, ghsv=6000h-1Heat
It is passed through h under coupling condition2The synthesis gas of/co=2.0 evaluates the higher alcohols synthesis performance of this bifunctional catalyst combined system, instead
Answer result as shown in table 1.
Embodiment 4
Prepare sba-15 molecular sieve with reference to patent zl 01126509.4.Pmma-sba- is prepared using emulsion polymerization in situ
15 composites: successively by 80g methyl methacrylate (mma) monomer, 0.5g dibenzoyl peroxide, 32gsba-15 (> 200
Mesh), 0.3g ammonium hydrogen carbonate, 120g water, 0.8g sodium lauryl sulphate and 1.0g alkylphenol polyoxyethylene op-9 be added to even
It is connected in the four-hole boiling flask of agitator, condensing tube, thermometer, at room temperature after ultrasonic wave concussion 60min, send out in 80 DEG C of water-baths
Raw polyreaction 2h, is cooled to less than 50 DEG C, is filtered with 100 mesh standard sieves, the emulsion mass fraction obtaining is 30% sulfur
Sour aluminum water solution breakdown of emulsion obtains solid product, and deionized water is rinsed for several times repeatedly, dries, pulverized in vacuum drying oven
100 mesh standard sieves obtain pmma-sba-15.Using preparation catalyst: by cu, fe, co, la, zr, k in catalyst
Mass fraction be respectively 25wt%, 22wt%, 3wt%, 1wt%, 1wt%, 1wt% weigh copper nitrate, ferric oxalate, cobalt nitrate,
Lanthanum (III) nitrate, zirconyl nitrate and potassium oxalate, are configured to the mixing water containing 10% ethylene glycol that total concentration of metal ions is 2.0mol/l
Solution, the pmma-sba-15 powder of above-mentioned preparation is added in this mixed solution and stirring dipping 8h at room temperature, then dries
Dry, 500 DEG C of roasting 4h, prepared catalyst a cu25fe22co3la1zr1k1/pmma-sba-15.
Prepare sour attapulgite modified atp with reference to patent cn 104815664a embodiment 5.Using solution combustion method preparation
atp-ce0.8zr0.2o2Composite: by atp/cexzr1-xo2(mass ratio)=4/1 and cerium zirconium sosoloid structural formula
ce0.8zr0.2o2(ce/zr mol ratio=4/1) weighs ce (no3)3·6h2O and zroci2·8h2O is dissolved in suitable quantity of water, obtains
Concentration is the cerium zirconium precursor water solution of 2.5mol/l, be added thereto to ethylene glycol (be 0.5 with the volume ratio of above-mentioned aqueous solvent:
1) stir, be subsequently adding atp powder, while stirring ultrasonic disperse 1h, resulting solution is placed directly within Muffle furnace with 5.0
DEG C/min ramp to 400 DEG C of roasting 7h, pulverized 100 mesh standard sieves obtain atp-ce0.8zr0.2o2Composite.Using
Preparation catalyst: the mol ratio according to cu/zn/fe/k in catalyst is 1/1/0.5/0.15 and their total load amount
For 80wt%, the metal ion total concentration prepared containing copper nitrate, zinc nitrate, ferric nitrate, potassium nitrate is the mixing water of 2.0mol/l
Solution, is added thereto to atp-ce0.8zr0.2o2Powder is simultaneously stirred at room temperature dipping 5h, then drying, 500 DEG C of roasting 2h, system
Obtain catalyst b cu1zn1fe0.5k0.15/atp-ce0.8zr0.2o2.
1:2 divides three layers of reaction zone filling in fixed bed hydrogenation reactor to catalyst a and catalyst b by volume, constitutes
Bifunctional catalyst combined system b//a//b.In 500 DEG C, 0.5mpa and 5000h-1Under the conditions of be passed through h2To this double-function catalyzing
After agent combined system reduction activation 2h, it is cooled to 80 DEG C, in t=180 DEG C, p=7.0mpa, ghsv=5000h-1Thermal coupling bar
It is passed through h under part2The synthesis gas of/co=3.0 evaluates the higher alcohols synthesis performance of this bifunctional catalyst combined system, reaction result
As shown in table 1.
Embodiment 5
Respectively refer to patent zl 01126509.4 and us 5102643 preparation sba-15 molecular sieve and mcm-41 molecular sieve.
Pmma＆pma-sba-15＆mcm-41 composite is prepared using emulsion polymerization in situ: successively by 10g acrylic acid methyl ester. (ma)
With 40g methyl methacrylate (mma) monomer, 0.2g potassium peroxydisulfate, 2.5gsba-15 (> 200 mesh) and 10gmcm-41 (> 200
Mesh), 0.3g sodium bicarbonate, 80g water, 0.2g dodecylbenzene sodium sulfonate and 0.4g polyoxyethylene carboxylate lae-9 be added to
It is connected with the four-hole boiling flask of agitator, condensing tube, thermometer, at room temperature after ultrasonic wave concussion 30min, in 75 DEG C of water-baths
There is polyreaction 3h, be cooled to less than 50 DEG C, filtered with 100 mesh standard sieves, the emulsion mass fraction obtaining is 10%
Aluminum sulfate aqueous solution breakdown of emulsion obtains solid product, and deionized water is rinsed for several times repeatedly, dries, pulverized in vacuum drying oven
100 mesh standard sieves obtain pmma＆pma-sba-15＆mcm-41 composite.Using preparation catalyst: by catalyst
The mass fraction of cu, fe, co, la, zr is respectively 18wt%, 24wt%, 6wt%, 2wt%, 1wt% and weighs copper nitrate, Fructus Citri Limoniae
Sour ferrum, cobaltous acetate, Lanthanum (III) nitrate and zirconium nitrate, are configured to the mixed aqueous solution that total concentration of metal ions is 1.8mol/l, will be above-mentioned
The pmma＆pma-sba-15＆mcm-41 powder of preparation adds in this mixed solution and stirring impregnates 2h at room temperature, then dries
Dry, 500 DEG C of roasting 4h, prepared catalyst a cu18fe24co6la2zr1/pmma&pma-sba-15&mcm-41.
Prepare sour attapulgite modified atp with reference to patent cn 104815664a embodiment 4.Using sol-gel process preparation
atp-ce0.3zr0.7o2Composite: by atp/cexzr1-xo2(mass ratio)=3/1 and cerium zirconium sosoloid structural formula
ce0.3zr0.7o2(ce/zr mol ratio=3/7) weighs ce (no3)3·6h2O and zro (no3)2·2h2O is dissolved in suitable quantity of water,
Obtain the cerium zirconium precursor water solution that concentration is 5.0mol/l, be added thereto to ethanol (be 4 with the mass ratio of above-mentioned aqueous solvent:
1) and citric acid (being 1:1 with the ratio of the molal quantity sum of ce, zr ion), magnetic agitation 5h forms colloidal sol, in gained colloidal sol
Add atp powder, continue magnetic agitation 1h, solvent evaporated in 60 DEG C of water-baths, gained gel is dried, and roast at 400 DEG C
Burn 7h, pulverized 100 mesh standard sieves and obtain atp-ce0.3zr0.7o2Composite.Using preparation catalyst: according to urging
In agent, the mol ratio of cu/zn/fe/co/mn/rh/k is 1/0.5/1/0.05/0.05/0.05/0.15 and their total load
Measure as 60wt%, prepare containing copper nitrate, zinc nitrate, ferric nitrate, cobalt oxalate, manganese oxalate, rhodium nitrate and potassium citrate metal from
Sub- total concentration is the mixed aqueous solution of 3.0mol/l, is added thereto to atp-ce0.3zr0.7o2Powder is simultaneously stirred at room temperature dipping
8h, then drying, 500 DEG C of roasting 4h, prepared catalyst b cu1zn0.5fe1co0.05mn0.05rh0.05k0.15/atp-
ce0.3zr0.7o2.
3:1 divides three layers of reaction zone filling in fixed bed hydrogenation reactor to catalyst a and catalyst b by volume, constitutes
Bifunctional catalyst combined system a//b//a.In 450 DEG C, 1.8mpa and 2000h-1Under the conditions of be passed through h2To this double-function catalyzing
After agent combined system reduction activation 6h, it is cooled to 80 DEG C, in t=280 DEG C, p=4.0mpa, ghsv=2000h-1, h2/ co=
The higher alcohols synthesis performance of this bifunctional catalyst combined system is evaluated, reaction result such as table 1 institute under the conditions of 1.0 thermal coupling
Show.
Embodiment 6
Prepare mcm-41 molecular sieve with reference to patent us 5102643.Pmma-mcm-41 is prepared using emulsion polymerization in situ
Composite: successively by 60g methyl methacrylate (mma) monomer, 0.2g azodiisobutyronitrile, 6gmcm-41 (> 200 mesh),
0.4g sodium bicarbonate, 80g water, 0.6g sodium lauryl sulphate and 0.2g alkylphenol polyoxyethylene op-10 are added to and are connected with
In agitator, condensing tube, the four-hole boiling flask of thermometer, at room temperature after ultrasonic wave concussion 20min, occur poly- in 80 DEG C of water-baths
Close reaction 3h, be cooled to less than 50 DEG C, filtered with 100 mesh standard sieves, the emulsion mass fraction obtaining is 10% calcium chloride
Aqueous solution breakdown of emulsion obtains solid product, and deionized water is rinsed for several times repeatedly, dries, pulverized 100 mesh in vacuum drying oven
Standard screen obtains pmma-mcm-41.
Using preparation catalyst: by cu, fe, co, la, k in catalyst mass fraction be respectively 22wt%,
18wt%, 8wt%, 3wt%, 2wt%, weigh copper nitrate, ferric nitrate, cobalt oxalate, lanthanum chloride and potassium chloride, are configured to total metal
Ion concentration is the mixed aqueous solution containing 30% ethanol of 2.5mol/l, and the pmma-mcm-41 powder of above-mentioned preparation is added should
Stir in mixed solution and at room temperature and impregnate 4h, then drying, 500 DEG C of roasting 4h, prepared catalyst a
cu22fe18co8la3k2/pmma-mcm-41.
Prepare sour attapulgite modified atp with reference to patent cn 104815664a embodiment 2.With reference to patent cn
104815664a embodiment 4 adopts coprecipitation to prepare atp-ce0.5zr0.5o2Composite.Using preparation catalyst:
Mol ratio according to cu/zn/fe/rh in catalyst is 1/0.6/0.1/0.01 and their total load amount is 40wt%, prepares
Metal ion total concentration containing Schweinfurt green, zinc nitrate, ferric nitrate, oxalic acid rhodium be 1.5mol/l mixed aqueous solution, thereto plus
Enter atp-ce0.5zr0.5o2Powder is simultaneously stirred at room temperature dipping 15h, then drying, 400 DEG C of roasting 3h, prepared catalyst
b——cu1zn0.6fe0.1rh0.01/atp-ce0.5zr0.5o2.
1:1 divides four layers of reaction zone filling in fixed bed hydrogenation reactor to catalyst a and catalyst b by volume, constitutes
Bifunctional catalyst combined system b//a//b//a.In 380 DEG C, 1.5mpa and 1600h-1Under the conditions of be passed through h2This difunctional is urged
After agent combined system reduction activation 6h, it is cooled to 80 DEG C, in t=230 DEG C, p=7.0mpa, ghsv=3000h-1Thermal coupling
Under the conditions of be passed through h2/ co=2.0 evaluates the higher alcohols synthesis performance of this bifunctional catalyst combined system.
Table 1 is that in embodiment 1～6, bifunctional catalyst combined system catalyzes and synthesizes the reaction that gas one-step method prepares higher alcohols
Performance reaction result, as shown in table 1.
Table 1
As can be seen from Table 1, the higher alcohols synthesis performance of different bifunctional catalyst combined systems is significantly different, but always
For body, the selectivity of higher alcohols all can reach more than 30%, and the content of higher alcohols all can reach more than 40wt%, and ch4、co2
By-product selectivity is relatively low.
Comparative example 1
This comparative example illustrates the improvement to higher alcohols synthesis performance for the bifunctional catalyst combined system.
The composition of catalyst a and catalyst b and prepare same as Example 4.
Ten kinds of modes as shown in table 2 fill in the reaction of fixed bed hydrogenation reactor to catalyst a and catalyst b respectively
Area.In 400 DEG C, 1.5mpa and 1200h-1Under the conditions of be passed through h2After these catalyst systems reduction activation 4h, it is cooled to 80 DEG C,
In t=250 DEG C, p=6.0mpa, ghsv=5000h-1Thermal coupling under the conditions of be passed through h2The synthesis gas of/co=2.0 evaluates them
Higher alcohols synthesis performance.
The impact to higher alcohols synthesis performance for the type of feed for catalyst a and catalyst b for the table 3, as shown in table 3.
Table 2
Table 3
As can be seen from Table 3, bifunctional catalyst combined system either a//b, or the type of feed of b//a, with list
Solely the catalyst a of filling compares with catalyst b, and its higher alcohols synthesis performance is all significantly improved: co conversion ratio increases,
co2Selectivity reduces, and alcohol yield improves.Additionally, compared with bifunctional catalyst combined system a//b or b//a of double-deck filling,
Bifunctional catalyst combined system a//b//a, b//a//b, a//b//a//b, b//a//b//a and a//b/ of multilamellar filling/
A//b//a is respectively provided with higher reactivity, higher alcohols selectivity and lower ch4、co2Deng by-product selectivity, its reaction is lived
Property, higher alcohols selectivity and lower ch4、co2All it is significantly increased Deng by-product selectivity.This exactly make use of two kinds of catalysis
The thermal coupling effect of agent and product conversion coupling effect, by the filling of different modes, make entirely to react towards higher alcohols synthesis
Direction carry out, and then show the more superior reactivity worth of the bifunctional catalyst combined system of more double-deck filling, and total
Catalyst packing volume do not change.
Embodiment 7
This example demonstrates that the admission space of bifunctional catalyst combined system b//a compares the shadow of higher alcohols synthesis performance
Ring.
The composition of catalyst a and catalyst b and prepare same as Example 1.In 350 DEG C, 2.0mpa and 1000h-1Condition
Under be passed through h2After these catalyst systems reduction activation 5h, it is cooled to 80 DEG C, in t=220 DEG C, p=5.5mpa, ghsv=
3000h-1Thermal coupling under the conditions of, be passed through h2The synthesis gas of/co=2.0 evaluates the higher alcohols of this bifunctional catalyst combined system
Synthesis performance.The impact that the admission space of bifunctional catalyst combined system b//a compares higher alcohols synthesis performance is as shown in table 4.
Table 4
Fig. 1 is by catalyst a cu in the embodiment of the present invention 130fe10co10k1/ pmma-sba-15 and catalyst
b——cu1zn0.5fe0.15mn0.05k0.05/atp-ce0.75zr0.25o2Through different volumes ratio (1/9～9/1) filling constituted double
Function catalyst combination system b//a catalyzes and synthesizes gas one-step method at a temperature of differential responses and prepares higher alcohols gained alcohol product
Carbochain growth factor α.Carbochain growth factor α reflects the carbochain growing ability of catalyst, as seen from Figure 1, difunctional urges
Agent combined system cu1zn0.5fe0.15mn0.05k0.05/atp-ce0.75zr0.25o2//cu30fe10co10k1/ pmma-sba-15 is relatively
There is under low reaction temperatures good higher alcohols synthesis performance, and alcohol product carbochain growing ability with reaction temperature raise by
Decrescence little.
As can be seen from Table 4, in bifunctional catalyst combined system b//a the admission space of catalyst a and b than for 5/5
When, alcohol yield and selectivity are highest, co2Minimum with the overall selectivity of hydro carbons, and the alcohol product carbochain growth at a temperature of this
It was confirmed there is good coupling effect between two kinds of catalyst in factor-alpha 0.7 (Fig. 1).Show simultaneously, of the present invention double
Function catalyst module cording has preferable one-step method from syngas to prepare higher alcohols industrial applications prospect.
A kind of bifunctional catalyst the combined system above present invention being provided is used for improving one-step method from syngas preparation height
The method of carbon alcohol reactivity worth is described in detail, and specific case used herein is to the principle of the present invention and embodiment party
Formula is set forth, and the explanation of above example is only intended to help and understands the method for the present invention and its core concept it should refer to
Go out, to those of ordinary skill in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (8)
1. a kind of bifunctional catalyst combined system is used for improving one-step method from syngas and prepares higher alcohols (c6+Alcohol) reactivity worth
Method it is characterised in that raw material of synthetic gas is introduced fixed bed hydrogenation reactor, by bifunctional catalyst combined system bed
Layer, reaction under the conditions of thermal coupling generates higher alcohols；
Described bifunctional catalyst combined system bed is made up of catalyst a and catalyst b, and described catalyst a is polymer/Jie
Hole silicon composite load cu-fe-co base catalyst, described catalyst b is sour attapulgite modified/cerium zirconium sosoloid composite wood
Material load cu-zn-fe base catalyst；
Described fixed bed hydrogenation reactor comprises more than two sections of reaction zone, the bifunctional catalyst assembly in two-stage reaction area
The order levels filling of a//b or b//a, the bifunctional catalyst group in more than three sections reaction zones are pressed along feed stream direction by system
The order equal volume multilamellar filling of a//b or b//a is pressed along feed stream direction by fit system；
The admission space of described catalyst a and described catalyst b is than for 1/9～9/1.
2. bifunctional catalyst combined system is used for improving one-step method from syngas and prepares higher alcohols (c according to claim 16+
Alcohol) reactivity worth method it is characterised in that described catalyst a expression formula be cua1feb1coc1m1d1/ pm-ms, wherein m1
Selected from one or more of la, zr or k, a1, b1, c1 and d1 are respectively the mass fraction that cu, fe, co and m1 account for catalyst, and
A1=10～30%, b1=10～30%, c1=1～10%, d1=1～5%；Described polymer pm is by monomer methyl acrylate
Or methyl methacrylate or the polymerization of both mixture are formed, when the mixture for both, acrylic acid methyl ester. or methyl-prop
The mass ratio of e pioic acid methyl ester is 1/4～4/1；Described mesoporous silicon ms divides selected from mcm-41 molecular sieve, mcm-48 molecular sieve, mcm-50
One of sub- sieve, sba-15 molecular sieve, sba-16 molecular sieve, msu-j molecular sieve, msu-h molecular sieve or hexagonal mesoporous silicon or
Two kinds, when the mixture for two kinds of mesoporous silicon materials, the mass ratio of this two kinds of mesoporous silicon materials is 1/4～4/1；Described mesoporous
Silicon is 0.005～0.4 with the mass ratio of described polymer monomer.
3. bifunctional catalyst combined system is used for improving one-step method from syngas and prepares higher alcohols (c according to claim 16+
Alcohol) reactivity worth method it is characterised in that described catalyst b expression formula be cua2znb2fec2m2d2/ pal-czo, wherein
M2 is selected from one or more of co, mn, rh or k, mol ratio a2/b2/c2/d2 of cu, zn, fe and m2 be 1/ (0.5～1)/
(0.05～1)/(0.01～0.3), the mass fraction that carrier pal-czo accounts for described catalyst b is 20～75%.
4. bifunctional catalyst combined system according to claim 1 or 3 is used for improving one-step method from syngas and prepares higher alcohols
(c6+Alcohol) reactivity worth method it is characterised in that the preparation method of described catalyst b comprises the steps:
(1) attapulgite modified by Pressure hydrometallurgical process preparation acid
By the solid mass ratio 3～8:1 of liquid, by mass concentration be 4～20% sulfuric acid solution and attapulgite mixing, mix homogeneously
Afterwards, closed reaction vessel, is warming up to 100～150 DEG C of constant temperature stirring reaction 0.5～3h, terminates rear blowing, quiet heavy rear upper strata slurry
Filtered, Cake Wash, to neutral, is dried, the acquisition acid that pulverizes and sieves is attapulgite modified；
(2) by coprecipitation or sol-gel process or solution combustion method preparation pal-czo carrier
During coprecipitation preparation pal-czo carrier, cerium salt, zirconates and sour modified attapulgite powder end are dissolved in the water, while stirring
Mix side ultrasonic disperse 1～5h and obtain mixed solution, carry out coprecipitated in being simultaneously added dropwise respectively to container with ammonia at 25～80 DEG C
Form sediment, maintain reaction system ph=8.0～10.0, after being added dropwise to complete, continue at the same temperature to stir aging 1～5h, filter, wash
Wash precipitate to neutral, filter cake is dried, and in 400～800 DEG C of roasting 3～7h, pulverize and sieve acquisition attapulgite/cerium zirconium solid solution
Composite material；
During sol-gel process preparation pal-czo carrier, cerium salt, zirconates are dissolved in the water, add ethanol and citric acid, magnetic force
Stirring 1～5h forms colloidal sol, is proportionally added into sour modified attapulgite powder end, continues magnetic agitation 1～5h in gained colloidal sol,
Solvent evaporated in 60～90 DEG C of water-baths, gained gel is dried in an oven, and in 400～800 DEG C of roasting 3～7h, pulverizes
Sieve obtains attapulgite/cerium zirconium sosoloid composite；
During solution combustion method preparation pal-czo carrier, cerium salt, zirconates are dissolved in the water, add ethylene glycol to stir, to institute
Obtain and in solution, add sour modified attapulgite powder end, ultrasonic disperse 1～5h while stirring, resulting solution is placed directly within Muffle furnace
With 1.0～5.0 DEG C/min ramp to 400～800 DEG C of roasting 3～7h, pulverize and sieve acquisition attapulgite/cerium zirconium sosoloid
Composite；
(3) by infusion process preparation pal-czo load cu-zn-fe base catalyst, will active component cu, zn, fe and auxiliary agent co,
The nitrate of at least one of mn, rh, k or acetate or oxalates or citrate are configured to metal ion total concentration and are
The mixed aqueous solution of 0.5～5.0mol/l, is added thereto to attapulgite/cerium zirconium sosoloid composite powder at room temperature
Stirring dipping 3～24h, then dries, puts in Muffle furnace after pulverizing, in 300～500 DEG C of roasting 2～6h；
Above-mentioned cerium salt is selected from cerous nitrate or ammonium ceric nitrate, and zirconates is selected from one of zirconium nitrate, zirconyl nitrate or zirconium oxychloride；
The ethanol adding in above-mentioned sol-gel process preparation process is 0.5～4:1 with the mass ratio of aqueous solvent, the Fructus Citri Limoniae of interpolation
Sour molal quantity is 1～2:1 with the ratio of cerium, the molal quantity sum of zirconium ion；
The ethylene glycol adding in above-mentioned solution combustion method preparation process is 0.5～2:1 with the volume ratio of aqueous solvent；
In above-mentioned attapulgite/cerium zirconium sosoloid composite, the attapulgite modified mass ratio with cerium zirconium sosoloid of acid is 2～
5:1；Cerium zirconium sosoloid consist of cexzr1-xo2, 0.05≤x≤0.95.
5. bifunctional catalyst combined system is used for improving one-step method from syngas and prepares higher alcohols (c according to claim 16+
Alcohol) reactivity worth method it is characterised in that the admission space of described catalyst a and described catalyst b is than for 5/5～9/1.
6. bifunctional catalyst combined system is used for improving one-step method from syngas and prepares higher alcohols (c according to claim 16+
Alcohol) reactivity worth method it is characterised in that described reaction zone be 2～5 sections.
7. bifunctional catalyst combined system is used for improving one-step method from syngas and prepares higher alcohols (c according to claim 16+
Alcohol) reactivity worth method it is characterised in that described bifunctional catalyst combined system is carried out at reduction activation before the reaction
Reason, reducing condition is: reduction temperature is 300～500 DEG C, and reduction pressure is 0.5～4.0mpa, reduction air speed for 1000～
5000h-1, also Primordial Qi is h2.
8. bifunctional catalyst combined system according to claim 1 and 6 is used for improving one-step method from syngas and prepares higher alcohols
(c6+Alcohol) reactivity worth method it is characterised in that described thermal coupling reaction condition is: reaction temperature be 180～280 DEG C, instead
Pressure is answered to be 4.0～7.0mpa, reaction velocity is 2000～6000h-1, h2The mol ratio of/co is 1.0～3.0.
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| CN109126818A (en) * | 2018-08-17 | 2019-01-04 | 新奥科技发展有限公司 | Composite catalyst and preparation method thereof |
| CN113856687A (en) * | 2021-11-04 | 2021-12-31 | 太原理工大学 | Preparation method of doped ZnO catalyst and preparation method for synthesizing higher alcohol by using doped ZnO catalyst |
| WO2024089306A1 (en) * | 2022-10-28 | 2024-05-02 | Consejo Superior De Investigaciones Científicas (Csic) | Gas-solid catalytic process for converting an olefin into alcohol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101164024B1 (en) * | 2009-12-24 | 2012-07-18 | 한국화학연구원 | Cobalt based catalysts for reforming of methane by carbon dioxide, and production method of synthesis gas using them |
| CN102500374B (en) * | 2011-12-02 | 2014-02-26 | 上海中科高等研究院 | Copper-based nano catalyst for preparing high-carbon alcohol from synthetic gas as well as preparation method and application thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101164024B1 (en) * | 2009-12-24 | 2012-07-18 | 한국화학연구원 | Cobalt based catalysts for reforming of methane by carbon dioxide, and production method of synthesis gas using them |
| CN102500374B (en) * | 2011-12-02 | 2014-02-26 | 上海中科高等研究院 | Copper-based nano catalyst for preparing high-carbon alcohol from synthetic gas as well as preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126818A (en) * | 2018-08-17 | 2019-01-04 | 新奥科技发展有限公司 | Composite catalyst and preparation method thereof |
| CN109126818B (en) * | 2018-08-17 | 2021-12-07 | 新奥科技发展有限公司 | Composite catalyst and preparation method thereof |
| CN113856687A (en) * | 2021-11-04 | 2021-12-31 | 太原理工大学 | Preparation method of doped ZnO catalyst and preparation method for synthesizing higher alcohol by using doped ZnO catalyst |
| WO2024089306A1 (en) * | 2022-10-28 | 2024-05-02 | Consejo Superior De Investigaciones Científicas (Csic) | Gas-solid catalytic process for converting an olefin into alcohol |
| ES2971408A1 (en) * | 2022-10-28 | 2024-06-04 | Consejo Superior Investigacion | GAS-SOLID CATALYTIC PROCESS FOR CONVERSION OF OLEFIN INTO ALCOHOL (Machine-translation by Google Translate, not legally binding) |
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