CN106824239B - Furfural hydrogenation prepares catalyst of furfuryl alcohol and preparation method thereof - Google Patents
Furfural hydrogenation prepares catalyst of furfuryl alcohol and preparation method thereof Download PDFInfo
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- CN106824239B CN106824239B CN201710026173.4A CN201710026173A CN106824239B CN 106824239 B CN106824239 B CN 106824239B CN 201710026173 A CN201710026173 A CN 201710026173A CN 106824239 B CN106824239 B CN 106824239B
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- filter cake
- calcium carbonate
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 82
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 41
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005751 Copper oxide Substances 0.000 claims abstract description 18
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 18
- 239000000470 constituent Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000012065 filter cake Substances 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 8
- 230000002045 lasting effect Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000001133 acceleration Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- -1 rare earth compound Chemical class 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- HWVBCNFHNCFLTO-UHFFFAOYSA-L calcium;sulfuric acid;carbonate Chemical compound [Ca+2].OC(O)=O.[O-]S([O-])(=O)=O HWVBCNFHNCFLTO-UHFFFAOYSA-L 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229940078480 calcium levulinate Drugs 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- HCAJEUSONLESMK-UHFFFAOYSA-N cyclohexylsulfamic acid Chemical compound OS(=O)(=O)NC1CCCCC1 HCAJEUSONLESMK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- GTUVXOOHBUUGBH-UHFFFAOYSA-N furan;methanol Chemical compound OC.C=1C=COC=1 GTUVXOOHBUUGBH-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the catalyst and preparation method thereof that a kind of furfural hydrogenation prepares furfuryl alcohol.The catalyst is using calcium carbonate as carrier, using copper oxide as active constituent；The weight of copper oxide is 32wt%~75wt% of total catalyst weight.The production cost of catalyst of the invention is significantly reduced, and furfural conversion ratio and hydrogenation selectivity are also relatively high.
Description
Technical field
The present invention relates to the catalyst and preparation method thereof that a kind of furfural hydrogenation prepares furfuryl alcohol.
Background technique
Furfuryl alcohol is a kind of important fine chemicals, is widely used in the industries such as synthetic fibers, rubber and pesticide.Furfuryl alcohol can
For manufacturing various kinds of resin, wherein the excellent plasticizer of cold tolerance can be made in furfuryl alcohol resin.In China, 80%~90% chaff
Alcohol is consumed in furane resins.Furane resins are widely used in foundary industry as binder.Furfuryl alcohol is the good molten of varnish, pigment etc.
Agent can also be used as rocket fuel.Levulic acid can be made through hydrolysis in furfuryl alcohol, be the intermediate of nutrient drug calcium levulinate.Chaff
Alcohol is also used to produce friction pulley thermostable phenolic resin binder, such as braking sheet for automobile etc..Furfuryl alcohol be also production fragrance,
Flavouring agent, medicine, pesticide intermediate.
Furfuryl alcohol is mainly derived from the deep processing of furfural, is that hydrogenation reaction occurs over just partial hydrogenation product on carbonyl.Chaff
Aldehyde hydrogenating catalyst includes SiO2The catalyst of load, TiO2-SiO2The catalyst of load, Al2O3The catalyst of load, class neatly
The catalyst etc. of stone load.From the catalyst for having Cr till now without Cr catalyst, developed to from imported catalyst domestic
The performance of catalyst, furfural catalyst is higher and higher.For technology, Technical furfural catalyst is with Cu/SiO2Based on, this is to urge
The advantages of agent is catalyst without Cr, but its selectivity has a certain gap compared with catalyst containing Cr.In addition, furfural hydrogenation
The production cost for preparing the catalyst of furfuryl alcohol is still relatively high.In order to the market competitiveness, it is also necessary to further reduce it
Production cost.
Currently, furfuraldehyde hydrogenation catalyst mostly uses greatly the oxide-based carrier such as silica or porous mass class carrier.
For example, patent document CN102247883A is using loaded copper oxide on silica gel-modenite complex carrier；CN103007941A is adopted
With copper oxide-silica composite oxides；Nano-metallic copper dispersion is anchored to shape on magnesia matrix by CN104841436A
At catalyst；The carrier of CN105148923A is carbon nanotube, carbon fiber, graphene, SBA-15, gama-alumina or titanium dioxide
Titanium；JP Tetsukai 2015-229657A is using transition metal such as mesoporous silicon oxide solid supported nickel, palladium, gold, copper, ruthenium and rhodiums；
US4185022A is used and is deposited with copper-sodium metasilicate float stone as catalyst；It includes copper and fumed silica that US5591873A, which is used,
Catalyst；US5977010A uses the catalyst including copper oxide, clay and the calcium silicates being formed in situ.For another example, non-patent
Document 1 (Li Guoan, Speciality Petrochemicals, the 1st phase, the 40-44 pages, nineteen ninety-five) discloses several preparing furancarbinol from liquid-phase furol hydrogenation
Catalyst, active constituent Cu, carrier are selected from γ-A12O3, active carbon, TM grades of white carbon blacks, general purpose grade SiO2、SiO2(40-120
Mesh) or SiO2(110-120 mesh).
The existing reduction for being mainly used for unsaturated carbon carbon bond using calcium carbonate as the catalyst of carrier, and grain is mostly used greatly
Spend biggish calcium carbonate.For example, CN101811042A discloses one kind using palladium as active component, calcium carbonate or barium sulfate are carrier
Selective hydrocatalyst.The catalyst is used to 1,4- butynediols being reduced to 1,4- butylene glycol.That is, this is urged
Reduction reaction of the agent for triple carbon-carbon bonds to carbon-carbon double bond.For another example, CN104394988A discloses a kind of part hydrogenated carbon carbon
The pull-up catalyst of woods moral of three keys, support material be partial size be greater than 10 μm, the calcium carbonate less than 120 μm, active constituent be Pd and
Pb.The catalyst is also the reduction reaction for triple carbon-carbon bonds to carbon-carbon double bond.The patent document also indicates that: when for calcium carbonate
When the partial size of support material is greater than 10 μm, the selectivity of hydrogenation process is significantly improved.It can be seen that it is existing with calcium carbonate be carry
The catalyst of body is not used to the reduction of carbon oxygen unsaturated bond (such as carbonyl).In addition, such existing catalyst requirement carbon
The granularity of sour calcium has to be larger than 10 μm.
To sum up, in the catalyst that existing furfural hydrogenation prepares furfuryl alcohol, there is no be using calcium carbonate as carrier, with copper
The catalyst of active constituent；Particular without using calcium carbonate superfine powder as carrier, using copper as the catalyst of active constituent.In furfural
Hydrogen is added to prepare in the industrialized production of furfuryl alcohol, catalyst occupies its very big cost.If can be made with cheap calcium carbonate
Palladium isoreactivity ingredient is replaced by carrier and with relatively inexpensive copper activity ingredient, then for reducing the production cost of furfuryl alcohol very
It is important, it is also most important for improving the furfuryl alcohol competitiveness of product in market.
Summary of the invention
It is an object of the present invention to provide the catalyst that a kind of furfural hydrogenation prepares furfuryl alcohol, production cost is shown
Writing reduces, and furfural conversion ratio and hydrogenation selectivity are also relatively high.
It is another object of the present invention to provide the preparation methods that furfural hydrogenation prepares the catalyst of furfuryl alcohol, are produced into
This significant decrease, product stability are good.
The application reaches above-mentioned purpose by following technical solution.
The present invention provides the catalyst that a kind of furfural hydrogenation prepares furfuryl alcohol, is to live with copper oxide using calcium carbonate as carrier
Property ingredient；The weight of copper oxide is 32wt%~75wt% of total catalyst weight.
Furfural hydrogenation according to the present invention prepares the catalyst of furfuryl alcohol, it is preferable that the weight of copper oxide is overall catalyst weight
40wt%~70wt% of amount.
Furfural hydrogenation according to the present invention prepares the catalyst of furfuryl alcohol, it is preferable that the catalyst is closed without containing silication
Object, rare earth compound and other transition metal in addition to copper.
Furfural hydrogenation according to the present invention prepares the catalyst of furfuryl alcohol, it is preferable that the partial size D50 of the calcium carbonate is
150~300nm, partial size D90 are 150~700nm.
Furfural hydrogenation according to the present invention prepares the catalyst of furfuryl alcohol, it is preferable that the partial size D50 of the calcium carbonate is
200~250nm, partial size D90 are 200~550nm.
Furfural hydrogenation according to the present invention prepares the catalyst of furfuryl alcohol, it is preferable that the catalyst is graininess, grain
Degree is 15~150 μm.
The present invention also provides the preparation methods that above-mentioned furfural hydrogenation prepares the catalyst of furfuryl alcohol, it is preferable that it includes as follows
Step:
(1) under lasting stirring action, ammonia aqua stream is added in copper-bath to form mixed liquor；Wherein, described
Calcium carbonate is dispersed in copper-bath；
(2) under lasting stirring action, by sodium hydroxide solution, gradually stream is added in the mixed liquor, and stream leads to after adding
Enter compressed gas to escape ammonia, so that slurries are formed, the Cu in the slurries2+No more than 30ppm；
(3) filter cake is obtained after filtering the slurries that step (2) obtains, is dried up filter cake using compressed gas；
(4) by step (3) drying after filter cake use be washed to filtrate pH value be 7~8, then with compressed gas will washing after
Filter cake drying；
(5) filter cake that step (4) obtains is heated to catalyst butt at 105~115 DEG C and is not less than 98wt%, then powder
The broken catalyst that furfuryl alcohol is prepared to get the furfural hydrogenation.
Preparation method according to the present invention, it is preferable that the copper-bath quality in step (1), in terms of cupric sulfate pentahydrate
It is 6~18:1 with ammonium hydroxide mass ratio, mixing speed is 110~300rpm；In step (2), the sulfuric acid in terms of cupric sulfate pentahydrate
Copper solution quality and sodium hydroxide mass ratio are 5~6:1, and mixing speed is 110~300rpm；In step (3), by step
(2) the slurries filtering obtained, gained filtrate cycle is filtered, until filtrate is limpid, is dried up gained filter cake using compressed gas,
Compressed gas therein is compressed air；In step (4), the filter cake after step (3) drying is used and is washed to filtrate pH value as 7
~7.5, then dried up the filter cake after washing with compressed gas, compressed gas therein is compressed air；In step (5), heating
Temperature is 108~112 DEG C, and heating time is 30~60 hours.
Furfural hydrogenation according to the present invention prepares the catalyst of furfuryl alcohol, it is preferable that in step (1), the stream of ammonium hydroxide accelerates
Degree is 0.2~1.0ml/min, and stream continues 15~60min of stirring after adding；In step (2), the stream of sodium hydroxide solution accelerates
Degree is 3~8ml/min, and stream is passed through compressed gas time after adding is 1~3 hour.
Furfural hydrogenation according to the present invention prepares the catalyst of furfuryl alcohol, it is preferable that in step (1), in copper-bath
Water and cupric sulfate pentahydrate mass ratio be 3.3~3.8:1；Water and hydroxide in step (2), in sodium hydroxide solution
The mass ratio of sodium is 1.6~2.0:1.
The present invention is catalyst that active constituent obtains that furfural hydrogenation prepares furfuryl alcohol by carrier, copper oxide of calcium carbonate,
Its production cost is substantially reduced, furfural high conversion rate, and hydrogenation selectivity is also high.Preferred technical solution according to the present invention,
Using the calcium carbonate superfine powder of specified particle size range, furfural conversion ratio and hydrogenation selectivity can be further improved.Using the present invention
Preparation method, the size distribution of adjustable copper oxide, to improve its catalytic activity.In addition, preparation method of the invention
Cost it is low, product stability is good.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
In the present invention, partial size D50 indicates that the cumulative particle sizes percentile of a sample reaches corresponding when 50%
Partial size.Partial size D90 indicates that the cumulative particle sizes percentile of a sample reaches partial size corresponding when 90%.
In the present invention, furfural is also referred to as 2 furan carboxyaldehyde, double with the carbon oxygen outside the carbon-carbon double bond and ring in ring
Key (that is, carbonyl).It is to restore the C=O bond outside ring, and carbon-carbon double bond is not reduced then, is detailed in that furfural hydrogenation, which prepares furfuryl alcohol,
Following formula.
<catalyst>
Furfural hydrogenation of the invention prepares the catalyst of furfuryl alcohol using calcium carbonate as carrier, using copper oxide as active constituent；Oxygen
The weight for changing copper is 32wt%~75wt% of total catalyst weight.The present invention replaces silica with cheap calcium carbonate completely
As carrier, the production cost of catalyst can be significantly reduced.According to the preferred embodiment of the present invention, the catalyst is not
Contain silicon compound, rare earth compound and other transition metal in addition to copper.The example of silicon compound includes silica solution, water
Glass etc..The example of other transition metal in addition to copper includes chromium, iron etc..
In the present invention, the partial size D50 of the calcium carbonate is 150~300nm, and partial size D90 is 150~700nm.As
It is preferred that the partial size D50 of the calcium carbonate is 200~250nm, partial size D90 is 200~550nm.More preferably, described
The partial size D50 of calcium carbonate is 210~230nm, and partial size D90 is 250~380nm.Above-mentioned partial size of the invention is all made of laser grain
Degree instrument is measured.The size controlling of calcium carbonate in above range, can be further improved the reduction of C=O bond by the present invention
Reaction, inhibits the reduction reaction of carbon-carbon double bond, and be conducive to the raising of catalytic activity.That is, being conducive to furfural so also
Originally it is furfuryl alcohol, and improves its conversion ratio.
In the present invention, the weight of copper oxide be total catalyst weight 32wt%~75wt%, preferably 40wt%~
70wt%, more preferably 48wt%~60wt%.Copper content control will be aoxidized in above range, can be lived not reducing catalyst
Property in the case where, as much as possible reduction production cost.
In the present invention, the catalyst be graininess, granularity be 15~150 μm, preferably 15~100 μm, more
Preferably 20~50 μm.Above-mentioned granularity is measured by the way of sieving.The granularity of catalyst is controlled can change in above range
The furfural conversion ratio of kind catalyst, and improve furfuryl alcohol hydrogenation selectivity.
<preparation method>
The present invention also provides the preparation methods that above-mentioned furfural hydrogenation prepares the catalyst of furfuryl alcohol comprising following steps:
(1) under lasting stirring action, ammonia aqua stream is added in copper-bath to form mixed liquor；Wherein, described
Calcium carbonate is dispersed in copper-bath；
(2) under lasting stirring action, by sodium hydroxide solution, gradually stream is added in the mixed liquor, and stream leads to after adding
Enter compressed gas to escape ammonia, so that slurries are formed, the Cu in the slurries2+No more than 30ppm；
(3) filter cake is obtained after filtering the slurries that step (2) obtains, is dried up filter cake using compressed gas；
(4) by step (3) drying after filter cake use be washed to filtrate pH value be 7~8, then with compressed gas will washing after
Filter cake drying；
(5) filter cake that step (4) obtains is heated to catalyst butt at 105~115 DEG C and is not less than 98wt%, then powder
It is broken to get the catalyst.
Step (1) of the invention carries out under the action of lasting stirring, and mixing speed can be 110~300rpm, preferably
For 120~150rpm.Calcium carbonate is dispersed in copper-bath of the invention.Calcium carbonate is added in copper-bath, ultrasound
Wavelength-division dissipates or mechanical stirring, obtains the copper-bath for being dispersed with calcium carbonate.In above-mentioned mixed liquor, the partial size D50 of calcium carbonate
It is 150~700nm for 150~300nm, partial size D90.Preferably, the partial size D50 of the calcium carbonate is 200~250nm,
Partial size D90 is 200~550nm.More preferably, the partial size D50 of the calcium carbonate is 210~230nm, and partial size D90 is 250
~380nm.Above-mentioned partial size of the invention is all made of laser particle analyzer and is measured.By the size controlling of calcium carbonate in above-mentioned model
It encloses, can be further improved selectivity and conversion ratio that furfural is reduced to furfuryl alcohol.In copper-bath of the invention, Yi Wushui
The copper-bath quality of copper sulfate and the mass ratio of calcium carbonate can be 0.05~25:1；Preferably 0.5~15:1；More
Preferably 2~10:1.
In step (1) of the invention, ammonia aqua stream is added in copper-bath.Such adding manner, which can improve, urges
The size distribution and dispersibility of copper oxide in agent product, and then improve its hydrogenation selectivity and conversion ratio.The stream of ammonium hydroxide adds
Speed can be 0.2~1.0ml/min, preferably 0.3~0.8ml/min, more preferably 0.4~0.6ml/min.In ammonia aqua stream
After adding, continue 15~60min of stirring, preferably 30~50min.The flow acceleration of ammonium hydroxide is controlled in above range, it can
Copper oxide particle to be better dispersed on calcium carbonate carrier.
Ammonium hydroxide of the invention is the aqueous solution that ammonia is formed, and concentration is 13~18wt%.A tool according to the present invention
Body embodiment, ammonia concn of the invention are 15.92wt%.In the present invention, the copper-bath in terms of cupric sulfate pentahydrate
Quality and ammonium hydroxide mass ratio are 6~18:1；Preferably 8~17:1；More preferably 9~16:1.In step (1), copper sulphate
The mass ratio of water and cupric sulfate pentahydrate in solution is 3.3~3.8:1, preferably 3.5~3.7:1.
Step (2) of the invention carries out under the action of lasting stirring, and mixing speed can be 110~300rpm, preferably
For 120~150rpm.By sodium hydroxide solution, gradually stream is added in the mixed liquor, and stream is passed through compressed gas for ammonia after adding
Gas evolution preferably all escapes ammonia, to form slurries.Cu in the slurries2+No more than 30ppm, preferably no greater than
15ppm.It can guarantee the copper ammonia complexation ion of reaction system lacking as far as possible in this way, and improve the dispersion of copper oxide in catalyst
Property.The flow acceleration of sodium hydroxide solution can be 3~8ml/min, preferably 5~7ml/min.By the stream of sodium hydroxide solution
Acceleration Control can obtain and copper oxide particle is better dispersed on calcium carbonate carrier in above range.After stream adds,
The time for being passed through compressed gas is 1~3 hour, preferably 2~2.5 hours.
Copper-bath quality and sodium hydroxide mass ratio in step (2) of the invention, in terms of cupric sulfate pentahydrate
For 5~6:1, preferably 5.1~5.6:1, more preferably 5.2~5.5:1.Sodium hydroxide of the invention is made in a manner of aqueous solution
With above-mentioned mass ratio is cupric sulfate pentahydrate and sodium hydroxide mass ratio.Water and sodium hydroxide in sodium hydroxide solution
Mass ratio is 1.6~2.0:1, preferably 1.8~1.9:1.
In step (3) of the invention, the slurries of step (2) are filtered, gained filtrate cycle is filtered, until filtrate is clear
It is clear, gained filter cake is dried up using compressed gas.Compressed gas of the invention includes compressed air.Circulating filtration is until filtrate is clear
Clear purpose is to save material, avoids wasting.
In step (4) of the invention, the filter cake after step (3) drying is used and is washed to filtrate pH value as 7~7.5,
Preferably 7~7.2, then dried up the filter cake after washing with compressed gas.Compressed gas of the invention includes compressed air.
In step (5) of the invention, the filter cake that step (4) obtains is heated to catalyst butt not at 105~115 DEG C
Less than 98wt%, then crush to get the catalyst.Heating temperature is preferably 108~112 DEG C.Heating time can be 30
~60 hours, preferably 35~50 hours.The mode of crushing is not particularly limited, such as polishing etc..It is urged smashed
Agent sieving, obtains granular catalyst prod.Catalyst of the invention can not need high-temperature roasting process, thus can be with
Mass energy is saved, to further decrease production cost.
Raw material used in the following embodiment is described as follows:
Calcium carbonate: calcium carbonate superfine powder, the D50 for using laser particle analyzer to measure is 150nm, D90 350nm.
Copper-bath: the mass ratio of water and cupric sulfate pentahydrate is 3.57.
Ammonium hydroxide: concentration is the aqueous solution of 15.92wt%.
Sodium hydroxide solution: the mass ratio of water and sodium hydroxide is 1.89.
Waterglass: Na2The content of O is 8.684wt%；SiO2Content is 28.46wt%.
Test method in following embodiment is described as follows:
Using the granularity of Malvern company, Britain MS-2000 laser particle analyzer measurement nanometer calcium carbonate, nanometer calcium carbonate is come
From Beijing Deco Dao Jin Science and Technology Ltd..Using the grain of Malvern company, Britain MS-2000 laser particle analyzer measurement catalyst
Degree.
Embodiment 1
1.5kg calcium carbonate is dispersed in the copper-bath containing 2.8kg cupric sulfate pentahydrate of 12.8kg and forms mixing
Then the mixed liquor is placed in container by liquid.356g ammonium hydroxide is added in separatory funnel, then according to the flow of 0.5ml/min,
Ammonia aqua stream is added in the container for filling mixed liquor, the mixing speed during stream adds is 150rpm.After stream adds, continue to tie up
Hold stirring 30min.According to the flow of 5ml/min, by 1.53kg sodium hydroxide solution, gradually stream is added in above-mentioned reaction system, stream
Mixing speed during adding is 150rpm.After stream adds, continue to stir, while being passed through compressed air to container bottom, tie up
2h or so is held, to guarantee that ammonia all escapes, Cu in slurries2+≯30ppm.Filter tunnel, filtrate cycle is added in the slurries
To after limpid, then with the dry filter cake of compressed air wind.Gained filter cake is repeated into washed several times with water, until filtrate pH=7, then with compressing
Air dries up filter cake.Filter cake is poured out, 48 hours are heated at 110 DEG C to catalyst butt ≮ 98wt%.Resulting material is crushed
To 38~48 μm, as catalyst P1.
The preparation process of embodiment 1 is repeated to catalyst P2, P3 secondary, then that obtain two batches.
Embodiment 2~3
Other than replacing with the material quality of addition shown in table 1, remaining step and condition are same as Example 1,
Successively obtain catalyst Q and R.
Comparative example 1
By according to the formula in table 1, the copper-bath containing 2.8kg cupric sulfate pentahydrate of 12.8kg is placed in container.It will
4.44kg waterglass and 178g ammonium hydroxide are separately added into separatory funnel, then according to waterglass 10ml/min and ammonium hydroxide 0.44ml/
Waterglass and ammonium hydroxide are added in the container for filling mixed liquor the flow of min in a manner of bifilar cocurrent, flow stirring during adding
Mixing speed is 150rpm.After stream adds, stirring 30min is continued to.According to the flow of 5ml/min, by 1.53g sodium hydroxide
Gradually stream adds in above-mentioned reaction system solution, and the mixing speed during stream adds is 150rpm.After stream adds, continue to stir
It mixes, while being passed through compressed air to container bottom, maintain 2h or so, to guarantee that ammonia all escapes, Cu in slurries2+≯30ppm。
The slurries are added filter tunnel, filtrate cycle is to after limpid, then with the dry filter cake of compressed air wind.Gained filter cake is repeated
Washed several times with water, until filtrate pH value 7, then dried up filter cake with compressed air.Filter cake is poured out, 48 hours are heated at 110 DEG C to urging
Agent butt ≮ 98wt%.Resulting material is crushed to 38~48 μm, as catalyst E.
Table 1
Experimental example
The catalyst of 15g Examples 1 to 3 and comparative example 1 is weighed respectively, and reaction kettle then is added together with 2580ml furfural
In, it is reacted 1.5 hours under conditions of temperature is 220 DEG C, Hydrogen Vapor Pressure 3.5MPa, speed of agitator are 300 revs/min.Experiment
As a result referring to table 2.
In embodiment 1, furfural conversion ratio, the furfuryl alcohol for the catalyst that different batches obtain are selectively close.This shows this
The preparation method of invention can be stable with production performance furfuraldehyde hydrogenation catalyst.Examples 1 to 3 is compared with comparative example 1, furfuryl alcohol choosing
Selecting property increases, and cost then substantially reduces.
Table 2
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (7)
1. the preparation method that a kind of furfural hydrogenation prepares the catalyst of furfuryl alcohol, it is characterised in that:
The catalyst is using calcium carbonate as carrier, using copper oxide as active constituent；The weight of copper oxide is total catalyst weight
32wt%~75wt%；The catalyst without containing silicon compound, rare earth compound and in addition to copper other transition gold
Belong to；The partial size D50 of the calcium carbonate is 150~300nm, and partial size D90 is 150~700nm；
It includes the following steps:
(1) under lasting stirring action, ammonia aqua stream is added in copper-bath to form mixed liquor；Wherein, the sulfuric acid
Calcium carbonate is dispersed in copper solution；
(2) under lasting stirring action, by sodium hydroxide solution, gradually stream is added in the mixed liquor, and stream is passed through pressure after adding
Contracting gas escapes ammonia, so that slurries are formed, the Cu in the slurries2+No more than 30ppm；
(3) filter cake is obtained after filtering the slurries that step (2) obtains, is dried up filter cake using compressed gas；
(4) filter cake after step (3) drying is used and is washed to filtrate pH value as 7~8, then with compressed gas by the filter after washing
Cake drying；
(5) filter cake that step (4) obtains is heated to catalyst butt not less than 98wt% at 105~115 DEG C, then crushed,
The catalyst of furfuryl alcohol is prepared up to the furfural hydrogenation.
2. preparation method according to claim 1, it is characterised in that:
In step (1), copper-bath quality and ammonium hydroxide mass ratio in terms of cupric sulfate pentahydrate are 6~18:1, mixing speed
For 110~300rpm；
In step (2), copper-bath quality and sodium hydroxide mass ratio in terms of cupric sulfate pentahydrate are 5~6:1, stirring speed
Degree is 110~300rpm；
In step (3), the slurries that step (2) is obtained are filtered, and gained filtrate cycle is filtered, until filtrate is limpid, using pressure
Contracting gas dries up gained filter cake, and compressed gas therein is compressed air；
In step (4), the filter cake after step (3) drying use and is washed to filtrate pH value as 7~7.5, then with compressed gas general
Filter cake drying after washing, compressed gas therein are compressed air；With
In step (5), heating temperature is 108~112 DEG C, and heating time is 30~60 hours.
3. preparation method according to claim 2, it is characterised in that:
In step (1), the flow acceleration of ammonium hydroxide is 0.2~1.0ml/min, and stream continues 15~60min of stirring after adding；With
In step (2), the flow acceleration of sodium hydroxide solution is 3~8ml/min, and stream is passed through the time of compressed gas after adding
It is 1~3 hour.
4. preparation method according to claim 3, it is characterised in that:
In step (1), the mass ratio of water and cupric sulfate pentahydrate in copper-bath is 3.3~3.8:1；With
In step (2), the mass ratio of water and sodium hydroxide in sodium hydroxide solution is 1.6~2.0:1.
5. preparation method according to claim 1, which is characterized in that the weight of copper oxide is total catalyst weight
40wt%~70wt%.
6. preparation method according to claim 5, which is characterized in that the partial size D50 of the calcium carbonate be 200~
250nm, partial size D90 are 200~550nm.
7. preparation method according to claim 5, which is characterized in that the catalyst is graininess, granularity 15
~150 μm.
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| CN102513107A (en) * | 2011-12-20 | 2012-06-27 | 淄博明新化工有限公司 | Copper-based catalyst for neopentylene glycol preparation from hydrogenation method and preparation method thereof |
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| CN102631930A (en) * | 2012-03-30 | 2012-08-15 | 南京熙辉新材料有限公司 | Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof |
| CN105498787B (en) * | 2014-09-25 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of methylfuran catalyst of preparation by furfural gas phase hydrogenation 2 and preparation method |
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| CN102513107A (en) * | 2011-12-20 | 2012-06-27 | 淄博明新化工有限公司 | Copper-based catalyst for neopentylene glycol preparation from hydrogenation method and preparation method thereof |
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| 纳米Cu(OH)2/SiO2催化剂的制备条件对糠醛加氢反应的影响;廉金超等;《石油炼制与化工》;20100228;第41卷(第2期);第41-44页 * |
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