CN106925293A - Nickel-base catalyst and its preparation method and application - Google Patents
Nickel-base catalyst and its preparation method and application Download PDFInfo
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- CN106925293A CN106925293A CN201710190670.8A CN201710190670A CN106925293A CN 106925293 A CN106925293 A CN 106925293A CN 201710190670 A CN201710190670 A CN 201710190670A CN 106925293 A CN106925293 A CN 106925293A
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- nickel
- base catalyst
- acetone
- alloying pellet
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 86
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004411 aluminium Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 238000005275 alloying Methods 0.000 claims description 52
- 239000002585 base Substances 0.000 claims description 52
- 239000008188 pellet Substances 0.000 claims description 52
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001994 activation Methods 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- HHAVHBDPWSUKHZ-UHFFFAOYSA-N propan-2-ol;propan-2-one Chemical compound CC(C)O.CC(C)=O HHAVHBDPWSUKHZ-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002699 waste material 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
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of nickel-base catalyst, isopropanol is prepared for being catalyzed acetone hydrogenation reaction, with the percent by weight of the nickel-base catalyst, including 35 60% nickel, 20 60% aluminium, 1 10% copper, 0.5 10% iron, and 0.5 5% manganese.The invention also discloses the preparation method of the nickel-base catalyst, and the application in acetone hydrogenation reaction fixed bed reactors in isopropanol acetone hydrogen chemical heat pump.Relative to prior art, nickel-base catalyst high mechanical strength of the invention, acetone conversion is high, isopropanol is selectively high, anti-poisoning capability is strong, and simple production process, is easy to industrialization, has a good application prospect and huge economic benefit.
Description
Technical field
The present invention relates to catalytic field and field of energy utilization, and in particular to one kind catalysis acetone hydrogenation reaction prepares isopropyl
Nickel-base catalyst of alcohol and preparation method thereof, and answering in acetone hydrogenation reaction in isopropanol-acetone-hydrogen chemical heat pump
With.
Technical background
Current China efficiency of energy utilization is relatively low, and be also greatly improved space compared with developed countries, waste heat recovery profit
The important means for having become and improving efficiency of energy utilization, solve energy crisis is recycled with especially low temperature exhaust heat.Low temperature
Waste heat taste is low, it is difficult to directly utilize, and major part is discharged and causes huge energy waste.The side of best utilization low temperature exhaust heat
Formula is, by the lifting of its temperature, to make it possible to be utilized.If this method is accomplished, energy profit can be not only increased substantially
With rate, and the scope of using energy source can be expanded, such as solar energy, geothermal energy low temperature natural energy resources, effectively alleviate energy danger
Machine.The recycling of industrial low-temperature waste heat has responded energy-saving and emission-reduction and the cleaning energy of whole world promotion with the exploitation of solar energy
The energy policy in source.
Realize that the device that low-temperature heat source heats up is heat pump, the heat pump of heating type is generally included：It is mechanical heat pump, absorption
Heat pump.The ability that mechanical heat pump needs is input into many, consumption greatly, and the temperature raising amplitude of mechanical heat pump is small；Although absorption heat pump
There is larger temperature raising amplitude, and with large-scale industrial application, but can be needed between the component of absorption heat pump very big
Pressure shifts energy, which results in operation and maintenance expense higher.Chemical heat pump can overcome mechanical heat pump and absorption
The deficiency of heat pump.Chemical heat pump be by chemically react fuel factor by thermal energy be chemical energy, specifically using working medium pair
Reversible chemical reaction, absorbed heat at different temperature and exothermic reaction, so as to realize energy conversion, storage and turn
Move.Chemical heat pump has a heat storage ability higher compared with other heat pumps, its reactant and product can with long-term storage, and
Energy stores will not cause any heat loss in chemical substance because of the temperature difference between environment.
Chemical heat pump turns into low-heat taste and carries the advantages of its high efficiency, pollution-free, low energy consumption, temperature lifting amplitude high
The first-selected device for rising.Isopropanol-acetone-hydrogen (IAH) chemical heat pump is then application potential is larger in numerous chemical heat pumps one
Kind.It utilizes a pair of reversible chemical reactions, isopropanol low temperature (80 DEG C) dehydrogenation that the endothermic reaction generation acetone and hydrogen, third occur
There is exothermic reaction generation isopropanol in (200 DEG C) hydrogenation of ketone high-temperature hydrogenation, so as to make it possible to the lifting of Low Temperature Thermal temperature in work
Directly applied in industry.With huge commercial application potentiality.
The key technology of IAH chemical heat pumps is the exploitation of efficient catalyst, and its development is also mainly by the property of catalyst
Can limitation.Catalyst has both sides to apply in IAH chemical heat pumps：One is the dehydrogenation reaction of isopropanol, and two is that acetone adds
Hydrogen reacts.Catalyst needs to have the condition of high selectivity, high activity, long lifespan.Dehydrogenation of isopropanol endothermic reaction catalyst agent master
If noble metal catalyst such as Pt, Pd, Ru etc., carrier is based on activated carbon, in addition also copper zinc catalyst.Acetone hydrogenation reacts
Mainly loaded noble metal catalyst such as Ru/C, Ru/Al2O3, Pt/C and nickel-base catalyst and copper-based catalysts.But at present
The catalyst of most of preparing isopropyl alcohol by acetone hydrogenation all in the laboratory research stage, industrial alternative acetone hydrogenation
Catalysts do not have substantially.
The content of the invention
The present invention be directed to the deficiencies in the prior art, it is proposed that can meet industrial requirement for being catalyzed acetone hydrogenation
Reaction prepares the nickel-base catalyst of isopropanol, the preparation method of the nickel-base catalyst, and the acetone hydrogenation in IAH chemical heat pumps
Application in fixed bed.Present invention includes：
On the one hand, the invention discloses a kind of nickel-base catalyst, isopropanol is prepared for being catalyzed acetone hydrogenation reaction, with institute
State the percent by weight of nickel-base catalyst, including 35-60% nickel, the aluminium of 20-60%, the copper of 1-10%, 0.5-10%'s
Iron, and 0.5-5% manganese.
Further, nickel-base catalyst of the invention is graininess.Nickel-base catalyst granularity of the invention is 1.0-
10.0mm, it is preferable that granularity is 3.0-6.0mm；Or, a diameter of 1-10mm of nickel-base catalyst of the invention is highly 1-
10mm, it is preferable that a diameter of 2-6mm, is highly 2-6mm.The shape of the nickel-base catalyst include irregular shape, it is spherical, half
The combination of one or more in spherical, bar shaped, cylinder, rod, tooth form, hollow rod.
Further, the nickel-base catalyst includes active material outer surface layer and metal alloy kernel, the active matter
Matter outer surface layer is loose structure, and the metal alloy kernel is compact texture.The porous knot of the active material outer surface layer
The total pore volume of structure is more than 0.12ml/mlCatalyst, the volume accounting of mesopore and macropore in the loose structure in the range of 15-45%,
The volume accounting of micropore is in the range of 85-55%.In the present invention, micropore refers to hole of the average pore size less than 2nm, and mesopore is
Refer to the hole less than 50nm more than 2nm, macropore refers to the hole more than 50nm.The mean intensity of the metal alloy kernel is pressed for side
It is powerful in 300N.
Further, the nickel-base catalyst is the nickel-base catalyst activated by aqueous slkali.
On the other hand, the invention also discloses a kind of preparation method of nickel-base catalyst as described above, including：
Step one：Metal mixture is provided, with the percent by weight of the metal mixture, including：35-60%'s
The manganese of nickel, the aluminium of 20-60%, the copper of 1-10%, the iron of 0.5-10%, and 0.5-5%；
Step 2：The metal mixture is processed into alloying pellet；
Step 3：Activation process is carried out to the alloying pellet with aqueous slkali, the alloying pellet after being activated；And
Step 4：The alloying pellet after the activation is washed, the nickel-base catalyst is obtained.
Further, the preparation process of the alloying pellet in the step 2 includes：(1) high-temperature fusion technology is used
The metal mixture is smelted into fused solution alloy；(2) fused solution alloy cooling is obtained into solid alloy, it is described
It is cooled to quenching or ladder is cooled to normal temperature；(3) solid alloy is prepared into the alloying pellet, by the solid alloy
The method for being prepared into the alloying pellet includes：Screening obtains the alloying pellet after broken, or, the solid alloy is broken
Reshaping obtains the alloying pellet after being broken into powder.Wherein, it is described it is broken after screening refer to, using disintegrating machine to solid alloy
Crushed, then by screen cloth choose certain particle size alloying pellet, such as granularity in 1-10mm scopes, what the method was obtained
Alloying pellet is irregular shape, and disintegrating machine can be mechanical jaw crusher, impact crusher or hammer stone disintegrating machine.It is described
Reshaping refers to after being broken into powder, and it is thin that the particle that crusher in crushing is obtained yields less than 100 purposes by modes such as ball millings
Powder, is subsequently adding the forming agents such as aluminum oxide, water, binding agent, and alloying pellet, example are obtained by way of beating piece, extrusion or spin
Such as, cylindrical alloying pellet can be obtained by beating piece, the shapes such as cylinder, tooth form, hollow cylindrical can be obtained by extrusion
The alloying pellet of shape, the shape of alloying pellet depends on extrusion die, and reshaping granulation is general after solid alloy is broken into powder
Obtain the alloying pellet that granularity is 1-10mm.
Used as another embodiment, the preparation process of the alloying pellet in the step 2 can also use as follows
Method：(1) metal mixture is smelted into fused solution alloy using high-temperature fusion technology；And (2) use and pour casting
The fused solution alloy is processed into the alloying pellet by the method for grain or rotating granulation.Wherein, it is described casting granulation refer to
The liquid alloy of melting is carried out into casting straight forming and obtains little particle, shape includes spherical, hemispherical, rod or cuboid
Shape, is generally obtained the alloying pellet that granularity is 1-10mm.The rotating granulation refers to the liquid alloy that will be melted through overwinding
Turn granulation and obtain spheric granules, be generally obtained the alloying pellet that granularity is 1-10mm.
Further, in implementation method of the both the above about alloying pellet preparation process, described in the step (1)
The temperature of melting is 1300-1700 DEG C, and the smelting time is 0.2-0.5 hours.
Further, the activation process in the step 3 is anti-including the alloying pellet is placed in into a fixed bed
In answering device, make the aqueous slkali by the alloying pellet, the aqueous slkali include sodium hydroxide solution, potassium hydroxide solution or
Both mixtures.Preferably, the concentration of the aqueous slkali is 0.1-10wt%, and weight space velocity is 4-50h-1, at the activation
The temperature of reason is 20 DEG C -60 DEG C, and the time of the activation process is 2-12 hours.More preferably, concentration is 0.3-3wt%'s
Potassium hydroxide solution carries out activation process, and potassium hydroxide solution electrical conductivity is that the water of 10-150 μ s/cm is prepared, and potassium hydroxide is molten
The weight space velocity of liquid is 6-30h-1, activating treatment temperature scope is 20 DEG C -50 DEG C, and the activation process time is 4-10 hours.
Further, the washing process in the step 4 is included using deionized water to the alloying pellet after the activation
Washed, when the pH value of washing to cleaning solution is 7-9, stopped washing；The temperature of the washing is 20 DEG C -50 DEG C.
The third aspect, invention additionally discloses a kind of nickel-base catalyst as described above in isopropanol-acetone-hydrogen chemical heat
Application in the reaction of pump acetone hydrogenation, including：The acetone hydrogenation reaction is carried out in a fixed bed reactors, it is described Ni-based
The granularity of catalyst is 2-10mm, and the mol ratio of hydrogen/acetone is 1-20:1, reaction temperature is 180-210 DEG C, and pressure is 0.1-
6MPa, liquid air speed is 0.1-10h-1, the content of acetone is 60-100wt% in liquid.
Further, described nickel-base catalyst of the present invention is in isopropanol-acetone-hydrogen chemical heat pump acetone hydrogenation reaction
In application, wherein, the granularity of the nickel-base catalyst is 3-6mm, and the mol ratio of hydrogen/acetone is 1.5-10:1, pressure is
0.5-5MPa, liquid air speed is 0.5-6h-1, the content of acetone is 75-99wt% in liquid；Under this condition, the acetone adds
The high temperature heat source of sustainable 200 DEG C of the generation of hydrogen reaction.
Relative to prior art, the beneficial effects of the present invention are：
It is of the invention to prepare the nickel-base catalyst of isopropanol by nickel, aluminium, copper, iron and manganese group for being catalyzed acetone hydrogenation reaction
Into, with high mechanical strength, the characteristics of acetone conversion is high, isopropanol is selectively high, and the anti-poisoning energy of the nickel-base catalyst
Power is strong, long service life, has a good application prospect and huge economic benefit.
Nickel-base catalyst preparation process of the invention includes the step of by metal mixture granulation, activation, washing, producing work
Skill is simple, cost economy, be easy to industrialization.Quenching or ladder cooling technology means after the melting for wherein using, it is ensured that alloy is equal
Even segregation-free, alloy crystalline phase refinement controls alloy with uniformly by the electrical conductivity and concentration of lye of the water for controlling to prepare alkali lye
The active rate of grain, so that the activated centre dispersiveness for producing is high, pore distribution is suitable, and micropore and middle macropore ratio are reasonable.
Nickel-base catalyst of the invention is applied in IAH chemical heat pumps in acetone hydrogenation reaction, using fixed bed reactors,
It is simple to operate, process stabilizing, it is easy to industrialize, the acetone continuously hydrogen adding that will can be obtained using low-temperature heat source dehydrogenation of isopropanol,
And continue to produce 200 DEG C of high temperature heat sources, and make follow-up acetone and the reduction of isopropanol separating pressure, energy consumption reduction, therefore, it is possible to
Industrial low-temperature waste heat or solar energy are efficiently utilized, meets the energy-saving and emission-reduction of whole world promotion and the energy policy of clean energy resource.
Specific embodiment
Unless otherwise defined, the technical term or scientific terminology for being used in claims and specification should be this hair
The ordinary meaning that the personage with general technical ability is understood in bright art.
Below in conjunction with specific embodiment, the invention will be further described, it should be pointed out that embodiment described below purport
Being easy to the understanding of the present invention, and any restriction effect is not played to the scope of protection of present invention.
Embodiment 1-4 is respectively to prepare alloying pellet in a variety of ways using the metal mixture of heterogeneity, and right
Alloying pellet carries out the preparation process that alkali lye activation process prepares granular fixed bed nickel-base catalyst.
Embodiment 1
It is accurate to weigh nickel 400 gram of the purity more than 99%, aluminium 500 gram of the purity more than 99%, copper of the purity more than 99%
50 grams, 10 grams of the manganese that purity is more than 99% 40 grams of iron, purity is more than 99%, obtain metal mixture, by this after being well mixed
Metal mixture is placed in middle frequency furnace and is melted in 1650 DEG C, and the time, at 0.5 hour, is poured out in mould by quenching side
Formula is cooled down, and is crushed by jaw crusher, and sieve obtains to granularity the alloying pellet for 3-6mm.
Then, alloying pellet 200g obtained above is taken, is placed in the quartz glass tube that internal diameter is 60mm, be by concentration
The KOH solution (electrical conductivity of the water for preparing KOH solution is 50 μ s/cm) of 1.0wt% is with air speed 12h-1Speed from quartz
The bottom of glass tube flows into by alloying pellet bed and then is flowed out from top.Bed temperature is 30 DEG C, and the activation process time is 5
Hour.Washed with 40 DEG C of deionized water after alkali lye activation process, until the pH of solution is 7-9 after washing, stopped washing,
Graininess fixed bed nickel-base catalyst is obtained.
Embodiment 2
It is accurate to weigh nickel 420 gram of the purity more than 99%, aluminium 480 gram of the purity more than 99%, copper of the purity more than 99%
60 grams, 10 grams of the manganese that purity is more than 99% 30 grams of iron, purity is more than 99%, obtain metal mixture, by this after being well mixed
Metal mixture is placed in middle frequency furnace and is melted in 1650 DEG C, and the time, at 0.4 hour, is poured out in mould by ladder side
Formula is cooled down, and is crushed by hammering stone disintegrating machine into shape, and sieve obtains to granularity the alloying pellet for 3-6mm.
Then, alloying pellet 200g obtained above is taken, is placed in the quartz glass tube that internal diameter is 60mm, be by concentration
The KOH solution (electrical conductivity of the water for preparing KOH solution is 100 μ s/cm) of 0.8wt% is with air speed 15h-1Speed from quartz
The bottom of glass tube flows into by alloying pellet bed and then is flowed out from top.Bed temperature is 30 DEG C, and the activation process time is 6
Hour.Washed with 45 DEG C of deionized water after alkali lye activation process, until the pH of solution is 7-9 after washing, stopped washing,
Graininess fixed bed nickel-base catalyst is obtained.
Embodiment 3
It is accurate to weigh nickel 400 gram of the purity more than 99%, aluminium 550 gram of the purity more than 99%, copper of the purity more than 99%
30 grams, 10 grams of the manganese that purity is more than 99% 10 grams of iron, purity is more than 99%, obtain metal mixture, by this after being well mixed
Metal mixture is placed in middle frequency furnace and is melted in 1550 DEG C, and the time, at 0.3 hour, is poured out in mould by ladder side
Formula is cooled down, and alloyed powder of the particle diameter less than 200 mesh is obtained by jaw crusher and ball mill, be subsequently adding water, boehmite,
Binding agent, is obtained the rod alloying pellet of diameter 3mm, length 2-6mm after being extruded into bar, drying and roasting.
Then, by metal alloy particle 200g obtained above, it is placed in the quartz glass tube that internal diameter is 60mm, by concentration
Be 1.2wt% KOH solution (for prepare KOH solution water electrical conductivity be 90 μ s/cm) with air speed 25h-1Speed from stone
The bottom of English glass tube flows into by metal alloy particle bed and then is flowed out from top.Bed temperature is 30 DEG C, activation process
Time is 5 hours.Washed with 40 DEG C of deionized water after alkali lye activation process, until the pH of solution is 7-9 after washing, stopped
Only wash, graininess fixed bed nickel-base catalyst is obtained.
Embodiment 4
It is accurate to weigh nickel 350 gram of the purity more than 99%, aluminium 480 gram of the purity more than 99%, copper of the purity more than 99%
70 grams, 40 grams of the manganese that purity is more than 99% 60 grams of iron, purity is more than 99%, obtain metal mixture, by this after being well mixed
Metal mixture is placed in middle frequency furnace and is melted in 1600 DEG C, and the time, at 0.5 hour, is poured out in mould by quenching side
Formula is cooled down, and is crushed by jaw crusher, and screening obtains the alloying pellet that granularity is 3-6mm.
Then, by alloying pellet 200g obtained above, it is placed in the quartz glass tube that internal diameter is 60mm, is by concentration
The KOH solution (electrical conductivity of the water for preparing KOH solution is 150 μ s/cm) of 0.5wt% is with air speed 10h-1Speed is from quartzy glass
The bottom of glass pipe flows into by metal alloy particle bed and then is flowed out from top.Bed temperature is 35 DEG C, activation process time
It is 8 hours.Washed with 40 DEG C of deionized water after alkali lye activation process, until the pH of solution is 7-9 after washing, stop washing
Wash, graininess fixed bed nickel-base catalyst is obtained.
Comparative example 1
It is accurate to weigh 520 grams of the aluminium of 480 grams of nickel of the purity more than 99% and purity more than 99%, it is placed in middle frequency furnace
Row melting, fused materials are poured out in mould by natural cooling, are crushed by jaw crusher, and screening obtains granularity
It is the alloying pellet of 3-6mm.
Then, alloying pellet 200g obtained above is placed in the quartz glass tube that internal diameter is 60mm, is by concentration
The NaOH alkali lye of 1.0wt% is flowed into by alloying pellet bed then from top with the speed of 8L/h from the bottom of quartz glass tube
Outflow.The activation process time is 6 hours.Washed with deionized water after alkali lye activation process, until washing after solution pH
It is 7-9, stops washing, graininess fixed bed nickel-base catalyst is obtained.
Catalyst performance evaluation：
Acetone hydrogenation reaction is carried out in fixed bed reactors, and the Ni-based of preparation is urged in choosing embodiment 1-4 and comparative example 1
Each 100 grams of agent, is transferred in a diameter of 3 centimetres of fixed bed reaction, and reactor is opened with heating and cooling device, reactor
Beginning is heated to 180-210 DEG C, is passed through the acetone and hydrogen of preheating, and the mol ratio of hydrogen/acetone is 1.5-10:1, maintenance reaction pressure
Power 0.5-5MPa, liquid air speed 0.5-6h-1, acetone weight content 75-99% in liquid.The reaction maintenance stage stops heating, leads to
Cross reaction heat and cooling system and maintain temperature, product by analyzing product liquid content with gas-chromatography (GC) after condensation,
Calculate acetone conversion and isopropanol selectivity.
Reaction condition and reaction result are shown in Table 1.
Table 1.
For the life-span for illustrating nickel-base catalyst of the present invention and antitoxin performance, (sulphur is contained for 95.5% in content of acetone
0.5ppm), liquid air speed 3.5h-1, hydrogen is 4 with acetone mol ratio, under the conditions of pressure 3.5MPa, to maintain 200 DEG C of temperature
Time is obtained catalyst as the standard for investigating catalyst life, embodiment 4, is gone back in the case where not heating by 1000 hours
Can maintain 200 DEG C of high temperature, and nickel-base catalyst system obtained in comparative example 1, by after 400 hours, in situation about not heating
Under, temperature begins to decline (natural heat dissipation), illustrates that the nickel-base catalyst life-span of the invention is longer, and anti-poisoning capability is strong, Neng Gouman
Acetone hydrogenation reaction produces the requirement of high temperature heat source in sufficient IAH chemical heat pumps.
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only
It is specific embodiment of the invention, is not intended to limit the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion are substituted, and be should be included within the scope of the present invention.
Claims (12)
1. a kind of nickel-base catalyst, prepares isopropanol, it is characterised in that with the nickel catalyst for being catalyzed acetone hydrogenation reaction
The percent by weight of agent, including 35-60% nickel, the aluminium of 20-60%, the copper of 1-10%, the iron of 0.5-10%, and 0.5-
5% manganese, the nickel-base catalyst is graininess, and the granularity of the nickel-base catalyst is 1.0-10.0mm, or, a diameter of 1-
10mm, is highly 1-10mm, and the shape of the nickel-base catalyst includes irregular shape, spherical, hemispherical, bar shaped, cylinder, rod
The combination of one or more in shape, tooth form, hollow rod.
2. nickel-base catalyst according to claim 1, wherein, the nickel-base catalyst include active material outer surface layer and
Metal alloy kernel, the active material outer surface layer is loose structure, and the metal alloy kernel is compact texture.
3. nickel-base catalyst according to claim 1, wherein, the nickel-base catalyst be by aqueous slkali activate it is Ni-based
Catalyst.
4. a kind of preparation method of nickel-base catalyst as claimed in claim 1, including：
Step one：A kind of metal mixture is provided, with the percent by weight of the metal mixture, including：35-60%'s
The manganese of nickel, the aluminium of 20-60%, the copper of 1-10%, the iron of 0.5-10%, and 0.5-5%；
Step 2：The metal mixture is processed into alloying pellet；
Step 3：Activation process is carried out to the alloying pellet with aqueous slkali, the alloying pellet after being activated；
Step 4：The alloying pellet after the activation is washed, the nickel-base catalyst is obtained.
5. the preparation method of nickel-base catalyst according to claim 4, wherein, the alloying pellet in the step 2
Preparation process include：(1) metal mixture is smelted into fused solution alloy using high-temperature fusion technology；(2) by institute
State the cooling of fused solution alloy and obtain solid alloy, it is described to be cooled to quenching or ladder is cooled to normal temperature；(3) solid-state is closed
Gold is prepared into the alloying pellet, and the method that the solid alloy is prepared into the alloying pellet is included：Screened after broken
To the alloying pellet, or, reshaping obtains the alloying pellet after the solid alloy is broken into powder.
6. the preparation method of nickel-base catalyst according to claim 4, wherein, the alloying pellet in the step 2
Preparation process include：(1) metal mixture is smelted into fused solution alloy using high-temperature fusion technology；(2) use
The fused solution alloy is processed into the alloying pellet by the method for casting granulation or rotating granulation.
7. the preparation method of the nickel-base catalyst according to any one of claim 5 or 6, wherein, it is molten in the step (1)
The temperature of refining is 1300-1700 DEG C, and the smelting time is 0.2-0.5 hours.
8. the preparation method of nickel-base catalyst according to claim 4, wherein, the activation process in the step 3
Including the alloying pellet is placed in a fixed bed reactors, make the aqueous slkali by the alloying pellet, the alkali
Solution includes the mixture of sodium hydroxide solution, potassium hydroxide solution or both, and the concentration of the aqueous slkali is 0.1-10wt%,
Weight space velocity is 4-50h-1, the temperature of the activation process is 20 DEG C -60 DEG C, and the time of the activation process is 2-12 hours.
9. the preparation method of nickel-base catalyst according to claim 8, wherein, the aqueous slkali is potassium hydroxide solution,
Concentration is 0.3-3wt%, and weight space velocity is 6-30h-1, the potassium hydroxide solution electrical conductivity is that the water of 10-150 μ s/cm is matched somebody with somebody
System is formed.
10. the preparation method of nickel-base catalyst according to claim 4, wherein, the washing process bag in the step 4
Include the alloying pellet after the activation is washed using deionized water, when the pH value of washing to cleaning solution is 7-9, stop washing
Wash, the temperature of the washing is 20 DEG C -50 DEG C.
A kind of 11. nickel-base catalysts as claimed in claim 1 acetone hydrogenation in isopropanol-acetone-hydrogen chemical heat pump is anti-
Application in answering, including：The acetone hydrogenation reaction, the granularity of the nickel-base catalyst are carried out in a fixed bed reactors
It is 2-10mm, the mol ratio of hydrogen/acetone is 1-20:1, reaction temperature is 180-210 DEG C, and pressure is 0.1-6MPa, liquid-containing air
Speed is 0.1-10h-1, the content of acetone is 60-100wt% in liquid.
The acetone hydrogenation reaction in isopropanol-acetone-hydrogen chemical heat pump of 12. nickel-base catalysts according to claim 11
In application, wherein, the granularity of the nickel-base catalyst is 3-6mm, and the mol ratio of hydrogen/acetone is 1.5-10:1, pressure is
0.5-5MPa, liquid air speed is 0.5-6h-1, the content of acetone is 75-99wt% in liquid, and the acetone hydrogenation exothermic heat of reaction can
Persistently produce 200 DEG C of high temperature heat source.
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