CN106925293B - Nickel-based catalyst and preparation method and application thereof - Google Patents
Nickel-based catalyst and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 88
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 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 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 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 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 70
- 239000000956 alloy Substances 0.000 claims description 70
- 239000002245 particle Substances 0.000 claims description 69
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 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 description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 21
- 230000004913 activation Effects 0.000 description 16
- 239000003513 alkali Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002918 waste heat Substances 0.000 description 9
- 229910001092 metal group alloy Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 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
- 238000012546 transfer Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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 nickel-based catalyst for catalyzing acetone hydrogenation reaction to prepare isopropanol, which comprises, by weight, 35-60% of nickel, 20-60% of aluminum, 1-10% of copper, 0.5-10% of iron and 0.5-5% of manganese. The invention also discloses a preparation method of the nickel-based catalyst and application of the nickel-based catalyst in an acetone hydrogenation reaction fixed bed reactor in an isopropanol-acetone-hydrogen chemical heat pump. Compared with the prior art, the nickel-based catalyst has the advantages of high mechanical strength, high acetone conversion rate, high isopropanol selectivity, strong poisoning resistance, simple production process, easy industrialization, good application prospect and great economic benefit.
Description
Technical Field
The invention relates to the field of catalysis and the field of energy utilization, in particular to a nickel-based catalyst for preparing isopropanol by catalyzing acetone hydrogenation reaction, a preparation method thereof and application in the acetone hydrogenation reaction in an isopropanol-acetone-hydrogen chemical heat pump.
Technical Field
At present, the energy utilization efficiency of China is low, and compared with developed countries, the method has a great progress space, and waste heat recycling, especially low-temperature waste heat recycling, becomes an important means for improving the energy utilization efficiency and solving the energy crisis. The low-temperature waste heat has low taste and is difficult to be directly utilized, and most of the low-temperature waste heat is discharged to cause huge energy waste. The best way to utilize the low temperature waste heat is to raise the temperature of the waste heat so that the waste heat can be utilized. If the method is realized, the energy utilization rate can be greatly improved, the energy utilization range can be expanded, and energy crisis can be effectively relieved by using low-temperature natural energy such as solar energy, geothermal energy and the like. The recycling of industrial low-temperature waste heat and the development and utilization of solar energy respond to energy policies of energy conservation, emission reduction and clean energy advocated all over the world.
The device for raising the temperature of the low-temperature heat source is a heat pump system, and a heat pump of a temperature raising type generally includes: mechanical heat pump, absorption heat pump. The mechanical heat pump has the advantages of more required capacity input, large consumption and small temperature raising amplitude; although absorption heat pumps have a large temperature rise range and can be used in large-scale industry, the absorption heat pumps require a large pressure between components to transfer energy, which results in high operation and maintenance costs. The chemical heat pump can overcome the defects of a mechanical heat pump and an absorption heat pump. The chemical heat pump converts heat energy into chemical energy through the heat effect of chemical reaction, and particularly utilizes the reversible chemical reaction of a working medium pair to carry out endothermic and exothermic reactions at different temperatures, thereby realizing the conversion, storage and transfer of energy. Chemical heat pumps have a higher heat storage capacity than other heat pumps, their reactants and products can be stored for a long time, and the energy stored in the chemical substance does not cause any heat loss due to the temperature difference with the environment.
The chemical heat pump is a preferred device for improving the low-heat quality and taste due to the advantages of high efficiency, no pollution, low energy consumption, high temperature increase range and the like. An isopropanol-acetone-hydrogen (IAH) chemical heat pump is one of the chemical heat pumps with a large application potential. The method utilizes a pair of reversible chemical reactions, isopropanol is dehydrogenated at low temperature (80 ℃) to generate endothermic reaction to generate acetone and hydrogen, and acetone is hydrogenated at high temperature (200 ℃) to generate exothermic reaction to generate isopropanol, so that the low-temperature thermal temperature is raised, and the isopropanol can be directly applied in industry. Has great industrial application potential.
The key technology of IAH chemical heat pumps is the development of efficient catalysts, the development of which is also limited primarily by the performance of the catalyst. The catalyst has two applications in an IAH chemical heat pump: the dehydrogenation reaction of isopropanol and the hydrogenation reaction of acetone. The catalyst needs to have the conditions of high selectivity, high activity and long service life. The catalyst for the isopropanol dehydrogenation endothermic reaction is mainly a noble metal catalyst such as Pt, Pd, Ru and the like, and the carrier is mainly active carbon, in addition, the catalyst also comprises a copper-zinc catalyst. The acetone hydrogenation reaction is mainly carried out by using a supported noble metal catalyst such as Ru/C, Ru/Al2O3Pt/C and nickel-based catalysts and copper-based catalysts. However, most of the catalysts for preparing isopropanol by hydrogenating acetone are in the laboratory research stage at present, and the industrial alternative catalysts for hydrogenating acetone are basically not available.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the nickel-based catalyst which can meet the industrial requirements and is used for catalyzing the acetone hydrogenation reaction to prepare the isopropanol, the preparation method of the nickel-based catalyst and the application of the nickel-based catalyst in the acetone hydrogenation fixed bed in the IAH chemical heat pump. The invention comprises the following steps:
in one aspect, the invention discloses a nickel-based catalyst for catalyzing the hydrogenation reaction of acetone to prepare isopropanol, which comprises, by weight, 35-60% of nickel, 20-60% of aluminum, 1-10% of copper, 0.5-10% of iron, and 0.5-5% of manganese.
Further, the nickel-based catalyst of the present invention is in the form of particles. The nickel-based catalyst of the present invention has a particle size of 1.0 to 10.0mm, preferably, a particle size of 3.0 to 6.0 mm; alternatively, the nickel-based catalyst of the present invention has a diameter of 1 to 10mm and a height of 1 to 10mm, and preferably, a diameter of 2 to 6mm and a height of 2 to 6 mm. The shape of the nickel-based catalyst comprises one or a combination of more of irregular shape, spherical shape, hemispherical shape, strip shape, cylindrical shape, rod shape, tooth shape and hollow rod shape.
Further, the nickel-based catalyst comprises an active substance outer surface layer and a metal alloy inner core, wherein the active substance outer surface layer is of a porous structure, and the metal alloy inner core is of a compact structure. The total pore volume of the porous structure of the active substance outer surface layer is more than 0.12ml/mlCatalyst and process for preparing sameThe volume ratio of mesopores and macropores in the porous structure is in the range of 15 to 45%, and the volume ratio of micropores is in the range of 85 to 55%. In the present invention, micropores mean pores having an average pore diameter of less than 2nm, mesopores mean pores having a diameter of more than 2nm and less than 50nm, and macropores mean pores having a diameter of more than 50 nm. The average strength of the metal alloy core is that the side pressure is more than 300N.
Further, the nickel-based catalyst is a nickel-based catalyst activated by an alkaline solution.
In another aspect, the present invention also discloses a method for preparing the nickel-based catalyst, which comprises:
the method comprises the following steps: providing a metal mixture comprising, in weight percent of the metal mixture: 35-60% nickel, 20-60% aluminum, 1-10% copper, 0.5-10% iron, and 0.5-5% manganese;
step two: processing the metal mixture into alloy particles;
step three: activating the alloy particles by using an alkali solution to obtain activated alloy particles; and
step four: and washing the activated alloy particles to obtain the nickel-based catalyst.
Further, the preparation process of the alloy particles in the second step comprises the following steps: (1) melting the metal mixture into a molten liquid alloy using a high temperature melting technique; (2) cooling the molten liquid alloy to obtain a solid alloy, wherein the cooling is quenching or stepped cooling to normal temperature; (3) preparing the solid alloy into the alloy particles, the method of preparing the solid alloy into the alloy particles comprising: and screening to obtain the alloy particles after crushing, or crushing the solid alloy into powder and then forming to obtain the alloy particles. The screening after crushing means that a crusher is used for crushing the solid alloy, and then alloy particles with a certain particle size are selected through a screen, wherein the particle size is in a range of 1-10mm, the alloy particles obtained by the method are irregular in shape, and the crusher can be a mechanical jaw crusher, an impact crusher or a hammer crusher. The step of crushing into powder and then molding is to obtain fine powder with the particle size of less than 100 meshes by ball milling and the like, then adding forming agents such as alumina, water, binders and the like, obtaining alloy particles by flaking, extruding or rolling, for example, cylindrical alloy particles can be obtained by flaking, alloy particles with the shapes of cylinders, teeth, hollow cylinders and the like can be obtained by extruding, the shape of the alloy particles depends on an extrusion die, and the step of crushing solid alloy into powder and then molding and granulating to obtain the alloy particles with the particle size of 1-10 mm.
As another embodiment, the preparation process of the alloy particles in the second step may also adopt the following method: (1) melting the metal mixture into a molten liquid alloy using a high temperature melting technique; and (2) processing the molten liquid alloy into the alloy particles using a cast granulation or a rotary granulation method. Wherein, the casting granulation refers to casting the molten liquid alloy to directly form small particles, the shape of which comprises a sphere, a hemisphere, a bar or a cuboid, and the alloy particles with the particle size of 1-10mm can be obtained generally. The rotary granulation refers to that the molten liquid alloy is subjected to rotary granulation to obtain spherical particles, and alloy particles with the particle size of 1-10mm can be obtained generally.
Further, in the above two embodiments related to the preparation process of the alloy particles, the temperature of the smelting in the step (1) is 1300-1700 ℃, and the smelting time is 0.2-0.5 hour.
Further, the activation treatment in the third step includes placing the alloy particles in a fixed bed reactor, and passing the alkali solution through the alloy particles, wherein the alkali solution includes sodium hydroxide solution, potassium hydroxide solution or a mixture of the sodium hydroxide solution and the potassium hydroxide solution. Preferably, the concentration of the alkali solution is 0.1-10 wt%, and the weight space velocity is 4-50h-1The temperature of the activation treatment is 20-60 ℃, and the time of the activation treatment is 2-12 hours. More preferably, the activation treatment is carried out by using 0.3-3 wt% potassium hydroxide solution, the potassium hydroxide solution is prepared by water with conductivity of 10-150 mu s/cm, and the weight space velocity of the potassium hydroxide solution is 6-30h-1The activating treatment temperature range is 20-50 ℃, and the activating treatment time is 4-10 hours.
Further, the washing process in the fourth step includes washing the activated alloy particles with deionized water, and stopping washing until the pH value of the washing liquid is 7-9; the washing temperature is 20-50 ℃.
In a third aspect, the invention also discloses an application of the nickel-based catalyst in the acetone hydrogenation reaction of the isopropanol-acetone-hydrogen chemical heat pump, which comprises the following steps: the acetone hydrogenation reaction is carried out in a fixed bed reactor, the granularity of the nickel-based catalyst is 2-10mm, the molar ratio of hydrogen to acetone is 1-20:1, the reaction temperature is 180-210 ℃, the pressure is 0.1-6MPa, and the liquid space velocity is 0.1-10h-1The content of acetone in the liquid is 60-100 wt%.
Further, the application of the nickel-based catalyst in the chemical heat pump acetone hydrogenation reaction of isopropanol-acetone-hydrogenWherein the granularity of the nickel-based catalyst is 3-6mm, the molar ratio of hydrogen to acetone is 1.5-10:1, the pressure is 0.5-5MPa, and the liquid space velocity is 0.5-6h-1The content of acetone in the liquid is 75-99 wt%; under the condition, the acetone hydrogenation reaction can continuously generate a high-temperature heat source at 200 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the nickel-based catalyst for catalyzing the acetone hydrogenation reaction to prepare the isopropanol consists of nickel, aluminum, copper, iron and manganese, has the characteristics of high mechanical strength, high acetone conversion rate and high isopropanol selectivity, and has strong poisoning resistance, long service life, good application prospect and great economic benefit.
The preparation process of the nickel-based catalyst comprises the steps of granulating, activating and washing the metal mixture, and has the advantages of simple production process, low cost and easy industrialization. The technical means of quenching after melting or stepped cooling is adopted to ensure that the alloy is uniform and has no segregation, the alloy crystal phase is refined and uniform, and the activation rate of alloy particles is controlled by controlling the conductivity of water for preparing alkali liquor and the concentration of the alkali liquor, so that the generated active center has high dispersibility, the pore channel is properly distributed, and the proportion of micropores to mesopores is reasonable.
The nickel-based catalyst is applied to the acetone hydrogenation reaction in an IAH chemical heat pump, adopts a fixed bed reactor, is simple to operate, has stable process and easy industrialization, can continuously hydrogenate acetone obtained by dehydrogenation of isopropanol which is a low-temperature heat source, continuously generates a high-temperature heat source at 200 ℃, reduces the subsequent separation pressure of the acetone and the isopropanol, and reduces energy consumption, so that the nickel-based catalyst can efficiently utilize industrial low-temperature waste heat or solar energy, and conforms to the energy policy of energy conservation, emission reduction and clean energy advocated by the world.
Detailed Description
Unless otherwise defined, technical or scientific terms used in the claims and the specification should have the ordinary meaning as understood by those of ordinary skill in the art to which the invention belongs.
The present invention is further illustrated by the following examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the scope of the invention as claimed.
Examples 1 to 4 are processes for preparing granular fixed bed nickel-based catalysts, respectively, by preparing alloy particles using metal mixtures having different compositions by different methods and subjecting the alloy particles to alkali activation treatment.
Example 1
The method comprises the steps of accurately weighing 400 g of nickel with the purity of more than 99%, 500 g of aluminum with the purity of more than 99%, 50 g of copper with the purity of more than 99%, 40 g of iron with the purity of more than 99% and 10 g of manganese with the purity of more than 99%, uniformly mixing to obtain a metal mixture, placing the metal mixture in a medium-frequency electric furnace to be melted at 1650 ℃, pouring the metal mixture into a die for 0.5 hour, cooling the metal mixture in a quenching mode, crushing the metal mixture by a jaw crusher, and screening to obtain alloy particles with the particle size of 3-6 mm.
Then, 200g of the alloy particles obtained above were taken out and placed in a quartz glass tube having an inner diameter of 60mm, and a KOH solution having a concentration of 1.0 wt% (water for preparing a KOH solution having an electric conductivity of 50. mu.s/cm) was fed at a space velocity of 12 hours-1Flows from the bottom of the quartz glass tube through the bed of alloy particles and then flows out from the top. The bed temperature was 30 ℃ and the activation treatment time was 5 hours. And washing with deionized water at 40 ℃ after alkali liquor activation treatment until the pH of the washed solution is 7-9, and stopping washing to obtain the granular fixed bed nickel-based catalyst.
Example 2
420 g of nickel with the purity of more than 99 percent, 480 g of aluminum with the purity of more than 99 percent, 60 g of copper with the purity of more than 99 percent, 30 g of iron with the purity of more than 99 percent and 10 g of manganese with the purity of more than 99 percent are accurately weighed and evenly mixed to obtain a metal mixture, the metal mixture is placed in a medium-frequency electric furnace to be melted at 1650 ℃ for 0.4 hour, poured out into a die to be cooled in a stepped mode, crushed by a hammer crusher and sieved to obtain alloy particles with the particle size of 3-6 mm.
Then, 200g of the alloy particles obtained above were taken and placed in a quartz glass tube having an inner diameter of 60mm,KOH solution with a concentration of 0.8 wt.% (conductivity of water used for preparing the KOH solution is 100 mus/cm) is used at space velocity for 15h-1Flows from the bottom of the quartz glass tube through the bed of alloy particles and then flows out from the top. The bed temperature was 30 ℃ and the activation treatment time was 6 hours. And washing with deionized water at 45 ℃ after alkali liquor activation treatment until the pH of the washed solution is 7-9, and stopping washing to obtain the granular fixed bed nickel-based catalyst.
Example 3
The method comprises the steps of accurately weighing 400 g of nickel with the purity of more than 99%, 550 g of aluminum with the purity of more than 99%, 30 g of copper with the purity of more than 99%, 10 g of iron with the purity of more than 99% and 10 g of manganese with the purity of more than 99%, uniformly mixing to obtain a metal mixture, putting the metal mixture into a medium-frequency electric furnace to melt at 1550 ℃, pouring the metal mixture into a mold for 0.3 hour, cooling in a stepped mode, preparing alloy powder with the particle size of less than 200 meshes by using a jaw crusher and a ball mill, adding water, pseudo-boehmite and a binder, extruding the mixture into strips, drying and roasting to obtain rod-shaped alloy particles with the diameter of 3mm and the length of 2-6 mm.
Then, 200g of the metal alloy particles obtained above were placed in a quartz glass tube having an inner diameter of 60mm, and a KOH solution having a concentration of 1.2 wt% (water for preparing a KOH solution having an electric conductivity of 90. mu.s/cm) was fed at a space velocity of 25 hours-1Flows from the bottom of the quartz glass tube through the bed of metal alloy particles and then flows out from the top. The bed temperature was 30 ℃ and the activation treatment time was 5 hours. And washing with deionized water at 40 ℃ after alkali liquor activation treatment until the pH of the washed solution is 7-9, and stopping washing to obtain the granular fixed bed nickel-based catalyst.
Example 4
350 g of nickel with the purity of more than 99 percent, 480 g of aluminum with the purity of more than 99 percent, 70 g of copper with the purity of more than 99 percent, 60 g of iron with the purity of more than 99 percent and 40 g of manganese with the purity of more than 99 percent are accurately weighed and evenly mixed to obtain a metal mixture, the metal mixture is placed in a medium-frequency electric furnace to be melted at 1600 ℃ for 0.5 hour, poured out into a die to be cooled in a quenching mode, crushed by a jaw crusher, and screened to obtain alloy particles with the particle size of 3-6 mm.
Then, 200g of the alloy particles obtained above were placed in a quartz glass tube having an inner diameter of 60mm, and a KOH solution having a concentration of 0.5 wt% (conductivity of water used for preparing the KOH solution was 150. mu.s/cm) was fed at a space velocity of 10 hours-1The velocity flows from the bottom of the quartz glass tube through the bed of metal alloy particles and then out from the top. The bed temperature was 35 ℃ and the activation treatment time was 8 hours. And washing with deionized water at 40 ℃ after alkali liquor activation treatment until the pH of the washed solution is 7-9, and stopping washing to obtain the granular fixed bed nickel-based catalyst.
Comparative example 1
480 g of nickel with the purity of more than 99 percent and 520 g of aluminum with the purity of more than 99 percent are accurately weighed, the materials are placed in a medium-frequency electric furnace for melting, the melted materials are poured out of a die and naturally cooled, and are crushed by a jaw crusher, and alloy particles with the particle size of 3-6mm are obtained by screening.
Then, 200g of the alloy particles obtained above were placed in a quartz glass tube having an inner diameter of 60mm, and NaOH alkali solution having a concentration of 1.0 wt.% was caused to flow from the bottom of the quartz glass tube at a rate of 8L/h through the bed of the alloy particles and then to flow out from the upper portion. The activation treatment time was 6 hours. And (3) washing with deionized water after alkali liquor activation treatment until the pH of the washed solution is 7-9, and stopping washing to obtain the granular fixed bed nickel-based catalyst.
Evaluation of catalyst Performance:
the acetone hydrogenation reaction is carried out in a fixed bed reactor, 100 g of each nickel-based catalyst prepared in the examples 1-4 and the comparative example 1 is selected and transferred into the fixed bed reaction with the diameter of 3 cm, the reactor is provided with a heating and cooling device, the reactor is heated to 180 ℃ and 210 ℃, preheated acetone and hydrogen are introduced, the molar ratio of the hydrogen to the acetone is 1.5-10:1, the reaction pressure is maintained to be 0.5-5MPa, and the liquid airspeed is 0.5-6h-1The weight content of acetone in the liquid is 75-99%. And in the reaction maintaining stage, stopping heating, maintaining the temperature through a reaction heat and cooling system, condensing the reaction product, analyzing the content of the liquid product by using a Gas Chromatography (GC), and calculating the acetone conversion rate and the isopropanol selectivity.
The reaction conditions and the reaction results are shown in Table 1.
Table 1.
To illustrate the life and poison resistance of the nickel-based catalyst of the invention, the liquid space velocity was 3.5h at an acetone content of 95.5% (containing 0.5ppm of sulfur)-1The molar ratio of hydrogen to acetone is 4, the pressure is 3.5MPa, the time for maintaining the temperature at 200 ℃ is taken as the standard for investigating the service life of the catalyst, the catalyst prepared in example 4 can maintain the high temperature at 200 ℃ after 1000 hours without heating, and the temperature of the nickel-based catalyst system prepared in comparative example 1 begins to drop (naturally dissipate heat) after 400 hours without heating, which shows that the nickel-based catalyst of the invention has longer service life and strong poisoning resistance, and can meet the requirement of generating a high-temperature heat source by the acetone hydrogenation reaction in an IAH chemical heat pump.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar means that can be made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (5)
1. The preparation method of the nickel-based catalyst is characterized in that the nickel-based catalyst is used for catalyzing the hydrogenation reaction of acetone to prepare isopropanol and consists of 35-60 wt% of nickel, 20-60 wt% of aluminum, 1-10 wt% of copper, 0.5-10 wt% of iron and 0.5-5 wt% of manganese, the nickel-based catalyst is granular, the granularity of the nickel-based catalyst is 1.0-10.0mm, and the shape of the nickel-based catalyst comprises one or more of irregular shape, spherical shape, hemispherical shape, strip shape, cylindrical shape, rod shape, tooth shape and hollow rod shape;
the preparation method of the nickel-based catalyst comprises the following steps:
the method comprises the following steps: providing a metal mixture having, in weight percent of the metal mixture, 35-60% nickel, 20-60% aluminum, 1-10% copper, 0.5-10% iron, and 0.5-5% manganese;
step two: smelting the metal mixture at 1300-1700 ℃ for 0.2-0.5 h by using a high-temperature melting technology to obtain molten liquid alloy, cooling the molten liquid alloy to obtain solid alloy, and processing the solid alloy into alloy particles with the particle size of 1-10mm, wherein the cooling is quenching or stepped cooling to normal temperature;
step three: placing the alloy particles in a fixed bed reactor, and enabling a potassium hydroxide solution with the concentration of 0.3-3 wt% to be used for 6-30h-1The weight space velocity of the potassium hydroxide solution is adjusted to be the weight space velocity of the activated alloy particles, the activated alloy particles are obtained by activating the alloy particles, the potassium hydroxide solution is prepared by water with the conductivity of 10-150 mu s/cm, the temperature of the activating treatment is 20-60 ℃, and the time of the activating treatment is 2-12 h;
step four: and washing the activated alloy particles to obtain the nickel-based catalyst.
2. The method for preparing the nickel-based catalyst according to claim 1, wherein the step two comprises the steps of crushing the solid alloy into the alloy particles, screening the alloy particles, or crushing the solid alloy into powder, and then forming the powder to obtain the alloy particles.
3. The preparation method of the nickel-based catalyst according to claim 1, wherein the washing process in the fourth step comprises washing the activated alloy particles with deionized water, and the washing is stopped when the pH value of the washing solution is 7-9, wherein the washing temperature is 20-50 ℃.
4. Use of a nickel-based catalyst prepared according to the preparation method of any one of claims 1 to 3 in an acetone hydrogenation reaction in an isopropanol-acetone-hydrogen chemical heat pump, comprising: the acetone hydrogenation reaction is carried out in a fixed bed reactor, and the nickel-based catalystThe granularity of the catalyst is 2-10mm, the molar ratio of hydrogen to acetone is 1-20:1, the reaction temperature is 180-210 ℃, the pressure is 0.1-6MPa, and the liquid space velocity is 0.1-10h-1The content of acetone in the liquid is 60-100 wt%.
5. The use of the nickel-based catalyst according to claim 4 in the hydrogenation of acetone in an isopropanol-acetone-hydrogen chemical heat pump, wherein the particle size of the nickel-based catalyst is 3-6mm, the molar ratio of hydrogen to acetone is 1.5-10:1, the pressure is 0.5-5MPa, and the liquid space velocity is 0.5-6h-1The content of acetone in the liquid is 75-99 wt%, and the acetone hydrogenation reaction releases heat and can continuously generate a high-temperature heat source at 200 ℃.
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| CN101081825A (en) * | 2007-06-18 | 2007-12-05 | 大连理工大学 | Method for hydrogenation preparation of m-(beta-hydroxyethyl sulfone)aniline by amorphous alloy nickel catalysis of m-(beta-hydroxyethyl sulfone) nitrobenzene |
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