CN108097254B - Nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol and preparation method thereof - Google Patents
Nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims abstract description 13
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 8
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 29
- 238000012216 screening Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 16
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 18
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 abstract description 9
- 229940009827 aluminum acetate Drugs 0.000 abstract description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 abstract description 5
- 229940078494 nickel acetate Drugs 0.000 abstract description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000003801 milling Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 9
- 238000005457 optimization Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/51—Spheres
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- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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- Catalysts (AREA)
Abstract
The invention relates to the technical field of preparation of nickel-based catalysts by adopting a mechanochemical method, in particular to a nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol and a preparation method thereof. The nickel-based catalyst is obtained according to the following steps: weighing nickel nitrate hexahydrate or nickel acetate or nickel chloride, aluminum nitrate nonahydrate or aluminum acetate or aluminum chloride, ammonium carbonate or urea with required amount, ball-milling with a milling ball, and drying to obtain a precursor sample; roasting the mixture at high temperature to obtain a catalyst roasted body sample; by H2High-temperature reduction to prepare the nickel-based catalyst for synthesizing the 1, 4-butanediol by hydrogenating the 1, 4-butynediol. The invention is a simple and easy method for preparing the nickel-based catalyst, the prepared nickel-based catalyst has the grain diameter of about 80nm to 120nm, narrow distribution, good selectivity, high conversion rate of 1, 4-butynediol and yield of 1, 4-butanediol, low preparation cost and easy industrialization.
Description
Technical Field
The invention relates to the technical field of nickel-based catalysts prepared by a mechanochemical method, in particular to a nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol and a preparation method thereof.
Background
Butanediol (BDO) is an important basic organic raw material and has important and wide application in the fields of medicine, textile, military industry and the like. Particularly, the Reppe method BDO process has the unique advantage in China due to the abundant coal resources. Among the BDO synthesis methods, the Reppe process using formaldehyde and acetylene as raw materials is a route which is most adopted and has the most obvious economic benefit at present. At present, the main technology adopted for realizing industrial production in China is also a Reppe method. Although China has made a great progress through the innovation of digestion and absorption for nearly 20 years, the hydrogenation catalyst, which is the core technology in the whole process, is always dependent on foreign companies, and poses a threat to the economic safety of the 1, 4-butanediol industry in China. In view of the current situation, research and development work of the hydrogenation catalyst is carried out, and industrial application of the catalyst is realized.
One of the documents is "Ni/Al" published by Zhang Jianping, Li Hai Tao, Gao Chun Guang and Zhao Yong in Shanxi university school newspaper, 2010,33(3):413-2O3The preparation of the catalyst and the research on the hydrogenation reaction of the butynediol are disclosed, wherein mixed salt of nickel formate and nickel nitrate is used as a precursor, an isometric impregnation method is adopted to prepare the Ni/Al2O3 catalyst with the load of 17% by mass, and the influence of factors such as reaction temperature, pressure, time and catalyst dosage on the hydrogenation reaction of the butynediol is examined through an orthogonal experimental method. The result shows that the prepared catalyst active component is highly dispersed, orthogonal experiment shows that the temperature is the primary factor influencing the hydrogenation performance, the carbonyl value of the product after hydrogenation reaction rises along with the reaction temperature and pressure, and the reaction timeIncrease in catalyst usage and decrease; when the temperature is too high, byproducts can be generated, the subsequent rectification process is difficult, and the catalyst selectivity in industrial production is poor.
The second literature is prepared by using a mechanochemical method of preparing methanation Ni/Al, which is published in applied chemistry 2017 Vol.26.NO 2.141-146 by Chinese dream, Mafengyun, Muwenlong, Kongtao, Liujing plum, Slim and Xiaoyan2O3Catalyst performance research, namely methanation Ni/Al prepared by mechanochemical method2O3The catalyst shows better catalytic activity.
Studies have shown that the conversion of 1, 4-butynediol is virtually nil in the absence of catalyst. But in the presence of a catalyst, the conversion can exceed 90%. In the process of developing a Reppe method for preparing 1, 4-Butanediol (BDO), the research on the hydrogenation catalyst has important practical application value and has important theoretical research significance on the structure, selectivity and hydrogenation performance of the catalyst.
Disclosure of Invention
The invention provides a nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol and a preparation method thereof. The catalyst can effectively solve the problems that the conversion rate of 1, 4-butynediol is not high, the selectivity of 1, 4-butanediol is poor, the yield is low and the like when the existing catalyst is used for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol.
One of the technical schemes of the invention is realized by the following measures: a nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol is obtained according to the following steps: firstly, respectively weighing required amounts of one of nickel nitrate hexahydrate, nickel acetate or nickel chloride, one of aluminum nitrate nonahydrate, aluminum acetate or aluminum chloride, and one of ammonium carbonate or urea according to a stoichiometric ratio, placing the weighed amounts of the nickel nitrate hexahydrate, the aluminum acetate or the aluminum chloride, and the weighed amounts of the aluminum nitrate nonahydrate, the aluminum acetate or the aluminum chloride together with grinding balls into a ball milling tank of a planetary ball mill, carrying out ball milling for 0.5 to 2 hours, taking out materials, placing the materials into a blast drying oven, and drying the materials at 100 to 110 ℃ for 10 to 12 hours to prepare a catalyst precursor sample; secondly, the procedure of heating the precursor sample to 350-800 ℃ and roasting for 2-6 hours, taking out, cooling, grinding, screening, controlling the grain size at 80The mesh is 120 meshes, and a catalyst roasted body sample is prepared; thirdly, loading the roasted sample into a fixed bed reaction tube, and introducing H with the purity of 99.99 percent at the high temperature of 600-900 DEG C2And reducing for 2 to 6 hours to prepare a catalyst reduction sample, wherein the mass percentage of the catalyst reduction sample is as follows: ni 10-60 wt%, gamma-Al2O3From 40 to 90 wt%; and fourthly, taking out the reduction sample, cooling, tabletting, and screening by using a 40-60-mesh screening tool to obtain the nickel-based catalyst for synthesizing the 1, 4-butanediol by hydrogenating the 1, 4-butynediol.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the grinding ball comprises a big ball and a small ball, and the mass ratio of the big ball to the small ball is as follows: 2:1.
The grinding ball comprises a big ball and a small ball, and the mass ratio of the big ball to the small ball is as follows: 1:1.
The grinding ball comprises a big ball and a small ball, and the mass ratio of the big ball to the small ball is as follows: 1:2.
The diameter of the big ball is 6 mm, and the diameter of the small ball is 3 mm.
The mass ratio of the grinding balls to the total material is as follows: 2:1.
The mass ratio of the grinding balls to the total material is as follows: 3:1.
The mass ratio of the grinding balls to the total material is as follows: 4:1.
In the second step, the temperature programming rate of the precursor sample is 10 ℃/min to 40 ℃/min; or/and, in the third step, H with the purity of 99.99 percent is introduced2，H2The volume flow rate of (A) is 0.20 mL/min to 0.60 mL/min.
The second technical scheme of the invention is realized by the following measures: a preparation method of a nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol comprises the following steps: firstly, respectively weighing one of nickel nitrate hexahydrate, nickel acetate or nickel chloride, one of aluminum nitrate nonahydrate, aluminum acetate or aluminum chloride, and one of ammonium carbonate or urea according to a stoichiometric ratio, placing the materials and grinding balls into a ball milling tank of a planetary ball mill, ball milling for 0.5-2 hours, taking out the materials, and placing the materials into a drumDrying in an air drying oven at 100-110 deg.c for 10-12 hr to obtain catalyst precursor sample; secondly, heating the precursor sample to 350-800 ℃ by a program, roasting for 2-6 hours, taking out, cooling, grinding, screening, and controlling the particle size between 80-120 meshes to prepare a catalyst roasted sample; thirdly, loading the roasted sample into a fixed bed reaction tube, and introducing H with the purity of 99.99 percent at the high temperature of 600-900 DEG C2And reducing for 2 to 6 hours to prepare a catalyst reduction sample, wherein the mass percentage of the catalyst reduction sample is as follows: ni 10-60 wt%, gamma-Al2O3From 40 to 90 wt%; and fourthly, taking out the reduction sample, cooling, tabletting, and screening by using a 40-60-mesh screening tool to obtain the nickel-based catalyst for synthesizing the 1, 4-butanediol by hydrogenating the 1, 4-butynediol.
The invention is a simple and easy method for preparing the nickel-based catalyst, the prepared nickel-based catalyst has the grain diameter of about 80nm to 120nm, narrow distribution, good selectivity, high conversion rate of 1, 4-butynediol and yield of 1, 4-butanediol, low preparation cost and easy industrialization.
Drawings
FIG. 1 is an SEM electron microscope picture of the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the present invention are all mass percentages unless otherwise specified.
The invention is further described below with reference to the following examples:
example 1: the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol is obtained according to the following steps: firstly, respectively weighing the required amount of nickel nitrate hexahydrate or nickel acetate or nickel chloride, aluminum nitrate nonahydrate or aluminum acetate or aluminum chloride and carbonic acid according to the stoichiometric ratioOne of ammonium or urea is placed in a ball milling tank of a planetary ball mill together with a milling ball, ball milling is carried out for 0.5 to 2 hours, materials are taken out and put into a blast drying oven to be dried for 10 to 12 hours at the temperature of 100 to 110 ℃, and a catalyst precursor sample is prepared; secondly, heating the precursor sample to 350-800 ℃ by a program, roasting for 2-6 hours, taking out, cooling, grinding, screening, and controlling the particle size between 80-120 meshes to prepare a catalyst roasted sample; thirdly, loading the roasted sample into a fixed bed reaction tube, and introducing H with the purity of 99.99 percent at the high temperature of 600-900 DEG C2And reducing for 2 to 6 hours to prepare a catalyst reduction sample, wherein the mass percentage of the catalyst reduction sample is as follows: ni 10-60 wt%, gamma-Al2O3From 40 to 90 wt%; and fourthly, taking out the reduction sample, cooling, tabletting, and screening by using a 40-60-mesh screening tool to obtain the nickel-based catalyst for synthesizing the 1, 4-butanediol by hydrogenating the 1, 4-butynediol.
The preparation method of the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol adopts a mechanochemical method to prepare the required catalyst, and is simple and quick to operate.
The reaction mechanism of the nickel nitrate hexahydrate, the aluminum nitrate nonahydrate and the ammonium carbonate is as follows:
(NH4)2CO3+Ni2+=NiCO3+2NH4 +(1-1)
3(NH4)2CO3+2Al3++3H2O=2Al(OH)3+6NH4 ++3CO2(1-2)
the reaction mechanism of the nickel nitrate hexahydrate, the aluminum nitrate nonahydrate and the urea is as follows:
(NH2)2CO+Ni2++2H2O=Ni（OH）2+2NH4 ++CO2(1-1)
3(NH2)2CO+2Al3++6H2O=2 Al(OH)3+6NH4 ++3CO2(1-2)
the screening means is a screen or mesh or other screening device as known in the art.
Example 2: the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol is obtained according to the following steps: firstly, respectively weighing required amounts of one of nickel nitrate hexahydrate, nickel acetate or nickel chloride, one of aluminum nitrate nonahydrate, aluminum acetate or aluminum chloride, and one of ammonium carbonate or urea according to a stoichiometric ratio, placing the weighed amounts of the nickel nitrate hexahydrate, the aluminum acetate or the aluminum chloride, and the weighed amounts of the aluminum nitrate nonahydrate, the aluminum acetate or the aluminum chloride together with grinding balls into a ball milling tank of a planetary ball mill, carrying out ball milling for 0.5 hour or 2 hours, taking out materials, placing the materials into a blast drying oven, and drying the materials at 100 ℃ or 110 ℃ for 10 hours or 12 hours to obtain a catalyst precursor sample; secondly, heating the program of the precursor sample to 350 ℃ or 800 ℃ and roasting for 2 hours or 6 hours, taking out, cooling, grinding and screening to control the particle size to be 80 meshes or 120 meshes to prepare a catalyst roasted sample; thirdly, loading the roasted sample into a fixed bed reaction tube, and introducing H with the purity of 99.99 percent at the high temperature of 600 ℃ or 900 DEG C2And reducing for 2 hours or 6 hours to prepare a catalyst reduction sample, wherein the mass percentage of the catalyst reduction sample is as follows: ni 10 wt% or 60 wt%, gamma-Al2O340 wt% or 90 wt%; and fourthly, taking out the reduction sample, cooling, tabletting, and screening by using a 40-mesh or 60-mesh screening tool to obtain the nickel-based catalyst for synthesizing the 1, 4-butanediol by hydrogenating the 1, 4-butynediol.
Example 3: as the optimization of the above embodiment, the grinding ball comprises a big ball and a small ball, and the mass ratio of the big ball to the small ball is as follows: 2:1.
Example 4: as the optimization of the above embodiment, the grinding ball comprises a big ball and a small ball, and the mass ratio of the big ball to the small ball is as follows: 1:1.
Example 5: as the optimization of the above embodiment, the grinding ball comprises a big ball and a small ball, and the mass ratio of the big ball to the small ball is as follows: 1:2.
Example 6: as an optimization of the above embodiment, the diameter of the large ball is 6 mm and the diameter of the small ball is 3 mm.
Example 7: as the optimization of the above embodiment, the mass ratio of the grinding balls to the total material is as follows: 2:1.
Example 8: as the optimization of the above embodiment, the mass ratio of the grinding balls to the total material is as follows: 3:1.
Example 9: as the optimization of the above embodiment, the mass ratio of the grinding balls to the total material is as follows: 4:1.
Example 10: as the optimization of the above embodiment, in the second step, the temperature programming rate of the precursor sample is 10 ℃/min to 40 ℃/min; or/and, in the third step, H with the purity of 99.99 percent is introduced2，H2The volume flow rate of (A) is 0.20 mL/min to 0.60 mL/min.
Example 11: the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol is obtained according to the following steps: firstly, 16.52 g of nickel nitrate hexahydrate, 36.78 g of aluminum nitrate nonahydrate, 19.63 g of ammonium carbonate and 145.86 g of large and small grinding balls are weighed according to the stoichiometric ratio, placed in a ball milling tank of a planetary ball mill (97.24 g of large balls and 48.62g of small balls), ball milled for 1 hour, taken out materials, and subjected to forced air drying at 110 ℃ for 12 hours to prepare a catalyst precursor sample; secondly, heating the program of the precursor sample to 400 ℃, roasting for 4 hours, taking out, cooling, grinding, screening, and sieving with a sieve of 80 meshes to 120 meshes to obtain a roasted sample; thirdly, using 99.99% H at 800 DEG C2Reducing for 4 hours, taking out, cooling, grinding, screening, and sieving with a 40-60 mesh sieve to obtain the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol.
Example 12: the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol is obtained according to the following steps: firstly, 16.52 g of nickel nitrate hexahydrate, 36.78 g of aluminum nitrate nonahydrate, 12.22 g of urea and 131.04 g of large and small ball-milling balls are weighed according to the stoichiometric ratio and placed in a ball-milling tank of a planetary ball mill (87.36 g of large balls and 43.68g of small balls), ball-milling is carried out for 1 hour, materials are taken out, and forced air drying is carried out for 12 hours at 110 ℃ to prepare a catalyst precursor sample; secondly, heating the program of the precursor sample to 400 ℃, roasting for 4 hours, taking out, cooling, grinding, screening, and sieving with a sieve of 80 meshes to 120 meshes to obtain a roasted sample; thirdly, 99.99 percent of H is used at 850 DEG C2Reducing for 4 hours, taking out, cooling, grinding, screening, and sieving with a 40-60 mesh sieve to obtain the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol.
The nickel-based catalysts prepared in the above examples 11 and 12 for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol have the particle size of about 80-120nm and narrow particle distribution, and the SEM electron micrographs are shown in FIG. 1.
Evaluation experiment 1: 0.60 g of the nickel-based catalyst sample for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol, which is prepared in the above example 11, is weighed and added into a slurry reactor. The evaluation reaction conditions were: the reaction temperature is 110 ℃, H2The pressure is 4MPa, the stirring speed is 600 r/min, the reaction time is 3 hours, and the adding amount of 1, 4-butynediol is 30 mL. Evaluation results were as follows: the conversion rate of 1, 4-butynediol in the reaction kettle reaches 98.4 percent, the selectivity of 1, 4-butanediol reaches 84.3 percent, and the carbonyl value is 1.49 mg (KOH)/g.
Evaluation experiment 2: the nickel-based catalyst sample for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol, prepared in example 12, was weighed and subjected to an evaluation experiment in the same manner as in evaluation experiment 1. Evaluation results were as follows: the conversion rate of 1, 4-butynediol in the reaction kettle reaches 99.2 percent, the selectivity of 1, 4-butanediol reaches 86.7 percent, and the carbonyl value is 1.37 mg (KOH)/g.
The evaluation results of the evaluation experiments 1 and 2 show that the nickel-based catalyst for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol, which is prepared in the examples 11 and 12, has good selectivity, high conversion rate of 1, 4-butynediol and high yield of 1, 4-butanediol when 1, 4-butanediol is synthesized by hydrogenating 1, 4-butynediol.
In conclusion, the invention is a simple and rapid method for preparing the nickel-based catalyst, the particles of the nickel-based catalyst obtained by the method are uniformly distributed, the nickel-based catalyst has the characteristics of good selectivity, high conversion rate of 1, 4-butynediol and high yield of 1, 4-butanediol, and the nickel-based catalyst prepared by the method is low in cost and convenient for industrial production.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (17)
1. Hydrogenation synthesis of 1, 4-butanediol from 1, 4-butynediolNickel-based catalyst for alcohols, characterized in that it is obtained according to the following steps: firstly, respectively weighing one of nickel nitrate hexahydrate, aluminum nitrate nonahydrate, ammonium carbonate or urea with required amount according to stoichiometric ratio, placing the weighed materials and grinding balls into a ball milling tank of a planetary ball mill, carrying out ball milling for 1 hour, taking out the materials, placing the materials into a blast drying oven, and drying the materials at 110 ℃ for 12 hours to prepare a catalyst precursor sample; secondly, heating the precursor sample to 400 ℃ by a program, roasting for 4 hours, taking out, cooling, grinding, screening, and controlling the particle size to be between 80 meshes and 120 meshes to prepare a catalyst roasted sample; thirdly, loading the roasted sample into a fixed bed reaction tube, and introducing H with the purity of 99.99 percent at the high temperature of 800 DEG C2And reducing for 4 hours to prepare a catalyst reduction sample, wherein the mass percentage of the catalyst reduction sample is as follows: ni 10-60 wt%, gamma-Al2O3From 40 to 90 wt%; and fourthly, taking out the reduction sample, cooling, tabletting, and screening by using a 40-60-mesh screening tool to obtain the nickel-based catalyst for synthesizing the 1, 4-butanediol by hydrogenating the 1, 4-butynediol.
2. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol as recited in claim 1, wherein the grinding balls comprise big balls and small balls, and the mass ratio of the big balls to the small balls is: 2:1.
3. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol as recited in claim 1, wherein the grinding balls comprise big balls and small balls, and the mass ratio of the big balls to the small balls is: 1:1.
4. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol as recited in claim 1, wherein the grinding balls comprise big balls and small balls, and the mass ratio of the big balls to the small balls is: 1:2.
5. The nickel-based catalyst for the hydrogenation of butynediol 1,4 to butanediol as claimed in claim 2, 3 or 4, wherein the diameter of the large spheres is 6 mm and the diameter of the small spheres is 3 mm.
6. The nickel-based catalyst for the hydrogenation of butynediol 1,4 to butanediol as claimed in claim 1 or 2 or 3 or 4, wherein the mass ratio of grinding balls to total feed is: 2:1.
7. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol according to claim 5, wherein the mass ratio of the grinding balls to the total material is: 2:1.
8. The nickel-based catalyst for the hydrogenation of butynediol 1,4 to butanediol as claimed in claim 1 or 2 or 3 or 4, wherein the mass ratio of grinding balls to total feed is: 3:1.
9. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol according to claim 5, wherein the mass ratio of the grinding balls to the total material is: 3:1.
10. The nickel-based catalyst for the hydrogenation of butynediol 1,4 to butanediol as claimed in claim 1 or 2 or 3 or 4, wherein the mass ratio of grinding balls to total feed is: 4:1.
11. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol according to claim 5, wherein the mass ratio of the grinding balls to the total material is: 4:1.
12. The nickel-based catalyst for the hydrogenation of butynediol 1,4 to butanediol according to claim 1 or 2 or 3 or 4 or 7 or 9 or 11, wherein in the second step the temperature programming rate of the precursor sample is from 10 ℃/min to 40 ℃/min; or/and, in the third step, H with the purity of 99.99 percent is introduced2，H2The volume flow rate of (A) is 0.20 mL/min to 0.60 mL/min.
13. The process of claim 5 for the hydro-synthesis of 1, 4-butynediol to 1The nickel-based catalyst of the 4-butanediol is characterized in that in the second step, the temperature programming rate of a precursor sample is 10 ℃/min to 40 ℃/min; or/and, in the third step, H with the purity of 99.99 percent is introduced2，H2The volume flow rate of (A) is 0.20 mL/min to 0.60 mL/min.
14. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol as recited in claim 6, wherein in the second step, the temperature programming rate of the precursor sample is 10 ℃/min to 40 ℃/min; or/and, in the third step, H with the purity of 99.99 percent is introduced2，H2The volume flow rate of (A) is 0.20 mL/min to 0.60 mL/min.
15. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol as recited in claim 8, wherein in the second step, the temperature programming rate of the precursor sample is 10 ℃/min to 40 ℃/min; or/and, in the third step, H with the purity of 99.99 percent is introduced2，H2The volume flow rate of (A) is 0.20 mL/min to 0.60 mL/min.
16. The nickel-based catalyst for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol as recited in claim 10, wherein in the second step, the temperature programming rate of the precursor sample is 10 ℃/min to 40 ℃/min; or/and, in the third step, H with the purity of 99.99 percent is introduced2，H2The volume flow rate of (A) is 0.20 mL/min to 0.60 mL/min.
17. A process for the preparation of a nickel-based catalyst for the hydrogenation of butynediol 1,4 to butanediol according to any of claims 2 to 16, characterised in that it is carried out according to the following steps: firstly, respectively weighing one of nickel nitrate hexahydrate, aluminum nitrate nonahydrate, ammonium carbonate or urea with required amount according to stoichiometric ratio, placing the weighed materials and grinding balls into a ball milling tank of a planetary ball mill, carrying out ball milling for 1 hour, taking out the materials, placing the materials into a blast drying oven, and drying the materials at 110 ℃ for 12 hours to prepare a catalyst precursor sample; second, the precursor is sampledHeating to 400 ℃ and roasting for 4 hours, taking out, cooling, grinding and screening to control the particle size between 80 meshes and 120 meshes to prepare a catalyst roasted sample; thirdly, loading the roasted sample into a fixed bed reaction tube, and introducing H with the purity of 99.99 percent at the high temperature of 800 DEG C2And reducing for 4 hours to prepare a catalyst reduction sample, wherein the mass percentage of the catalyst reduction sample is as follows: ni 10-60 wt%, gamma-Al2O3From 40 to 90 wt%; and fourthly, taking out the reduction sample, cooling, tabletting, and screening by using a 40-60-mesh screening tool to obtain the nickel-based catalyst for synthesizing the 1, 4-butanediol by hydrogenating the 1, 4-butynediol.
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