CN108097254A - Nickel-base catalyst for 1,4- butynediols hydrogenation synthesis 1,4- butanediols and preparation method thereof - Google Patents
Nickel-base catalyst for 1,4- butynediols hydrogenation synthesis 1,4- butanediols and preparation method thereof Download PDFInfo
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- CN108097254A CN108097254A CN201711421702.7A CN201711421702A CN108097254A CN 108097254 A CN108097254 A CN 108097254A CN 201711421702 A CN201711421702 A CN 201711421702A CN 108097254 A CN108097254 A CN 108097254A
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- nickel
- ball
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- base catalyst
- isosorbide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims description 63
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims abstract description 10
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 7
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229940009827 aluminum acetate Drugs 0.000 claims abstract description 7
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 4
- 239000011324 bead Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000012216 screening Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract description 10
- 238000010303 mechanochemical reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011156 evaluation Methods 0.000 description 10
- 238000005457 optimization Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical class [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 class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009941 weaving Methods 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/23—
-
- B01J35/40—
-
- B01J35/51—
-
- 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
Abstract
It is a kind of for nickel-base catalyst of Isosorbide-5-Nitrae butynediols hydrogenation synthesis Isosorbide-5-Nitrae butanediol and preparation method thereof the present invention relates to prepare nickel-base catalyst technical field using mechanochemical reaction.The nickel-base catalyst obtains as steps described below：The desired amount of six water nickel nitrate or nickel acetate or nickel chloride, nine water aluminum nitrates or aluminum acetate or aluminium chloride, ammonium carbonate or urea are weighed, it is dry together with abrading-ball after ball milling, obtain presoma sample；By its high-temperature roasting, catalyst roasting body sample is obtained；Use H2The nickel-base catalyst of Isosorbide-5-Nitrae butynediols hydrogenation synthesis Isosorbide-5-Nitrae butanediol is made in high temperature reduction.The present invention is a kind of succinct easy method for preparing nickel-base catalyst, and prepared nickel-base catalyst grain size is about 80nm to 120nm, and narrowly distributing, and selectivity is good, and the conversion ratio and Isosorbide-5-Nitrae butanediol yield of Isosorbide-5-Nitrae butynediols are high, and manufacturing cost is low, is easy to industrialization.
Description
Technical field
The present invention relates to mechanochemical reactions to prepare nickel-base catalyst technical field, is that a kind of Isosorbide-5-Nitrae-butynediols that is used for is hydrogenated with
Synthesize nickel-base catalyst of 1,4- butanediols and preparation method thereof.
Background technology
Butanediol (BDO) is a kind of important basic organic, in medicine, weaving, the fields such as military project have it is important and
Extensive purposes.Particularly in China because of rich coal resources, Reppe method BDO techniques have advantageous advantage.Numerous
In BDO synthetic methods, the Reppe method techniques using formaldehyde and acetylene as raw material are current using at most, and economic benefit is most significant
One route.For now, the domestic major technique for realizing that industrialized production uses is also Reppe methods.It is most for the technology
Pipe passes through the innovation of nearly 20 years, and China has obtained significant progress, however, the core skill in entire technique
Art --- hydrogenation catalyst relies on offshore company always, threatens safely to the 1,4- butanediols industrial economy in China.For
This present situation, we have carried out the research and development of the hydrogenation catalyst, and realize the industrial applications of catalyst.
One of document is published in by Zhang Jianping, Li Haitao, high spring scenery, Zhao Yongxiang《University Of Shanxi's journal》,2010,33(3):
" the Ni/Al of 413-4172O3The preparation of catalyst and the research of a butynediols hydrogenation reaction " text, with nickel formate and nickel nitrate
Salt-mixture for predecessor, the Ni/Al2O3 catalyst of load capacity mass fraction 17% is prepared for using equi-volume impregnating, is passed through
Orthogonal experimental method has investigated shadow of the factors such as reaction temperature, pressure, time and catalyst amount to butynediols hydrogenation reaction
It rings.The result shows that:Prepared catalyst activity component high degree of dispersion orthogonal experiments show that temperature is influence Hydrogenation
Primary factor, the carbonyl value of product is with the rise of reaction temperature, pressure, the extension in reaction time and catalyst after hydrogenated reaction
The increase of dosage and reduce；When the temperature is excessively high, the generation of by-product can be caused, follow-up distillation process has difficulties, industrial production
Middle catalyst choice is poor.
The two of document are published in by Zou Meng, Ma Fengyun, Mo Wenlong, Kong Lingtao, Liu Jingmei, Zhong Mei and Xiao Yan et al.《Using
Chemical industry》" the mechanochemical reaction preparation methanation Ni/Al of 2017. Vol.26.NO 2.141~1462O3Catalyst performance is studied "
One text, the methanation Ni/Al prepared using mechanochemical reaction2O3Catalyst shows preferable catalytic activity.
If research shows exist without catalyst, the conversion ratio of Isosorbide-5-Nitrae-butynediols is almost nil.But exist in catalyst
Under, conversion ratio can be more than 90%.Carry out Reppe legal system 1,4- butanediols（BDO）In the process, the research of hydrogenation catalyst has
Important actual application value, and there is important theoretical research for the structure, selectivity and Hydrogenation of catalyst
Meaning.
The content of the invention
The present invention provides a kind of nickel-base catalysts and its system for 1,4- butynediols hydrogenation synthesis 1,4- butanediols
Preparation Method.The catalyst can effectively solve the problem that existing catalyst in Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, 1,
The problems such as 4- butynediols conversion ratios are not high, and 1,4-butanediol poor selectivity, yield are low.
One of technical scheme is realized by following measures：One kind is used for 1,4- butynediols hydrogenation synthesis 1,4-
The nickel-base catalyst of butanediol, obtains as steps described below：The first step stoichiometrically weighs the desired amount of six water nitre respectively
Sour nickel or one kind in nickel acetate or nickel chloride, nine water aluminum nitrates or one kind, ammonium carbonate or urea in aluminum acetate or aluminium chloride
In one kind, be placed in together with abrading-ball in the ball grinder of planetary ball mill, ball milling 0.5 hour to 2 it is small when, take out material, put
Enter air dry oven, when drying 10 to 12 is small at 100 DEG C to 110 DEG C, catalyst precursor sample is made；Second step, will
Presoma sample program be warming up at 350 DEG C to 800 DEG C roast 2 hours to 6 it is small when, take out, cool down, grind, screening, grain size
In 80 mesh between 120 mesh, obtained catalyst roasts body sample for control；Roasting body sample is packed into fixed bed reaction by the 3rd step
Pipe under 600 DEG C to 900 DEG C hot conditions, is passed through the H that purity is 99.99%2, reductase 12 hour to 6 it is small when, be made catalysis
Agent Reduction Body sample, mass percent composition are：Ni is 10 wt% to 60 wt%, γ-Al2O3For 40 wt% to 90 wt%；The
Four steps, take out Reduction Body sample, cooling, and tabletting is sieved with 40 mesh to 60 mesh screening media and added to get for Isosorbide-5-Nitrae-butynediols
Hydrogen synthesizes the nickel-base catalyst of 1,4- butanediols.
Here is the further optimization and/or improvements to one of foregoing invention technical solution：
Above-mentioned abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：2:1.
Above-mentioned abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：1:1.
Above-mentioned abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：1:2.
A diameter of 6 mm of above-mentioned big ball, the small ball's diameter are 3 mm.
The mass ratio of above-mentioned abrading-ball and total material is：2:1.
The mass ratio of above-mentioned abrading-ball and total material is：3:1.
The mass ratio of above-mentioned abrading-ball and total material is：4:1.
In above-mentioned second step, presoma sample program heating rate is 10 DEG C/min to 40 DEG C/min；Or/and the 3rd
In step, the H that purity is 99.99% is passed through2,H2Volume flow be 0.20 mL/min to 0.60 mL/min.
The two of technical scheme are realized by following measures：One kind is used for 1,4- butynediols hydrogenation synthesis 1,4-
The preparation method of the nickel-base catalyst of butanediol carries out as steps described below：The first step stoichiometrically weighs required respectively
Six water nickel nitrates of amount or one kind in nickel acetate or nickel chloride, nine water aluminum nitrates or one kind in aluminum acetate or aluminium chloride, carbon
One kind in sour ammonium or urea is placed in together with abrading-ball in the ball grinder of planetary ball mill, ball milling 0.5 hour to 2 it is small when, take
Go out material, be put into air dry oven, when drying 10 to 12 is small at 100 DEG C to 110 DEG C, catalyst precursor sample is made；
Second step, presoma sample program is warming up at 350 DEG C to 800 DEG C roast 2 hours to 6 it is small when, take out, cool down, grinding,
Screening, for size controlling in 80 mesh between 120 mesh, obtained catalyst roasts body sample；Roasting body sample is packed into solid by the 3rd step
Fixed bed reaction tube under 600 DEG C to 900 DEG C hot conditions, is passed through the H that purity is 99.99%2, reductase 12 hour to 6 it is small when,
Catalyst reduction body sample is made, mass percent composition is：Ni is 10 wt% to 60 wt%, γ-Al2O3For 40 wt% extremely
90 wt%；4th step, take out Reduction Body sample, cooling, tabletting, with 40 mesh to 60 mesh screening media sieve to get for Isosorbide-5-Nitrae-
The nickel-base catalyst of butynediols hydrogenation synthesis 1,4- butanediols.
The present invention is a kind of succinct easy method for preparing nickel-base catalyst, and prepared nickel-base catalyst grain size is about
80nm to 120nm, and narrowly distributing, selectivity is good, and the conversion ratio and 1,4-butanediol yield of Isosorbide-5-Nitrae-butynediols are high, are prepared into
This is low, is easy to industrialization.
Description of the drawings
Attached drawing 1 is the present invention for the SEM Electronic Speculum of the nickel-base catalyst of 1,4- butynediols hydrogenation synthesis 1,4- butanediols
Figure.
Specific embodiment
The present invention from following embodiments limitation, can technique according to the invention scheme and actual conditions determine specifically
Embodiment.Various chemical reagent and chemical article are previously mentioned in the present invention unless otherwise specified, is public in the prior art
Know common chemical reagent and chemical article；Percentage in the present invention is as being mass percent without specified otherwise.
With reference to embodiment, the invention will be further described：
Embodiment 1：This is used for the nickel-base catalyst of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, as steps described below
It arrives：The first step stoichiometrically weighs the desired amount of six water nickel nitrate or one kind in nickel acetate or nickel chloride, nine water respectively
One kind in aluminum nitrate or one kind in aluminum acetate or aluminium chloride, ammonium carbonate or urea, is placed in planetary type ball-milling together with abrading-ball
In the ball grinder of machine, ball milling 0.5 hour to 2 it is small when, take out material, be put into air dry oven, done at 100 DEG C to 110 DEG C
It is dry 10 to 12 it is small when, catalyst precursor sample is made；Presoma sample program is warming up to 350 DEG C to 800 DEG C by second step
Lower roasting 2 hours to 6 it is small when, take out, cool down, grind, between 120 mesh, catalyst roasting is made in 80 mesh in screening, size controlling
Burn body sample；Roasting body sample is packed into fixed bed reaction pipe, under 600 DEG C to 900 DEG C hot conditions, is passed through by the 3rd step
Purity is 99.99% H2, reductase 12 hour to 6 it is small when, catalyst reduction body sample is made, mass percent composition is：Ni
For 10 wt% to 60 wt%, γ-Al2O3For 40 wt% to 90 wt%；4th step takes out Reduction Body sample, cooling, tabletting, with 40
Mesh to 60 mesh screening media are sieved to get the nickel-base catalyst for Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol.
This is used for the preparation method of the nickel-base catalyst of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, using mechanization
Required catalyst is made in method, easy to operate, quick.
The reaction mechanism of six water nickel nitrates, nine water aluminum nitrates and 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 six water nickel nitrates, nine water aluminum nitrates and 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)
Screening media is the sieve in existing known technology or sieve or other screening plants.
Embodiment 2：This is used for the nickel-base catalyst of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, as steps described below
It obtains：The first step stoichiometrically weighs the desired amount of six water nickel nitrate or one kind in nickel acetate or nickel chloride, nine respectively
One kind in water aluminum nitrate or one kind in aluminum acetate or aluminium chloride, ammonium carbonate or urea, is placed in planetary ball together with abrading-ball
In the ball grinder of grinding machine, when ball milling 0.5 is small or when 2 is small, material is taken out, air dry oven is put into, at 100 DEG C or 110 DEG C
When drying 10 or 12 is small, catalyst precursor sample is made；Presoma sample program is warming up to 350 DEG C or 800 by second step
It when roasting 2 is small at DEG C or when 6 is small, takes out, cools down, grind, catalyst is made between 80 mesh or 120 mesh in screening, size controlling
Roast body sample；Roasting body sample is packed into fixed bed reaction pipe, under 600 DEG C or 900 DEG C of hot conditions, led to by the 3rd step
Enter the H that purity is 99.99%2, when reductase 12 is small or when 6 is small, catalyst reduction body sample is made, mass percent composition is：
Ni is 10 wt% or 60 wt%, γ-Al2O3For 40 wt% or 90 wt%；4th step, takes out Reduction Body sample, cooling, and tabletting is used
40 mesh or the screening of 60 mesh screening media are to get the nickel-base catalyst for Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol.
Embodiment 3：As the optimization of above-described embodiment, abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：2:
1。
Embodiment 4：As the optimization of above-described embodiment, abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：1:
1。
Embodiment 5：As the optimization of above-described embodiment, abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：1:
2。
Embodiment 6：As the optimization of above-described embodiment, a diameter of 6 mm of big ball, the small ball's diameter is 3 mm.
Embodiment 7：As the optimization of above-described embodiment, the mass ratio of abrading-ball and total material is：2:1.
Embodiment 8：As the optimization of above-described embodiment, the mass ratio of abrading-ball and total material is：3:1.
Embodiment 9：As the optimization of above-described embodiment, the mass ratio of abrading-ball and total material is：4:1.
Embodiment 10：As the optimization of above-described embodiment, in second step, presoma sample program heating rate for 10 DEG C/
Min to 40 DEG C/min；Or/and the 3rd in step, is passed through the H that purity is 99.99%2,H2Volume flow for 0.20 mL/min extremely
0.60 mL/min。
Embodiment 11：This is used for the nickel-base catalyst of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, according to following steps
Suddenly obtain：The first step stoichiometrically weighs six water nickel nitrates, nine water aluminum nitrates, 19.63 g of 36.78 g of 16.52 g
Ammonium carbonate and 145.86 g size abrading-ball, be placed in the ball grinder of planetary ball mill（97.24 g of big ball, bead 48.62
g）, when ball milling 1 is small, material is taken out, when forced air drying 12 is small at 110 DEG C, catalyst precursor sample is made；Second step, it is preceding
It drives body sample program and is warming up to 400 DEG C, when roasting 4 is small, take out, cool down, grind, 80 mesh to 120 mesh sieves are crossed in screening, and roasting is made
Burn body sample；3rd step under the conditions of 800 DEG C, uses 99.99%H2Reduce 4 it is small when, take out, cool down, grind, screening, cross 40 mesh
To 60 mesh sieves, the nickel-base catalyst of obtained Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol.
Embodiment 12：This is used for the nickel-base catalyst of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, according to following steps
Suddenly obtain：The first step stoichiometrically weighs six water nickel nitrates, nine water aluminum nitrates, 12.22 g of 36.78 g of 16.52 g
Urea and the sizes of balls abrading-ball of 131.04 g be placed in the ball grinder of planetary ball mill（87.36 g of big ball, bead 43.68
g）, when ball milling 1 is small, material is taken out, when forced air drying 12 is small at 110 DEG C, catalyst precursor sample is made；Second step, it is preceding
It drives body sample program and is warming up to 400 DEG C, when roasting 4 is small, take out, cool down, grind, 80 mesh to 120 mesh sieves are crossed in screening, and roasting is made
Burn body sample；3rd step under the conditions of 850 DEG C, uses 99.99%H2Reduce 4 it is small when, take out, cool down, grind, screening, cross 40 mesh
To 60 mesh sieves, the nickel-base catalyst of obtained Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol.
Above-described embodiment 11 and embodiment 12 are obtained for the Ni-based of 1,4- butynediols hydrogenation synthesis 1,4- butanediols
Catalyst, grain size are about 80-120nm, and distribution of particles is narrow, and SEM electron microscopes are as shown in Figure 1.
Evaluation experimental 1：It weighs made from above-described embodiment 11 for 1,4- butynediols hydrogenation synthesis 1,4- butanediols
0.60 g of nickel-base catalyst sample adds in slurry reactor kettle.Evaluation response condition is：Reaction temperature is 110 DEG C, H2Pressure is 4
MPa, 600 r/min of stir speed (S.S.), when the reaction time 3 is small, Isosorbide-5-Nitrae-butynediols addition is 30 mL.Evaluation result：It measures anti-
Isosorbide-5-Nitrae in kettle-butynediols conversion ratio is answered to reach 98.4%, the selectivity of 1,4-butanediol reaches 84.3%, and carbonyl value is 1.49 mg
(KOH)/g。
Evaluation experimental 2：It weighs made from above-described embodiment 12 for 1,4- butynediols hydrogenation synthesis 1,4- butanediols
Nickel-base catalyst sample carries out evaluation experimental with 1 same procedure of evaluation experimental.Evaluation result：Measure 1,4- butine in reaction kettle
Two alcohol conversions reach 99.2%, and the selectivity of 1,4-butanediol reaches 86.7%, and carbonyl value is 1.37 mg (KOH)/g.
Evaluation experimental 1, the evaluation result of evaluation experimental 2 show obtained for Isosorbide-5-Nitrae-butine two by embodiment 11 and 12
The nickel-base catalyst of alcohol hydrogenation synthesis 1,4-butanediol, in Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, selectivity is good,
High conversion rate, the 1,4- butanediol high incomes of 1,4- butynediols.
In conclusion the present invention is a kind of simple, quick method for preparing nickel-base catalyst, what the present invention obtained Ni-based urges
Catalyst particles are evenly distributed, which there is good, Isosorbide-5-Nitrae-butynediols the high conversion rate of selectivity, 1,4-butanediol to receive
The characteristics of rate is high, nickel-base catalyst made from this method is at low cost, convenient for industrialized production.
More than technical characteristic constitutes the embodiment of the present invention, can basis with stronger adaptability and implementation result
Actual needs increases and decreases non-essential technical characteristic, to meet the needs of different situations.
Claims (10)
1. a kind of nickel-base catalyst for Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, it is characterised in that according to following steps
Suddenly obtain：The first step, stoichiometrically weigh respectively the desired amount of six water nickel nitrate or one kind in nickel acetate or nickel chloride,
One kind in nine water aluminum nitrates or one kind in aluminum acetate or aluminium chloride, ammonium carbonate or urea, is placed in planetary together with abrading-ball
In the ball grinder of ball mill, ball milling 0.5 hour to 2 it is small when, take out material, air dry oven be put into, at 100 DEG C to 110 DEG C
When lower drying 10 to 12 is small, catalyst precursor sample is made；Presoma sample program is warming up to 350 DEG C extremely by second step
Roasted at 800 DEG C 2 hours to 6 it is small when, take out, cool down, grind, screening, size controlling between 120 mesh, is made and urges in 80 mesh
Agent roasts body sample；Roasting body sample is packed into fixed bed reaction pipe, in 600 DEG C to 900 DEG C hot conditions by the 3rd step
Under, it is passed through the H that purity is 99.99%2, reductase 12 hour to 6 it is small when, catalyst reduction body sample, mass percent group is made
Become：Ni is 10 wt% to 60 wt%, γ-Al2O3For 40 wt% to 90 wt%；4th step takes out Reduction Body sample, cools down, pressure
Piece is sieved with 40 mesh to 60 mesh screening media to get the nickel catalyst for Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol
Agent.
2. the nickel-base catalyst according to claim 1 for Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, special
Sign is that abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：2:1.
3. the nickel-base catalyst according to claim 1 for Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, special
Sign is that abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：1:1.
4. the nickel-base catalyst according to claim 1 for Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, special
Sign is that abrading-ball has big ball and a bead, and the mass ratio of big ball and bead is：1:2.
5. the nickel catalyst for 1,4- butynediols hydrogenation synthesis 1,4- butanediols according to Claims 2 or 3 or 4
Agent, it is characterised in that a diameter of 6 mm of big ball, the small ball's diameter are 3 mm.
6. it is used for the Ni-based of 1,4- butynediols hydrogenation synthesis 1,4- butanediols according to claim 1 or 2 or 3 or 4 and 5
Catalyst, it is characterised in that the mass ratio of abrading-ball and total material is：2:1.
7. it is used for the Ni-based of 1,4- butynediols hydrogenation synthesis 1,4- butanediols according to claim 1 or 2 or 3 or 4 and 5
Catalyst, it is characterised in that the mass ratio of abrading-ball and total material is：3:1.
8. it is used for the Ni-based of 1,4- butynediols hydrogenation synthesis 1,4- butanediols according to claim 1 or 2 or 3 or 4 and 5
Catalyst, it is characterised in that the mass ratio of abrading-ball and total material is：4:1.
9. it is used for 1,4- butynediols hydrogenation synthesis 1,4- fourths according to claim 1 or 2 or 3 or 4 and 5 or 6 or 7 or 8
The nickel-base catalyst of glycol, it is characterised in that in second step, presoma sample program heating rate for 10 DEG C/min to 40 DEG C/
min；Or/and the 3rd in step, is passed through the H that purity is 99.99%2,H2Volume flow be 0.20 mL/min to 0.60 mL/
min。
10. it is a kind of according to claim 1 to 9 any one for 1,4- butynediols hydrogenation synthesis 1,4- butanediols
The preparation method of nickel-base catalyst, it is characterised in that carry out as steps described below：The first step stoichiometrically weighs institute respectively
Six water nickel nitrates of requirement or one kind in nickel acetate or nickel chloride, nine water aluminum nitrates or one kind in aluminum acetate or aluminium chloride,
One kind in ammonium carbonate or urea is placed in together with abrading-ball in the ball grinder of planetary ball mill, ball milling 0.5 hour to 2 it is small when,
Material is taken out, is put into air dry oven, when drying 10 to 12 is small at 100 DEG C to 110 DEG C, catalyst precursor examination is made
Sample；Second step, presoma sample program is warming up at 350 DEG C to 800 DEG C roast 2 hours to 6 it is small when, take out, cooling, grind
Mill, screening, for size controlling in 80 mesh between 120 mesh, obtained catalyst roasts body sample；3rd step, by roasting body sample dress
Enter fixed bed reaction pipe, under 600 DEG C to 900 DEG C hot conditions, be passed through the H that purity is 99.99%2, reductase 12 hour is to 6 small
When, catalyst reduction body sample is made, mass percent composition is：Ni is 10 wt% to 60 wt%, γ-Al2O3For 40 wt%
To 90 wt%；4th step, takes out Reduction Body sample, cooling, tabletting, is sieved with 40 mesh to 60 mesh screening media to get for 1,
The nickel-base catalyst of 4- butynediols hydrogenation synthesis 1,4- butanediols.
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|---|---|---|---|---|
| CN102974353A (en) * | 2012-12-07 | 2013-03-20 | 新疆大学 | NiO/gamma-Al2O3 catalyst of methane and carbon dioxide reforming synthesis gas and method for preparing NiO/gamma-Al2O3 catalyst of methane and carbon dioxide reforming synthesis gas |
| CN106040246A (en) * | 2016-06-27 | 2016-10-26 | 中触媒新材料股份有限公司 | Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol |
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| CN102974353A (en) * | 2012-12-07 | 2013-03-20 | 新疆大学 | NiO/gamma-Al2O3 catalyst of methane and carbon dioxide reforming synthesis gas and method for preparing NiO/gamma-Al2O3 catalyst of methane and carbon dioxide reforming synthesis gas |
| CN106040246A (en) * | 2016-06-27 | 2016-10-26 | 中触媒新材料股份有限公司 | Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol |
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