CN102029160B - Catalyst for use in preparation of paraphenyldimethylamine and preparation method thereof - Google Patents
Catalyst for use in preparation of paraphenyldimethylamine and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 35
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- 239000003426 co-catalyst Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007868 Raney catalyst Substances 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical class O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- -1 dimethoxy nitrile Chemical class 0.000 description 20
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- GOECOOJIPSGIIV-UHFFFAOYSA-N copper iron nickel Chemical compound [Fe].[Ni].[Cu] GOECOOJIPSGIIV-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for use in the preparation of paraphenyldimethylamine, which is a supported nickel catalyst. The carrier of the catalyst is gamma-Al2O3 type aluminum oxide, the specific surface area of the carrier is 170 to 200m<2>/g, the pore volume is 0.35 to 0.45cm<3>/g, and the aperture is 4.5 to 6.0nm, the carrier is loaded with nickel and an auxiliary catalyst which may be copper, cobalt, iron or zinc or one or two of copper, cobalt, iron or zinc, the loaded nickel accounts for 5 to 25 percent of the total mass of the catalyst, the auxiliary catalyst accounts for 3 to 8 percent of the total mass, and the carrier aluminum oxide accounts for the balance. When the catalyst disclosed by the invention is used, paraphenyldimethylamine can be prepared by hydrogenation of isophthalodinitrile under milder conditions, the conversion rate of isophthalonitrile is 100 percent, and the selectivity of the paraphenyldimethylamine can reach 98.8 percent. The invention also discloses the preparation method of the catalyst.
Description
Technical field
The present invention relates to Raney nickel, specifically, is a kind of Raney nickel of support type, the invention still further relates to the preparation of m-xylene diamine.
Technical background
M-xylene diamine is not only a kind of excellent performance and broad-spectrum epoxy curing agent, but also is a kind of important fine-chemical intermediate, and its main application has: 1. seriation epoxy curing agent; 2. new engineering material additive; 3. rubber chemicals, agricultural chemicals, fibre finish agent, antirust agent, intercalating agent, lubricant, paper conversion auxiliary agent and electronic chemical product are the high added value fine chemicals that has a extensive future.
At present, m-xylene diamine all adopts the production of isophthalodinitrile catalytic hydrogenation process, catalyst system therefor, and common have Raney's nickel, modification Raney's nickel or an amorphous nickel etc., and these catalyst metals nickel content reach more than 60%, the manufacturing cost height.
Existing catalyst initial activity is good, but less stable uses a period of time in reactor, and catalyst hydrogenation activity descends significantly, and its possible cause is: 1. small amount of impurities exists and may cause the catalyst member inactivation in the isophthalodinitrile; 2. the dimerization of hydrogenation reaction generation or poly by-product deposition cause catalyst activity reduction at catalyst surface.
In addition, existing catalyst is applicable to the gap still reaction, and production scale is little, and catalyst granules is tiny, uses easy efflorescence under stirring condition repeatedly, causes inferior separating effect, and catalyst attrition is also bigger.With regard to the still reaction production technology of gap, hydrogen utilization ratio has only 50-60%, has problems such as production cost is higher, poor stability.
Summary of the invention
The objective of the invention is to:
1. develop that a kind of cost is low, the operating procedure route is simple, environmental pollution is little, the isophthalodinitrile hydrogenation of excellent catalytic effect produces the m-xylene diamine new catalyst;
2. provide the production technology of this catalyst in the tank reactor of gap, and the continuous production technology in fixed bed reactors, for scale, the serialization cleaner production of m-xylene diamine provides technical foundation.
Technical scheme of the present invention is as follows:
A kind of catalyst for the preparation of m-xylene diamine, it is the Raney nickel of support type, carrier is γ-Al
2O
3The aluminium oxide of type, its specific area are 170-200 m
2/ g, pore volume are 0.35-0.45 cm
3/ g, the aperture is 4.5-6.0 nm, load has nickel and co-catalyst on it, co-catalyst is copper, cobalt, iron or zinc, co-catalyst can be a kind of of above-mentioned element or two kinds of compositions, wherein the nickel of load accounts for the 5-25% of catalyst gross mass, and co-catalyst accounts for the 3-8% of catalyst gross mass, and all the other are alumina catalyst support.
A kind of method for preparing above-mentioned catalyst, it comprises the following steps:
The preparation of step 1. catalyst carrier:
To be the bead of 1-2 mm with the diameter of boehmite preparation, in air atmosphere, 500-700 ℃ of calcining, obtain corresponding γ-Al
2O
3The alumina support of type, its specific area are 191 m
2/ g, pore volume are 0.40 cm
3/ g, the aperture is 6.0 nm;
The preparation of step 2. catalyst precarsor:
Six water nickel nitrate and cobalt nitrate hexahydrates with metering, one or two or more kinds material in nitrate trihydrate copper and the six water ferric nitrates makes up, weigh, add a certain amount of deionized water, under condition of stirring, make its whole dissolvings, its concentration is: 0.5-6.0 mol/l, the compositing formula of pressing catalyst adds the carrier of step 1 preparation, under agitation, with solution impregnation to carrier, the carrier that flooded catalyst activity component and co-catalyst at 100 ℃ of dry 10-24 h, after the drying is warmed up to its program in air atmosphere 400 ℃ (3 ℃/min) and keep 4 h, obtain catalyst precarsor;
Step 3. at 400 ℃, is carried out reduction activation 4-5 h with catalyst precarsor in the pure hydrogen of normal pressure, namely get the catalyst for the preparation of m-xylene diamine of going back ortho states.
The technology of the catalyst batch preparation m-xylene diamine that a kind of usefulness is above-mentioned, it is in tank reactor, it is 60-80 ℃ in temperature, pressure is 6.0 MPa, atmosphere is pure hydrogen, and (the two volume ratio=1:4) is solvent, and the mass percentage concentration of isophthalodinitrile is 5-10% for methyl alcohol and toluene mixture, carried out hydrogenation reaction 1-1.5 hour, and namely got m-xylene diamine.
The above-mentioned catalyst continous way of a kind of usefulness prepares the technology of m-xylene diamine, it is in fixed bed reactors, it is 90-120 ℃ in temperature, pressure is 6.0 MPa, atmosphere is pure hydrogen, (the two volume ratio=1:4) is solvent, and the mass percentage concentration of isophthalodinitrile is 2-4%, hydrogen gas space velocity 1000 h for methyl alcohol and toluene mixture
-1, liquid air speed 2.5 h
-1, continuously produce m-xylene diamine.
Catalyst nickel content for the preparation of m-xylene diamine of the present invention is low, with low cost, and catalyst activity is strong, can prepare m-xylene diamine under relatively mild condition, and environmental friendliness.
The specific embodiment
Embodiment one:
At 500 ℃, in air atmosphere, calcining is the bead 4 hours of 1-2 mm with the diameter of boehmite preparation, obtains the corresponding oxidation alumina supporter.Be γ-Al after testing
2O
3Type, its specific area are 191 m
2/ g, pore volume are 0.40 cm
3/ g, the aperture is 6.0 nm.
Embodiment two:
Six water nickel nitrates, 6.2 g add 25 ml distilled water wiring solution-formings, are impregnated on the alumina support of embodiment one preparation, and the content that makes metallic nickel in the catalyst is 5 wt%.Flooded the carrier of nickel component at 100 ℃ of drying 10 h.With dried catalyst, 400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 5 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back the target catalyst of ortho states.
Get above-mentioned catalyst 5.0g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 5.0%, reactant liquor volume 125 ml add in the reactor, reaction pressure=6.0M Pa, reaction temperature=70 ℃, behind the h of reaction time=1.5, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 62.4%, m-xylene diamine selectively be 25.5%.
Embodiment three:
Six water nickel nitrates, 31.0 g add 25 ml distilled water wiring solution-formings, are impregnated on the alumina support of embodiment one preparation, and the content that makes metallic nickel in the catalyst is 25 wt%.Flooded the carrier of nickel component at 100 ℃ of drying 24 h.With dried catalyst, 400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back ortho states target catalyst.
Get above-mentioned catalyst 5 g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 7.5%, reactant liquor volume 125 ml add in the reactor, reaction pressure=6.0M Pa, reaction temperature=70 ℃, behind the h of reaction time=1, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 100%, m-xylene diamine selectively be 86.8%.
Embodiment four:
Content by metallic nickel is 20 wt%, and metallic copper content is 5 wt%, and metal Ferrum content is 3 wt%, take by weighing six water nickel nitrates, 24.8 g, nitrate trihydrate copper 5.8 g, six water ferric nitrates, 4.7 g, add 25 ml distilled water wiring solution-formings, be impregnated on the alumina support of embodiment one preparation.Flooded the carrier of nickel-copper-iron component at 100 ℃ of drying 24 h.With dried catalyst, 400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 5 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back ortho states target catalyst.
Get above-mentioned catalyst 5 g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 7.5%, reactant liquor volume 125 ml add in the reactor, reaction pressure=6.0M Pa, reaction temperature=70 ℃, behind the h of reaction time=1.5, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 99.8%, m-xylene diamine selectively be 83.4%.
Embodiment five:
Content by metallic nickel is 20 wt%, and metallic copper content is 3 wt%, takes by weighing six water nickel nitrates, 24.8 g, and nitrate trihydrate copper 3.5 g add 25 ml distilled water wiring solution-formings, is impregnated on the alumina support of embodiment one preparation.Flooded the carrier of nickel-copper component at 100 ℃ of drying 24 h.With dried catalyst, 400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back ortho states target catalyst.
Get above-mentioned catalyst 5g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 7.5%, reactant liquor volume 125 ml add in the reactor, reaction pressure=6.0M Pa, reaction temperature=70 ℃, behind the h of reaction time=1, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 100%, m-xylene diamine selectively be 92.0%.
Embodiment six:
Content by metallic nickel is 20 wt%, and metallic cobalt content is 5 wt%, takes by weighing six water nickel nitrates, 24.8 g, and cobalt nitrate hexahydrate 6.2 g add 25 ml distilled water wiring solution-formings, is impregnated on the alumina support of embodiment one preparation.Flooded the carrier of nickel-cobalt component at 100 ℃ of drying 24 h.With dried catalyst, 400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back ortho states target catalyst.
Get above-mentioned catalyst 5 g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 7.5%, reactant liquor volume 125 ml add in the reactor, reaction pressure=6.0M Pa, reaction temperature=70 ℃, behind the h of reaction time=1, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 100%, m-xylene diamine selectively be 90.3%.
Embodiment seven:
Content by metallic nickel is 20 wt%, and metallic copper content is 3 wt%, and metallic cobalt content is 5 wt%, take by weighing six water nickel nitrates, 24.8 g, nitrate trihydrate copper 3.5 g, cobalt nitrate hexahydrate 6.2 g, add 25 ml distilled water wiring solution-formings, be impregnated on the alumina support of embodiment one preparation.Flooded the carrier of nickel-copper-cobalt component at 100 ℃ of drying 24 h.With dried catalyst, 400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back ortho states target catalyst.
Get above-mentioned catalyst 5 g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 7.5%, reactant liquor volume 125ml adds in the reactor, reaction pressure=6.0M Pa, reaction temperature=70 ℃, behind the h of reaction time=1, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 100%, m-xylene diamine selectively be 98.8%.
Embodiment eight:
Catalyst composition, preparation method and activation processing are with embodiment seven.
Get above-mentioned catalyst 5g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 10.0%, reactant liquor volume 125 ml add in the reactor, reaction pressure=6.0M Pa, reaction temperature=70 ℃, behind the h of reaction time=1, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 100%, m-xylene diamine selectively be 93.3%.
Embodiment nine:
Catalyst composition, preparation method and activation processing are with embodiment seven.
Get above-mentioned catalyst 5 g, (the two volume ratio=1:4) is solvent with methyl alcohol and toluene mixture, between the concentration of dimethoxy nitrile be 7.5%, reactant liquor volume 125 ml add in the reactor, reaction pressure=6.0M Pa, reaction temperature=80 ℃, behind reaction time=1h, the sampling chromatography, between the conversion ratio of dimethoxy nitrile be 100%, m-xylene diamine selectively be 94.5%.
Embodiment ten:
Catalyst composition, preparation method and activation processing are with embodiment seven.
Carrying out the hydrogenation activity evaluation in fixed bed reactors, is solvent with methyl alcohol and toluene mixture (the two ratio is 1:4), and the concentration of a dimethoxy nitrile is 3.5%, reaction pressure 6.0 MPa, 100 ℃ of reaction temperatures, hydrogen gas space velocity 1000h
-1, liquid air speed 2.5 h
-1, catalyst loading amount 50 ml react sample analysis behind 4 h, the conversion ratio of isophthalodinitrile is 100%, m-xylene diamine selectively be 92.1%.
Embodiment 11:
Catalyst composition, preparation method and activation processing are with embodiment seven.
Carrying out the hydrogenation activity evaluation in fixed bed reactors, is solvent with methyl alcohol and toluene mixture (the two ratio is 1:4), and the concentration of a dimethoxy nitrile is 3.5%, reaction pressure 6.0 MPa, 120 ℃ of reaction temperatures, hydrogen gas space velocity 500 h
-1, liquid air speed 2.0 h
-1, catalyst loading amount 60 ml, catalytic reaction 500 h, the conversion ratio of isophthalodinitrile are 100%, m-xylene diamine selectively be 91.5%.
Embodiment 12:
Catalyst composition, preparation method and activation processing are with embodiment seven.
Carrying out the hydrogenation activity evaluation in fixed bed reactors, is solvent with methyl alcohol and toluene mixture (the two ratio is 1:4), and the concentration of a dimethoxy nitrile is 4.0%, reaction pressure 6.0 MPa, 90 ℃ of reaction temperatures, hydrogen gas space velocity 500 h
-1, liquid air speed 2.0 h
-1, catalyst loading amount 60 ml, catalytic reaction 5 h, the conversion ratio of isophthalodinitrile are 90.2%, m-xylene diamine selectively be 85.4%.
Embodiment 13:
Catalyst composition, preparation method and activation processing are with embodiment seven.
Carrying out the hydrogenation activity evaluation in fixed bed reactors, is solvent with methyl alcohol and toluene mixture (the two ratio is 1:4), and the concentration of a dimethoxy nitrile is 2.0%, reaction pressure 6.0 MPa, 120 ℃ of reaction temperatures, hydrogen gas space velocity 500 h
-1, liquid air speed 2.0 h
-1, catalyst loading amount 60 ml, catalytic reaction 5 h, the conversion ratio of isophthalodinitrile are 100%, m-xylene diamine selectively be 96.2%.
Claims (4)
1. catalyst for the preparation of m-xylene diamine, it is characterized in that: it is the Raney nickel of support type, carrier is γ-Al
2O
3The aluminium oxide of type, its specific area are 191 m
2/ g, pore volume are 0.4 cm
3/ g, the aperture is 6 nm, and load has nickel and co-catalyst on it, and co-catalyst is copper, cobalt and iron, and wherein the nickel of load accounts for the 5-25% of catalyst gross mass, and co-catalyst accounts for the 3-8% of catalyst gross mass, and all the other are alumina catalyst support.
2. a method for preparing the described catalyst of claim 1 is characterized in that it comprises the following steps:
The preparation of step 1. catalyst carrier:
To be the bead of 1-2 mm with the diameter of boehmite preparation, in air atmosphere, 500-700 ℃ of calcining, obtain corresponding γ-Al
2O
3The alumina support of type, its specific area are 191 m
2/ g, pore volume are 0.40 cm
3/ g, the aperture is 6.0 nm;
The preparation of step 2. catalyst precarsor:
Six water nickel nitrate and cobalt nitrate hexahydrates with metering, one or two or more kinds material in nitrate trihydrate copper and the six water ferric nitrates makes up, weigh, add a certain amount of deionized water, under condition of stirring, make its whole dissolvings, its concentration is: 0.5-6.0 mol/l, the compositing formula of pressing catalyst adds the carrier of step 1 preparation, under agitation, with solution impregnation to carrier, with the carrier that flooded catalyst activity component and co-catalyst at 100 ℃ of dry 10-24 h, after the drying with its in air atmosphere with 3 ℃/min temperature programming to 400 ℃ and keep 4 h, obtain catalyst precarsor;
Step 3. at 400 ℃, is carried out reduction activation 4-5 h with catalyst precarsor in the pure hydrogen of normal pressure, namely get the catalyst for the preparation of m-xylene diamine of going back ortho states.
3. technology with the described catalyst batch preparation of claim 1 m-xylene diamine, it is characterized in that: it is in tank reactor, it is 60-80 ℃ in temperature, pressure is 6.0 MPa, atmosphere is pure hydrogen, and methyl alcohol and toluene are solvent with volume ratio=1: 4 mixture, and the mass percentage concentration of isophthalodinitrile is 5-10%, carried out hydrogenation reaction 1-1.5 hour, and namely got m-xylene diamine.
4. technology for preparing m-xylene diamine with the described catalyst continous way of claim 1, it is characterized in that: it is in fixed bed reactors, it is 90-120 ℃ in temperature, pressure is 6.0 MPa, atmosphere is pure hydrogen, methyl alcohol and toluene are solvent with volume ratio=1: 4 mixture, and the mass percentage concentration of isophthalodinitrile is 2-4%, hydrogen gas space velocity 1000h
-1, liquid air speed 2.5 h
-1, continuously produce m-xylene diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010547098.4A CN102029160B (en) | 2010-11-17 | 2010-11-17 | Catalyst for use in preparation of paraphenyldimethylamine and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010547098.4A CN102029160B (en) | 2010-11-17 | 2010-11-17 | Catalyst for use in preparation of paraphenyldimethylamine and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102029160A CN102029160A (en) | 2011-04-27 |
| CN102029160B true CN102029160B (en) | 2013-08-21 |
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|---|---|---|---|
| CN201010547098.4A Expired - Fee Related CN102029160B (en) | 2010-11-17 | 2010-11-17 | Catalyst for use in preparation of paraphenyldimethylamine and preparation method thereof |
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| CN102744071B (en) * | 2012-06-04 | 2014-07-30 | 赛鼎工程有限公司 | Supported urushibara nickel catalyst |
| CN103539676B (en) * | 2012-07-12 | 2016-06-08 | 中国石油化工股份有限公司 | The method of isophthalodinitrile Hydrogenation m-xylene diamine |
| CN106179362B (en) * | 2016-07-08 | 2020-06-09 | 中国石油化工股份有限公司 | Fixed bed continuous production device for preparing propionitrile and application thereof |
| CN106866428A (en) * | 2017-03-10 | 2017-06-20 | 合肥工业大学 | A kind of method that carrier nanometer catalyst catalyzes and synthesizes tetramethyl dipropylenetriamine |
| CN109046359A (en) * | 2018-08-06 | 2018-12-21 | 杭州更蓝生物科技有限公司 | A kind of catalyst preparing linalool for geraniol isomerization |
| CN113398932B (en) * | 2020-03-16 | 2023-10-31 | 中国石油化工股份有限公司 | Preparation method for preparing diamine by hydrogenation of dinitrile |
| CN114471572B (en) * | 2020-10-27 | 2023-08-08 | 中国石油化工股份有限公司 | Catalyst for preparing diamine by hydrogenation of dinitrile, preparation method and application thereof |
| CN115569655B (en) * | 2022-11-07 | 2024-04-26 | 中国科学院山西煤炭化学研究所 | Catalyst for selective hydrogenation olefin removal of reforming generated oil, and preparation method and application thereof |
| CN115739104A (en) * | 2022-11-30 | 2023-03-07 | 山东海科创新研究院有限公司 | M-xylylenediamine catalyst, and preparation method and application thereof |
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| EP1262232A1 (en) * | 2001-05-22 | 2002-12-04 | Mitsubishi Gas Chemical Company, Inc. | Catalysts and process for producing aromatic amines |
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