CN100574877C - A kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares the method for amino T acid - Google Patents
A kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares the method for amino T acid Download PDFInfo
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- CN100574877C CN100574877C CN200710011806A CN200710011806A CN100574877C CN 100574877 C CN100574877 C CN 100574877C CN 200710011806 A CN200710011806 A CN 200710011806A CN 200710011806 A CN200710011806 A CN 200710011806A CN 100574877 C CN100574877 C CN 100574877C
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- -1 amino T acid Chemical compound 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- 229910000545 Nickel–aluminium alloy Inorganic materials 0.000 title claims abstract description 16
- UBDHSURDYAETAL-UHFFFAOYSA-N 8-aminonaphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 UBDHSURDYAETAL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 241000233855 Orchidaceae Species 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the applied technical field of catalytic hydrogenation, relate to the method that a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares amino T acid, this method can be under temperate condition be reduced to nitro T acid the amino T acid of high-purity.This method is a catalyst precursor with the amorphous nickel aluminium alloy of special process preparation, the catalyst that obtains behind the alkali activation presoma can prepare amino T acid with nitro T acid high selectivity catalytic hydrogenation under relatively mild condition, the selectivity of amino T acid reaches 100%, the yield of amino T acid reaches more than 99.8%, it is catalyst that the outstanding feature of this technology adopts the amorphous nickel aluminium alloy of alkali activation, have high activity and selectivity, the product post processing is simple, catalyst can be applied mechanically repeatedly, compare with traditional handicraft, can effectively reduce production cost.
Description
Technical field
The invention belongs to the applied technical field of catalytic hydrogenation.Relate to the method that a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares amino T acid, this method can be under temperate condition be reduced to nitro T acid the amino T acid of high-purity.
Background technology
H-acid is the intermediate of preparation water-soluble dye, is mainly used in to produce acid dyes, direct dyes and reactive dye, and is directly black as acid day orchid, Reactive Brilliant Red K-2BP etc., and purposes is very extensive.
JP50142546 discloses early stage production technology: be raw material with the naphthalene, obtain 1,3 through three sulfonation, the 6-naphthalene trisulfonic acid nitratedly obtains nitro T acid with it, and in the alkali and back uses iron powder reducing to get amino T acid, and the amino T acid of alkali fusion obtains H acid.Wherein nitro T acid is reduced to one step of amino T acid iron powder reducing, SO
2Reduction, electrochemical reduction and four kinds of methods of catalytic hydrogenation.Adopting iron powder in the iron powder reducing method is reducing agent, electrolyte (FeCl
2) reduce under boiling temperature for catalyst, this is the main technique of domestic current.This technology is simple, but reduction step produces a large amount of three wastes, and both contaminated environment has increased the manufacturing cost of H-acid again.Therefore, be badly in need of the catalytic hydrogenation process that exploitation is cheap and clean.
Japan Patent (JP49127956) report uses thunder Buddhist nun (Raney) nickel to be catalyst, under 1.5～2.0MPa pressure, nitro T acid is reduced to amino T acid under 130 ℃.It is catalyst that DE2747714 also adopts Raney nickel, under 100～300bar pressure, and the amino T acid of 130～140 ℃ of catalysis nitro T acid hydrogenation preparing.But because the restriction of factors such as active and service life, during commercial Application, economic benefit is not remarkable.Japan Patent (JP50101349) report adopts Pd/C to make catalyst, and under 2.0MPa pressure, 60～200 ℃ of reduction nitro T acid is amino T acid, singly be because Metal Palladium costs an arm and a leg, and it is limited to apply mechanically number of times, is difficult to industrialization.Therefore, be badly in need of further improving catalytic activity, satisfy the industrialization needs.
Summary of the invention
At the deficiency of mentioning in the background technology, the amorphous state Ni-Al alloy catalyst that the purpose of this invention is to provide a kind of alkali activation, use it for the amino T acid of catalysis nitro T acid hydrogenation preparing, reaction temperature and reaction pressure have been reduced, catalyst can be applied mechanically repeatedly, effectively reduces the production cost of amino T acid.
Technical solution of the present invention is, a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares the method for amino T acid, and this method is finished by following steps: the amorphous state Ni-Al alloy catalyst after the nitro T acid of adding nitro T acid or alkali lye neutralization in still formula high-pressure reactor, deionized water and the activation of process alkali.The mass percent of catalyst and nitro T acid is 0.1%～10%, nitro T acid is 10%～60% with the mass percent of deionized water, earlier use hydrogen exchange again behind the airtight autoclave with nitrogen replacement, filling hydrogen to pressure then is 0.1～1MPa, the heating high-pressure still is to 50 ℃～200 ℃ of reaction temperatures, reaction pressure is the hydrogen of 0.5MPa～5MPa, stirs reaction 0.5～4h down;
Wherein, the step that the amorphous state Ni-Al alloy catalyst carries out the alkali activation before use is: the amorphous nickel Al alloy powder is slowly joined in 10～25%NaOH aqueous solution, activate 15～120min down at 70～100 ℃, after removing the Al in the alloyed powder, wash to solution with deoxidation deionized water repeated multiple times and to be neutral, form highly active hydrogenation catalyst, be kept in the deionized water standby.The preparation method of described amorphous nickel aluminium alloy is: with metallic nickel, aluminium and the modified component M of certain mass ratio, heat fused, the alloy of fusion with the cooling bronze drum quenching to 30 of at a high speed rotation～80 ℃, forms the thin bar of amorphous alloy in argon gas atmosphere, become stand-by behind the fine grained with ball mill grinding then, consisting of of amorphous nickel aluminium alloy, 40～50% aluminium, 52～46% nickel, all the other are modification component M, M is Fe, Cr, Mn, Mo, W, Cu, Sn, Zn, Pb, the mixture of one or more among the C.Described reaction system is neutrality or meta-alkalescence solution.
The reaction temperature first-selection is 100～150 ℃.The reaction pressure scope is 2～3MPa.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Get 12g nitro T acid and place beaker, add 20mL water and make its dissolving, with extremely neutral in 23% the NaOH aqueous solution with nitro T acid solution, nitro T acid solution after the neutralization of gained is transferred to together with the 0.1g catalyst carries out hydrogenation reaction in the 70mL autoclave, the nitrogen replacement air is 3 times behind the airtight autoclave, hydrogen exchange nitrogen 3 times, filling hydrogen to pressure then is 0.1MPa, the heating high-pressure still is to 110 ℃ of reaction temperatures, feeding pressure is the hydrogen of 2MPa, start magnetic stirring apparatus, reaction 2h is down stirred in the reaction beginning.Reaction to room temperature, leaches catalyst with the autoclave quenching after finishing, and gets filtrate and carries out efficient liquid phase chromatographic analysis, nitro T acid conversion ratio 98.6%, amino T acid selectivity 100%.
Embodiment 2
Get 12g nitro T acid and place beaker, add 20mL water and make its dissolving, the nitro T acid solution of gained is transferred to together with the 0.3g catalyst carries out hydrogenation reaction in the 70mL autoclave, the nitrogen replacement air is 3 times behind the airtight autoclave, hydrogen exchange nitrogen 3 times, filling hydrogen to pressure then is 0.1MPa, the heating high-pressure still is to 110 ℃ of reaction temperatures, and feeding pressure is the hydrogen of 1MPa, starts magnetic stirring apparatus, reaction 1h is down stirred in the reaction beginning.Reaction to room temperature, leaches catalyst with the autoclave quenching after finishing, and gets filtrate and carries out efficient liquid phase chromatographic analysis, nitro T acid conversion ratio 99.6%, amino T acid selectivity 100%.
Embodiment 3
Get 12g nitro T acid and place beaker, add 20mL water and make its dissolving, with extremely neutral in 23% the NaOH aqueous solution with nitro T acid solution, nitro T acid solution after the neutralization of gained is transferred to together with the 0.2g catalyst carries out hydrogenation reaction in the 70mL autoclave, the nitrogen replacement air is 3 times behind the airtight autoclave, hydrogen exchange nitrogen 3 times, filling hydrogen to pressure then is 0.1MPa, the heating high-pressure still is to 80 ℃ of reaction temperatures, feeding pressure is the hydrogen of 1MPa, start magnetic stirring apparatus, reaction 1h is down stirred in the reaction beginning.Reaction to room temperature, leaches catalyst with the autoclave quenching after finishing, and gets filtrate and carries out efficient liquid phase chromatographic analysis, nitro T acid conversion ratio 99.0%, amino T acid selectivity 100%.
Embodiment 4
Get 6g nitro T acid and place beaker, add 20mL water and make its dissolving, with extremely neutral in 23% the NaOH aqueous solution with nitro T acid solution, nitro T acid solution after the neutralization of gained is transferred to together with the 0.2g catalyst carries out hydrogenation reaction in the 70mL autoclave, the nitrogen replacement air is 3 times behind the airtight autoclave, hydrogen exchange nitrogen 3 times, filling hydrogen to pressure then is 0.1MPa, the heating high-pressure still is to 80 ℃ of reaction temperatures, feeding pressure is the hydrogen of 1MPa, start magnetic stirring apparatus, reaction 80min is down stirred in the reaction beginning.Reaction to room temperature, leaches catalyst with the autoclave quenching after finishing, and gets filtrate and carries out efficient liquid phase chromatographic analysis, nitro T acid conversion ratio 99.3%, amino T acid selectivity 100%.
Claims (5)
1, a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares the method for amino T acid, it is characterized in that, this method is finished by following steps: the nitro T acid that adds nitro T acid or alkali lye neutralization in still formula high-pressure reactor, amorphous state Ni-Al alloy catalyst after deionized water and the activation of process alkali, the mass percent of catalyst and nitro T acid is 0.1%～10%, nitro T acid is 10%～60% with the mass percent of deionized water, earlier use hydrogen exchange again behind the airtight autoclave with nitrogen replacement, filling hydrogen to pressure then is 0.1～1MPa, the heating high-pressure still is to 50 ℃～200 ℃ of reaction temperatures, reaction pressure is the hydrogen of 0.5MPa～5MPa, stirs reaction 0.5～4h down;
Wherein, the step that the amorphous state Ni-Al alloy catalyst carries out the alkali activation before use is: the amorphous nickel Al alloy powder is slowly joined in 10～25%NaOH aqueous solution, activate 15～120min down at 70～100 ℃, after removing the Al in the alloyed powder, wash to solution with deoxidation deionized water repeated multiple times and to be neutral, form highly active hydrogenation catalyst, be kept in the deionized water standby.
2, a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl according to claim 1 prepares the method for amino T acid, it is characterized in that, the preparation method of described amorphous nickel aluminium alloy is: with the metallic nickel of certain mass ratio, aluminium and modified component M, heat fused, the alloy of fusion with the cooling bronze drum quenching to 30 of at a high speed rotation～80 ℃, forms the thin bar of amorphous alloy in argon gas atmosphere, become stand-by behind the fine grained with ball mill grinding then, consisting of of amorphous nickel aluminium alloy, 40～50% aluminium, 52～46% nickel, all the other are modification component M, M is Fe, Cr, Mn, Mo, W, Cu, Sn, Zn, Pb, the mixture of one or more among the C.
3, a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl according to claim 1 prepares the method for amino T acid, it is characterized in that, described reaction system is neutrality or meta-alkalescence solution.
4, a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl according to claim 1 prepares the method for amino T acid, it is characterized in that, described reaction temperature is 100～150 ℃.
5, a kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl according to claim 1 prepares the method for amino T acid, it is characterized in that, described reaction pressure scope is 2～3MPa.
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| CN200710011806A CN100574877C (en) | 2007-06-18 | 2007-06-18 | A kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares the method for amino T acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106587494A (en) * | 2016-12-06 | 2017-04-26 | 浙江力禾集团有限公司 | Method for improving ammonia-nitrogen content of H acid wastewater |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103302257A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Preparation method of aniline hydrogenating amorphous nickel-aluminum catalyst |
| CN106607057B (en) * | 2015-10-26 | 2019-08-20 | 中国石油化工股份有限公司 | A kind of coal bed gas deoxidation catalyst and its preparation method and application |
| CN106824199A (en) * | 2016-12-10 | 2017-06-13 | 河南开祥精细化工有限公司 | A kind of low-voltage hydrogenation catalyst for preparing 1,4 butanediols and preparation method thereof |
| CN112958114A (en) * | 2021-02-09 | 2021-06-15 | 大连理工大学 | Raney nickel catalyst for hydrogenation of aromatic nitro compound in fixed bed and application thereof |
| CN113105372B (en) * | 2021-03-03 | 2023-01-31 | 宁夏锦兴化工有限公司 | Method and device for preparing amino T acid by continuous hydrogenation of nitro-T acid salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1568023A (en) * | 1977-01-26 | 1980-05-21 | Bayer Ag | Process for the preparation of aminoaphthalenesulphonic acids |
| GB1576608A (en) * | 1975-12-10 | 1980-10-08 | Ici Ltd | Catalytic reduction of nitronaphthalene sulphonic acids |
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2007
- 2007-06-18 CN CN200710011806A patent/CN100574877C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1576608A (en) * | 1975-12-10 | 1980-10-08 | Ici Ltd | Catalytic reduction of nitronaphthalene sulphonic acids |
| GB1568023A (en) * | 1977-01-26 | 1980-05-21 | Bayer Ag | Process for the preparation of aminoaphthalenesulphonic acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587494A (en) * | 2016-12-06 | 2017-04-26 | 浙江力禾集团有限公司 | Method for improving ammonia-nitrogen content of H acid wastewater |
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