CN102408362A - Method for producing CLT acid by reducing 6-chloro-3-aminotoluene-4-sulfonic acid - Google Patents
Method for producing CLT acid by reducing 6-chloro-3-aminotoluene-4-sulfonic acid Download PDFInfo
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- CN102408362A CN102408362A CN2011104390614A CN201110439061A CN102408362A CN 102408362 A CN102408362 A CN 102408362A CN 2011104390614 A CN2011104390614 A CN 2011104390614A CN 201110439061 A CN201110439061 A CN 201110439061A CN 102408362 A CN102408362 A CN 102408362A
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- chloro
- sulfonic acid
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- acid
- clt
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- 239000002253 acid Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- VYZCFAPUHSSYCC-UHFFFAOYSA-N 2-amino-5-chloro-4-methylbenzenesulfonic acid Chemical compound CC1=CC(N)=C(S(O)(=O)=O)C=C1Cl VYZCFAPUHSSYCC-UHFFFAOYSA-N 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 13
- JTZLIGVBEAGAFZ-UHFFFAOYSA-N 5-chloro-4-methyl-2-nitrobenzenesulfonic acid Chemical compound CC1=CC([N+]([O-])=O)=C(S(O)(=O)=O)C=C1Cl JTZLIGVBEAGAFZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WYUHTVDGHDRPDW-UHFFFAOYSA-N 3-hydroxy-N-phenyl-4-phenyldiazenylnaphthalene-2-carboxamide Chemical compound C1(=CC=CC=C1)N=NC1=C(C(=CC2=CC=CC=C12)C(=O)NC1=CC=CC=C1)O WYUHTVDGHDRPDW-UHFFFAOYSA-N 0.000 description 1
- 206010000372 Accident at work Diseases 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000012739 red 2G Nutrition 0.000 description 1
- 239000004180 red 2G Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VVNRQZDDMYBBJY-UHFFFAOYSA-M sodium 1-[(1-sulfonaphthalen-2-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 VVNRQZDDMYBBJY-UHFFFAOYSA-M 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for producing CLT acid by reducing 6-chloro-3-aminotoluene-4-sulfonic acid relates to a chemical synthesis method, in particular to the technical field of synthesis of pigment intermediates. The method selects the palladium-carbon catalyst to participate in the reaction, can be recycled, and has low requirement on the purity of the raw material 6-chloro-3-nitrotoluene-4-sulfonic acid by the Pa/C catalyst; the invention has mild reaction process, low reaction pressure, low reaction temperature, no solvent in the material reaction process, easy control in the hydrogenation reduction process and high yield of 96.3 percent.
Description
Technical field
The present invention relates to chemical synthesis process, particularly the synthesis technical field of Pigment Intermediates.
Background technology
CLT acid has another name called 6-chloro-3-phenylmethylamine-4-sulfonic acid, is mainly used in to make bright red color lake C, Lithol Red 2G, is widely used in preparation printing ink etc.This Pigment Intermediates is mainly used in the manufacturing bronze red C, the bright red isochrome variable pigments of bright red LG of rubber and plastics.
Existing from raw material 6-chloro-3-nitrotoluene-4-sulfonic acid reduction preparation 6-chloro-3-phenylmethylamine-4-sulfonic acid (CLT acid), three kinds of methods are arranged:
Method one: make catalyzer in order to platinum/carbon, the liquid-phase hydrogenatin reduction exists reaction process too fast, is difficult for grasping, and causes industrial accident easily.And the difficult collection fully of reaction back platinum/carbon, price comparison is high, has increased production cost, and this method generally is used for the laboratory.
Method two: with nickel as catalyzer; The process of hydrogenating reduction to the requirement of material purity than higher; Because nickel catalyzator is very easily destroyed by raw material impurity wherein, and reaction process need accomplish under the highly compressed situation, and reaction pressure reaches 4.0～4.3Mpa; Also high to equipment requirements, be not suitable for the industriallization continuous production.
Method three: as catalyzer, the production process of China CLT acid at present mainly is to take this method with iron powder.Though iron powder reducing is less demanding to material purity, product yield and purity are not high yet, in reaction process, need a large amount of iron powders to participate in reaction, and the reaction back produces a large amount of mud and sewage, are difficult for handling, and have problem of environmental pollution.
Summary of the invention
Goal of the invention is to propose a kind of method that is beneficial to industriallization continuous production, oligosaprobic reduction 6-chloro-3-phenylmethylamine-4-sulfonic acid production CLT acid.
Technical scheme of the present invention is: under oxygen free condition; Pa/C catalyzer, amine promotor, 6-chloro-3-nitrotoluene-4-sulfonic acid are dropped into reaction kettle; Under the 0.8Mpa pressure condition, stir, and slowly be warmed up to 70～75 ℃, feed hydrogen; Be to react 3.5～4 hours under the condition of 1.8～2.0Mpa at reacting kettle inner pressure, temperature of reaction is controlled at 85～90 ℃; After reaction finishes, treat that material is cooled to 30～40 ℃ naturally after, blowing; Again through after the press filtration, acid out, drying, dry product.
In addition, the Pa content of Pa/C catalyzer according to the invention is 5%, and when feeding intake, the mass ratio of said Pa/C catalyzer, amine promotor and 6-chloro-3-nitrotoluene-4-sulfonic acid is 1 ︰, 8 ︰ 1500.
The present invention chooses palladium-carbon catalyst (Pa/C) and participates in reaction, can recycle.The Pa/C catalyzer is not high to the purity requirement of raw material 6-chloro-3-nitrotoluene-4-sulfonic acid; Reaction process of the present invention is gentle, and reaction pressure is low, and temperature of reaction is low, and the material reaction process is easy to the control in the hydrogenating reduction process without solvent, and yield is up to 96.3%.
Embodiment
One, CLT acid industriallization reaction process:
5%Pa/C catalyzer, amine promotor, 6-chloro-3-nitrotoluene-4-sulfonic acid are dropped into reaction kettle according to mass ratio 1:8:1500.
Closed reactor goes out air with 0.3MPa nitrogen is twice replaced, go out nitrogen with the 0.5MPa hydrogen exchange again after, with the hydrogen pressurize of 0.8Mpa, confirm that reactor drum do not reveal.
After definite reactor drum is not revealed, open stirring, slowly be warmed up to 70～75 ℃; Open the hydrogen feed valve, adjust hydrogen pressure at 1.8～2.0Mpa, sustained reaction 3.5～4 hours; Temperature of reaction is controlled at 85～90 ℃, reacts not heat release and lowers the temperature naturally and be reaction end.
After reaction finishes, material is cooled to 30～40 ℃, through after the press filtration, through acid out, dry after, dry product, yield is up to 96.3%.
Two, product performance:
Outward appearance: white or blush pressed powder
Content: (total amino value): >=98.0
Moisture :≤1.0%
Ash content :≤1.0%
Dissolving situation in ammoniacal liquor: limpid be clear to almost limpid transparent.
Claims (2)
1. one kind is reduced 6-chloro-3-phenylmethylamine-4-sulfonic acid and produces the method for CLT acid; It is characterized in that: under oxygen free condition, Pa/C catalyzer, amine promotor, 6-chloro-3-nitrotoluene-4-sulfonic acid are dropped into reaction kettle, under the 0.8Mpa pressure condition, stir; And slowly be warmed up to 70～75 ℃; Feeding hydrogen, is to react 3.5～4 hours under the condition of 1.8～2.0Mpa at reacting kettle inner pressure, and temperature of reaction is controlled at 85～90 ℃; After reaction finishes, treat that material is cooled to 30～40 ℃ naturally after, blowing; Again through after the press filtration, acid out, drying, dry product.
2. ask reduction 6-chloro-3-phenylmethylamine-4-sulfonic acid to produce the method for CLT acid according to claim 1; The Pa content that it is characterized in that said Pa/C catalyzer is 5%; When feeding intake, the mass ratio of said Pa/C catalyzer, amine promotor and 6-chloro-3-nitrotoluene-4-sulfonic acid is 1 ︰, 8 ︰ 1500.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104390614A CN102408362A (en) | 2011-12-26 | 2011-12-26 | Method for producing CLT acid by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104390614A CN102408362A (en) | 2011-12-26 | 2011-12-26 | Method for producing CLT acid by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
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| CN102408362A true CN102408362A (en) | 2012-04-11 |
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| CN2011104390614A Pending CN102408362A (en) | 2011-12-26 | 2011-12-26 | Method for producing CLT acid by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675162A (en) * | 2012-05-09 | 2012-09-19 | 辽宁大学 | Method for synthesizing CLT acid |
| CN102702043A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase |
| CN102702042A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN104402774A (en) * | 2014-11-21 | 2015-03-11 | 浙江秦燕化工有限公司 | Method for preparing CLT acid through continuous catalytic hydrogenation reduction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54151945A (en) * | 1978-05-18 | 1979-11-29 | Hodogaya Chem Co Ltd | Preparation of 6-chloro-3-toluidine-4-sulfonic acid |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN101906057A (en) * | 2010-08-06 | 2010-12-08 | 延边大学 | Production of CLT acid by direct nitration of o-chlorotoluene |
-
2011
- 2011-12-26 CN CN2011104390614A patent/CN102408362A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54151945A (en) * | 1978-05-18 | 1979-11-29 | Hodogaya Chem Co Ltd | Preparation of 6-chloro-3-toluidine-4-sulfonic acid |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN101906057A (en) * | 2010-08-06 | 2010-12-08 | 延边大学 | Production of CLT acid by direct nitration of o-chlorotoluene |
Non-Patent Citations (4)
| Title |
|---|
| 《化工时刊》 20040131 贾志刚等 "液相催化加氢法制取芳胺的研究进展" 第2页, 1.1 1-2 第18卷, 第1期 * |
| 《化工科技》 19980331 白彦兵 "6-氯-3-硝基甲苯-4-磺酸液相加氢制备CLT酸的研究" 第35-39页 1-2 第6卷, 第3期 * |
| 白彦兵: ""6-氯-3-硝基甲苯-4-磺酸液相加氢制备CLT酸的研究"", 《化工科技》, vol. 6, no. 3, 31 March 1998 (1998-03-31), pages 35 - 39 * |
| 贾志刚等: ""液相催化加氢法制取芳胺的研究进展"", 《化工时刊》, vol. 18, no. 1, 31 January 2004 (2004-01-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675162A (en) * | 2012-05-09 | 2012-09-19 | 辽宁大学 | Method for synthesizing CLT acid |
| CN102675162B (en) * | 2012-05-09 | 2014-03-26 | 辽宁大学 | Method for synthesizing CLT acid |
| CN102702043A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase |
| CN102702042A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN102702042B (en) * | 2012-05-18 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN102702043B (en) * | 2012-05-18 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase |
| CN104402774A (en) * | 2014-11-21 | 2015-03-11 | 浙江秦燕化工有限公司 | Method for preparing CLT acid through continuous catalytic hydrogenation reduction |
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Application publication date: 20120411 |