CN1810779A - Catalytical hydrogenation process to produce II acid - Google Patents
Catalytical hydrogenation process to produce II acid Download PDFInfo
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- CN1810779A CN1810779A CN 200510062386 CN200510062386A CN1810779A CN 1810779 A CN1810779 A CN 1810779A CN 200510062386 CN200510062386 CN 200510062386 CN 200510062386 A CN200510062386 A CN 200510062386A CN 1810779 A CN1810779 A CN 1810779A
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Abstract
The present invention relates to catalytical hydrogenation process to produce H acid, and solves the technological problem of providing one new type of catalyst to lower the reaction pressure, reaction temperature and production cost effectively. The process includes the following steps: 1. regulating the nitroso value of nitro T acid and its solution as material to 15-45 g/L and the pH value to 7-10; 2. catalytical hydrogenation through adding the regulated solution and Ni-Co catalyst with Co content of 0.5-25 wt% and in the amount of 0.1-5 wt% of nitro T acid into high pressure reactor, introducing H2 of 1.0-4.5 Mpa pressure at 90-220 deg.c, and hydrogenating catalytically for 2-5 hr to obtain amino T acid and its solution; 3. alkali fusing; and 4. acid out to obtain the product.
Description
Technical field
The present invention relates to organic chemistry filed, specifically is a kind of Catalytical hydrogenation process to produce II acid.
Background technology
H acid (formula I) is the intermediate that is used to prepare water-soluble dye, use very extensive,
JP 50142546 discloses early stage production technique: three sulfonation that mainly contain (1) naphthalene of several steps obtain naphthalene 1,3, the 6-trisulfonic acid, (2) are with naphthalene 3,6, the 8-trisulfonic acid is nitrated, obtain nitro T acid (formula II), the neutralization of (3) alkali, (4) use iron powder reducing nitro T acid to obtain amino T acid (formula III), (6) the amino T acid of alkali fusion obtains H acid, and (5) acid out goes out H acid.DE 3020441 improves it, with in the ammoniacal liquor and replace the alkali neutralization, after the iron powder reducing, with sodium salt the ammonium salt of reduzate is replaced into sodium salt, through T acid sodium-salt segregation, obtains H acid through alkali fusion, acid out then.This is improved one's methods and can access high purity T acid, can also improve H acid productive rate, but aforesaid method has a large amount of ammonium salts to remove in T acid segregation, has increased operation steps and difficulty, and T acid segregation process produces a large amount of waste water.This method is the main method of present domestic production H acid.Czech patents CS 173326 uses in the lime carbonate after nitrated and itrated compound, removes by filter the calcium sulfate residue, behind the filtrate process iron powder reducing, and direct alkali fusion, segregation, the T acid mother liquor of having avoided T acid segregation technology and it to bring.
(formula II),
Because iron powder reducing technology can produce the iron mud that easily causes pollution, catalytic hydrogenation process cheap and cleaning also is widely studied.JP 49127956 public use Raney nickel are catalyzer, at 15-20kg/cm
2Under the pressure, 130 ℃ is amino T acid with nitro T acid hydro-reduction.JP 50101349 public use Pd-C are catalyzer, at 20kg/cm
2Under the pressure, 60-200 ℃ is amino T acid with nitro T acid hydro-reduction.DE 2747714 discloses and has used Raney nickel to be catalyzer, under 100-300bar pressure, and the mixture of 130～140 ℃ of catalytic hydrogenation nitro T acid isomer bodies, also result that can be good.
It is catalyzer with nickel respectively that GB 1576608 discloses, be catalyzer with platinum, under 150-300psig pressure, 90-130 ℃ is napthylamine sulfonic acid with the nitro-naphthalene-monosulfonic acid catalytic hydrogenation.
When using nickel as catalyzer, demanding pressure and temperature, catalytic capability is medium.Use Pd-C that catalytic capability is preferably arranged, but use the equipment requirements of catalyzer higher reclaiming.Platinum is a kind of excellent property catalyzer, but the cost costliness.
Summary of the invention
The technical issues that need to address of the present invention are, overcome disadvantages of background technology, provide a kind of new catalyzer that uses, with the Catalytical hydrogenation process to produce II acid of effective reduction reaction pressure, temperature and cost thereof.Specifically be by in nickel catalyzator, adding the performance that cocatalyst is promoted nickel catalyzator.
Shortening method of the present invention is produced H acid (referring to contain the Industrial products of H acid and salt thereof) technology, it is characterized in that comprising the steps:
1) raw material tone pitch: the nitrite number of nitro T acid and salts solution thereof is adjusted into 15～45g/L, and the pH value is adjusted into 7～10;
2) catalytic hydrogenation: in autoclave, adding solution behind the tone pitch and containing the cobalt amount is 0.5～25% nickel-cobalt catalyst, catalyst levels is with 0.1～5% of nitro T acid weight metering, again under 90～220 ℃ of temperature, feeding pressure is the hydrogen of 1.0～4.5Mpa, and the catalytic hydrogenation time is that 1～5hr gets amino T acid and salts solution thereof;
3) alkali fusion: be common process;
4) acid out: be common process, acid out gets H acid.
As preferably, the nitrite number of described itrated compound solution is 25～35g/L, and the pH value is 7.5～9.5; The parameter of catalytic hydrogenation: the cobalt amount that contains of nickel-cobalt catalyst is 1～20%, and catalyst levels is that temperature is 100～180 ℃ with 0.5～4% of nitro T acid weight metering, and pressure is 1.5～4.0MPa, and the catalytic hydrogenation time is 1.5～4hr.
This technology is amino T acid and salt thereof with nitro T acid and the direct catalytic hydrogenation of salt thereof under the nickel-cobalt catalyst effect, obtains finished product H acid later on through alkali fusion, acid out.The use of this catalyzer is comparatively easy, can put into autoclave simultaneously with particulate state and reactant, in 100～105 ℃ under the condition of 1.5～2.0MPa hydrogen pressure, carry out preliminary hydrogenation hydrogenation under the high-speed stirring, again in 120～180 ℃, pressure is under the condition of 2.0～4.0MPa hydrogen pressure that the hydrogenation catalyzed reaction is complete, and alkali fusion, acid out obtain H acid Industrial products later on then.
Catalyzer is granular nickel cobalt (alloy), and particle diameter 0.5～5mm can be obtained by the nickel cobalt (alloy) pulverizing.As preferably, can also contain weight and be 1～10% iron to reduce cost.
The process of this technology after catalytic hydrogenation adopts conventional alkali fusion, acid out technology, with reference to expired patent JP 50142546, CS 173326, DE 3020441.Wherein add solid sodium hydroxide and methyl alcohol alkali fusion the time.
The consumption that this technology adds catalyzer, sodium hydroxide, methyl alcohol is with nitro T acid weight metering, promptly obtain containing in the reaction mass weight (just the actual weight of nitro T acid and salt thereof in the reaction mass all is converted into and contains nitro T acid weight in the reaction mass) of nitro T acid according to analyzing and testing, wherein catalyst levels is 0.5～4% of a nitro T acid weight metering, sodium hydroxide concentration is for 50～100% of nitro T acid weight metering, and methanol usage is for 45～90% of nitro T acid weight metering.
Description of drawings
Fig. 1 is the technological process synoptic diagram that the present invention produces H acid.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Conventional process of the present invention is,
1) raw material tone pitch: the nitrite number of nitro T acid and salts solution thereof is adjusted into 25～35g/L, and the pH value is adjusted into 7.5～9.5;
2) catalytic hydrogenation: in autoclave, adding solution behind the tone pitch and containing the cobalt amount is 1～20% nickel-cobalt catalyst, catalyst levels is with 0.5～4% of nitro T acid weight metering, again under 100～180 ℃ of temperature, feeding pressure is the hydrogen of 1.5～4.0MPa, and the catalytic hydrogenation time is that 1.5～4hr gets amino T acid and salts solution thereof;
3) alkali fusion: concentrate amino T acid solution, the adjustment nitrite number is 35～45g/L, adds solid sodium hydroxide and methyl alcohol, and sodium hydroxide concentration is for 50～100% of nitro T acid weight metering, methanol usage is for 45～90% of nitro T acid weight metering, and reacting by heating gets the alkali fusion thing;
4) acid out: the alkali fusion thing is added in the mixing solutions of 2～3 times of alkali fusion thing weight, this mixed solution is mixed by the clear water of 1 times of weight of last acid out waste liquid and alkali fusion thing of 1～2 times of weight of alkali fusion thing and obtains, this mixed solution can also add the washing water of last H acid, drip sulfuric acid then to acidity 5～10, can obtain H acid by acid out.H acid acid out waste liquid can most of recycled in the acid out process.
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1:
With the amino value is that T acid of 25g/L nitro and salts solution adjusting pH thereof are 7.5, change in the autoclave, adding is 0.5% catalyzer with nitro T acid weight metering, this catalyzer is the compound nickel-cobalt catalyst that contains cobalt 20%, the elder generation high-speed stirring under under the hydrogen pressure of 1.0～2.0MPa 100～105 ℃ the reaction 2 hours, feed again hydrogen to pressure 2.5MPa in 120 ℃ of following further catalyzed reactions 2 hours, HPLC detects transformation efficiency＞95 of amino T acid then.
Embodiment 2～10 (the catalytic hydrogenation temperature among the following embodiment, time, reaction are meant the second step reaction, all 100～105 ℃ of reactions 2 hours under the hydrogen pressure of 1.0～2.0MPa of the first step hydrogenation bar):
| The embodiment sequence number | The amino value of nitro T acid solution (g/L) | The pH value | Catalyst levels | Cobalt contents in the catalyzer (%) | Iron level in the catalyzer (%) | Reaction times (hr) | Temperature of reaction (℃) | Reaction pressure (MPa) | Nitro T acid transformation efficiency (%) |
| 2 | 15 | 7.5 | 0.1 | 20 | 0 | 4 | 140 | 3.0 | ＞93 |
| 3 | 25 | 7 | 1 | 1 | 0 | 1 | 120 | 2.0 | ＞96 |
| 4 | 25 | 9 | 3 | 15 | 0 | 4 | 180 | 3.0 | ＞98 |
| 5 | 35 | 8 | 3 | 20 | 0 | 2 | 180 | 3.5 | ＞98.5 |
| 6 | 35 | 8.5 | 1 | 10 | 0 | 1.5 | 180 | 2.5 | ＞98 |
| 7 | 35 | 9 | 4 | 20 | 0 | 4 | 180 | 4.0 | ＞99 |
| 8 | 35 | 10 | 3 | 20 | 0 | 2 | 130 | 2.5 | ＞96.5 |
| 9 | 30 | 8.5 | 0.5 | 10 | 0 | 1.5 | 150 | 2.0 | ＞96 |
| 10 | 40 | 9 | 2.5 | 5 | 1 | 2 | 200 | 2.0 | ＞98.5 |
| 11 | 45 | 7.5 | 5 | 10 | 10 | 3 | 220 | 3.0 | ＞99 |
Embodiment 11
The nitro T acid HPLC content＞nitrite number of 98 solution is concentrated and is adjusted to 35g/L, add in the autoclave, adding solid sodium hydroxide is 50% of nitro T acid weight metering, and adding methyl alcohol is 45% of nitro T acid weight metering, 185 ℃ of alkali fusion 2hr promptly can obtain the alkali fusion thing.HPLC detects the alkali fusion transformation efficiency of amino T acid greater than 96%.
Embodiment 12
The nitro T acid HPLC content＞nitrite number of 98 solution is concentrated and is adjusted to 45g/L, add in the autoclave, adding solid sodium hydroxide is 100% of nitro T acid weight metering, and adding methyl alcohol is 90% of nitro T acid weight metering, 185 ℃ of alkali fusion 2hr promptly can obtain the alkali fusion thing.HPLC detects the alkali fusion transformation efficiency of amino T acid greater than 98.5%.
Embodiment 13
The alkali fusion thing that embodiment 11 is obtained adds in the clear water preparation mixed solution of the last H acid acid out mother liquor of its 1 times of weight and its 1 times of weight, the sulfuric acid of dropping 98%, regulate acidity and be about 5, acid out, filtration, promptly can obtain product H acid Industrial products, HPLC purity assay＞98.5%, this product are the mixture of H acid and salt thereof, and chemical analysis is converted into H acid content＞80%.
Embodiment 14
The alkali fusion thing that embodiment 12 is obtained adds in the clear water preparation mixed solution of the last H acid acid out mother liquor of its 2 times of weight and its 1 times of weight, the sulfuric acid of dropping 98%, regulate acidity and be about 10, acid out, filtration, promptly can obtain product H acid Industrial products, HPLC purity assay＞98%, this product are the mixture of H acid and salt thereof, and chemical analysis is converted into H acid content＞85%.
Claims (5)
1, a kind of Catalytical hydrogenation process to produce II acid is characterized in that comprising the steps:
1) raw material tone pitch: the nitrite number of nitro T acid and salts solution thereof is adjusted into 15～45g/L, and the pH value is adjusted into 7～10;
2) catalytic hydrogenation: in autoclave, adding solution behind the tone pitch and containing the cobalt amount is 0.5～25% nickel-cobalt catalyst, catalyst levels is with 0.1～5% of nitro T acid weight metering, again under 90～220 ℃ of temperature, feeding pressure is the hydrogen of 1.0～4.5Mpa, and the catalytic hydrogenation time is that 2～5hr gets amino T acid and salts solution thereof;
3) alkali fusion: be common process;
4) acid out: be common process, acid out gets the H acid product.
2, Catalytical hydrogenation process to produce II acid according to claim 1, the nitrite number that it is characterized in that described itrated compound solution is 25～35g/L, the pH value is 7.5～9.5; The parameter of catalytic hydrogenation: the cobalt amount that contains of nickel-cobalt catalyst is 1～20%, and catalyst levels is that temperature is 100～180 ℃ with 0.5～4% of nitro T acid weight metering, and pressure is 1.5～4.0MPa, and the catalytic hydrogenation time is 2.5～6hr.
3, Catalytical hydrogenation process to produce II acid according to claim 1 and 2 is characterized in that described
3) alkali fusion: concentrate amino T acid solution, the adjustment nitrite number is 35～45g/L, adds solid sodium hydroxide and methyl alcohol, and sodium hydroxide concentration is for 50～100% of nitro T acid weight metering, methanol usage is for 45～90% of nitro T acid weight metering, and reacting by heating gets the alkali fusion thing;
4) acid out: the alkali fusion thing is added in the mixing solutions of 2～3 times of alkali fusion thing weight, this mixed solution is mixed by the clear water of 1 times of weight of last acid out waste liquid and alkali fusion thing of 1～2 times of weight of alkali fusion thing and obtains, drip sulfuric acid then to acidity 5～10, can obtain H acid Industrial products by acid out; The washing water of H acid product once on perhaps in described mixed solution, adding.
4, Catalytical hydrogenation process to produce II acid according to claim 1 and 2 is characterized in that can also containing in institute's catalyzer weight and is 1～10% iron.
5, Catalytical hydrogenation process to produce II acid according to claim 3 is characterized in that can also containing in institute's catalyzer weight and is 1～10% iron.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739524A (en) * | 2014-01-10 | 2014-04-23 | 江苏明盛化工有限公司 | Preparation method for H acid monosodium salt |
| CN105268450A (en) * | 2015-05-25 | 2016-01-27 | 兰州洁源环保科技有限公司 | Method for synthesis of monosodium 8-amino-1-naphthol-3,6-disulfonate through hydrogenation catalysis and catalyst |
| CN105669500A (en) * | 2016-02-29 | 2016-06-15 | 江苏吉华化工有限公司 | Method adopting clean process for preparing H-acid |
| CN105753744A (en) * | 2016-02-29 | 2016-07-13 | 江苏吉华化工有限公司 | Energy-saving H-acid preparation device |
| CN106748901A (en) * | 2015-11-25 | 2017-05-31 | 江苏扬农化工集团有限公司 | A kind of alkali fusion and aftertreatment technology of H acid |
| CN109096155A (en) * | 2018-07-09 | 2018-12-28 | 山东垚石化工科技有限公司 | A kind of technique that H acid is produced by alkali fusion mother liquid recycling |
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2005
- 2005-12-31 CN CNB200510062386XA patent/CN100439328C/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739524A (en) * | 2014-01-10 | 2014-04-23 | 江苏明盛化工有限公司 | Preparation method for H acid monosodium salt |
| CN103739524B (en) * | 2014-01-10 | 2015-11-04 | 江苏明盛化工有限公司 | A kind of preparation method of H acid monosodium salt |
| CN105268450A (en) * | 2015-05-25 | 2016-01-27 | 兰州洁源环保科技有限公司 | Method for synthesis of monosodium 8-amino-1-naphthol-3,6-disulfonate through hydrogenation catalysis and catalyst |
| CN105268450B (en) * | 2015-05-25 | 2017-08-04 | 兰州洁源环保科技有限公司 | The catalyst that a kind of hydrogenation catalyst synthesizes the method for the disulfonate sodium of 8 amino, 1 naphthols 3,6 and its used |
| CN106748901A (en) * | 2015-11-25 | 2017-05-31 | 江苏扬农化工集团有限公司 | A kind of alkali fusion and aftertreatment technology of H acid |
| CN106748901B (en) * | 2015-11-25 | 2018-11-06 | 江苏扬农化工集团有限公司 | A kind of alkali fusion and aftertreatment technology of H acid |
| CN105669500A (en) * | 2016-02-29 | 2016-06-15 | 江苏吉华化工有限公司 | Method adopting clean process for preparing H-acid |
| CN105753744A (en) * | 2016-02-29 | 2016-07-13 | 江苏吉华化工有限公司 | Energy-saving H-acid preparation device |
| CN105753744B (en) * | 2016-02-29 | 2017-06-16 | 江苏吉华化工有限公司 | A kind of H acid preparation facilities with energy-saving effect |
| CN109096155A (en) * | 2018-07-09 | 2018-12-28 | 山东垚石化工科技有限公司 | A kind of technique that H acid is produced by alkali fusion mother liquid recycling |
| CN109096155B (en) * | 2018-07-09 | 2019-06-21 | 山东创蓝垚石环保技术有限公司 | A kind of technique that H acid is produced by alkali fusion mother liquid recycling |
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Owner name: JIANGSU JIHUA CHEMICAL CO., LTD. Free format text: FORMER OWNER: JIHUA CHEMICAL CO., LTD, HANGZHOU Effective date: 20100518 |
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