CN108129361A - H acid monosodium salt continuously hydrogen adding reducing process - Google Patents
H acid monosodium salt continuously hydrogen adding reducing process Download PDFInfo
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- CN108129361A CN108129361A CN201711265614.2A CN201711265614A CN108129361A CN 108129361 A CN108129361 A CN 108129361A CN 201711265614 A CN201711265614 A CN 201711265614A CN 108129361 A CN108129361 A CN 108129361A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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Abstract
The present invention provides a kind of H acid continuously hydrogen adding reducing process, and in particular to H acid monosodium salt production technical field comprises the technical steps that：S1, in reduction reaction kettle sequentially adds and 8 nitro of material, 1,3,6 naphthalene trisulfonic acid ammonium salt and molecular sieve catalyst, be stirred, then be passed through hydrogen, controlling reaction temperature and reaction pressure, lower charging, top discharge；S2, reaction mass is passed through into top discharge mouth automatic overflow, automatic precipitation filtering is carried out in into filter device, molecular sieve catalyst and 1 amino 3 of product are obtained after filtering, 6,8 naphthalene trisulfonic acid ammonium salts, molecular sieve catalyst reenters reaction solution use, and reduzate pump is delivered to next reaction member.The advantages of present invention, which has, shortens the reaction time, improves yield, and economic and environment-friendly, equipment investment is few, suitable industrialized production.
Description
Technical field
The invention belongs to H acid monosodium salt production technical fields, and in particular to a kind of H acid monosodium salt continuously hydrogen adding restores work
Skill.
Background technology
H acid monosodium salt, entitled 1- amino-8-naphthols -3, the 6- disulfonate sodium of Chinese, general one crystallization water of band are
A kind of important dyestuff intermediate.H acid monosodium salt is such as available mainly for the production of acid dyes, direct dyes or reactive dye
In production acid fuchsin 6b, acid red G, directly Acid Black 10B, black, Reactive Brilliant Red K-2BP, active purple k-3r, reactive dark blue
K-R etc. more than 90 plants dyestuff, these dyestuffs are used for wool spinning, and the dyeing of cotton fabric has good effect；In addition, H acid monosodium salt is also
Available for producing drug.At present, H acid monosodium salt is mainly produced as follows：(1) naphthalene sulfonation obtains 1,3,6- naphthalene sulphurs
Acid；(2) 1,3,6- naphthalene trisulfonic acids nitrification generation 1- nitros -3,6,8- naphthalene trisulfonic acids, and nitrating mixture is made to take off nitrogen dioxide；
(3) nitrating mixture is neutralized with ammonium hydroxide：(4) three ammonium salt of neutralized reaction product nitro naphthalene trisulfonic acid restores, and is precipitated also with sulfuric acid and salt
Former acidizing product amino T acid；(5) amino T acid is transformed into sodium salt, alkali fusion, acid out obtain H acid monosodium salt.Existing reduction work
Skill is 1,3,6- naphthalene trisulfonic acid ammonium salt of 8- nitros and hydrazine hydrate, and the reaction time is usually longer, and yield is relatively low, and reaction process is fierce,
Security risk is larger.
A kind of preparation method (the application number of H acid monosodium salt of patent：201410012300.1) disclose a kind of H acid monosodium salt
Preparation method, include the following steps：(1) in the presence of the heteropoly acid of catalytic amount, with sulfuric acid one sulfonating reaction occurs for refined naphthalene
A sulfonated products are obtained, sulfur trioxide is then added in and carries out secondary sulfonating reaction, sulfonation material is obtained after the reaction was complete；(2) will
Sulfonation material carries out nitration reaction with nitric acid and obtains nitrification material；(3) in the presence of hydrogenation catalyst, nitrification material occurs to add
Hydrogen reduction reaction obtains amino T acid；(4) methanol and sodium hydroxide are added in into amino T acid, alkali fusion object is obtained by the reaction in heating；(5)
Alkali fusion object is adjusted into pH value to 3~6, carries out acid out, the isolated H acid monosodium salt.The hydrogenation reduction of the invention
For the continuous reduction reaction of tubular type, also there are great problems at present：Reaction pressure is excessively high, can cause equipment deformation of being heated during reaction,
Cause poor sealing, easily reveal；Pipe reaction process is uncontrollable, causes material terminal point control difficult, causes material reaction
Not exclusively, product yield is substantially reduced, while influences product quality；Equipment investment is larger, a set of production system input nearly hundred million
Member causes the raisings such as later maintenance cost.
Therefore, it is badly in need of a kind of shortening reaction time, improves yield, equipment investment is few, is suitble to the single sodium of H acid of industrialized production
Salt continuously hydrogen adding reducing process.
Invention content
It is longer the purpose of the present invention is being directed to the existing H acid monosodium salt preparation process reaction time, it the problems such as yield is relatively low, carries
For a kind of H acid monosodium salt continuously hydrogen adding reducing process, have and shorten the reaction time, improve yield, equipment investment is few, is suitble to industry
The advantages of metaplasia is produced.
The present invention provides following technical solutions：
A kind of H acid monosodium salt continuously hydrogen adding reducing process, comprises the technical steps that：
S1, in reduction reaction kettle sequentially adds and material 8- nitros -1,3,6- naphthalene trisulfonic acids ammonium salt and molecular sieve catalytic
Agent is stirred, then is passed through hydrogen, controlling reaction temperature and reaction pressure, lower charging, top discharge；
S2, by reaction mass by top discharge mouth automatic overflow, into filter device in carry out automatic precipitation filtering, filtering
After obtain molecular sieve catalyst and product 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts, molecular sieve catalyst reenters reaction solution
It uses, reduzate pump is delivered to next reaction member.
The step S1 uses lower charging, and it is rambunctious to overcome the pipe reaction residence time for the mode of operation of top discharge
Shortcoming selects molecular sieve catalyst, shortens the reaction time.Molecular sieve catalyst can be filtered and used by the step S2, molecule
Sieve catalyst can be used for multiple times again after filtering, simplify process, save cost.
Preferably, 1,3,6- naphthalene trisulfonic acid ammonium salt of 8- nitros and hydrogen molar ratio are 1 in the step S1:1.21~
1.25。
Preferably, the mass ratio that molecular sieve catalyst accounts for 1,3,6- naphthalene trisulfonic acid ammonium salt of 8- nitros in the step S1 is
5 ‰~8 ‰.
Preferably, the step S1 reaction temperatures are 140~160 DEG C, and reaction pressure is 2.8~3.5Mpa.
Preferably, the step S1 is continuous operation, by charging rate come control material reaction time, it can be ensured that
The reaction was complete.
The 1- amino -3,6 measured according to the reaction condition, the yield of 8- naphthalene trisulfonic acid ammonium salts is 98~99%, the invention
Improve the yield of hydrogenation reaction product.
The beneficial effects of the invention are as follows：
1st, molecular sieve catalyst is selected, shortens the reaction time.
2nd, molecular sieve catalyst can be used for multiple times again after filtering, simplify process, save cost.
3rd, there are high-speed stirring apparatus and the distribution of chip shelves flow heat dissipation device in reduction reaction kettle, improve reaction rate.
4th, by charging rate come control material reaction time, it can be ensured that the reaction was complete.
Specific embodiment
Embodiment 1
A kind of H acid monosodium salt continuously hydrogen adding reducing process, comprises the technical steps that：
S1, in reduction reaction kettle sequentially adds and material 8- nitros -1,3,6- naphthalene trisulfonic acids ammonium salt and molecular sieve catalytic
Agent, molecular sieve catalyst account for the mass ratio 5 ‰ of 1,3,6- naphthalene trisulfonic acid ammonium salt of 8- nitros, are stirred, then be passed through hydrogen, 8- nitre
Base 1,3,6- naphthalene trisulfonic acids ammonium salt and hydrogen molar ratio are 1:1.21, at 140 DEG C, reaction pressure exists controlling reaction temperature
3.1Mpa, lower charging, top discharge, using continuous operation；
S2, by reaction mass by top discharge mouth automatic overflow, into filter device in carry out automatic precipitation filtering, filtering
After obtain molecular sieve catalyst and product 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts, molecular sieve catalyst reenters reaction solution
It uses, reduzate pump is delivered to next reaction member.
The final yield for measuring 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts is 98.2%.
Embodiment 2
A kind of H acid monosodium salt continuously hydrogen adding reducing process, comprises the technical steps that：
S1, in reduction reaction kettle sequentially adds and material 8- nitros -1,3,6- naphthalene trisulfonic acids ammonium salt and molecular sieve catalytic
Agent, molecular sieve catalyst account for the mass ratio 6 ‰ of 1,3,6- naphthalene trisulfonic acid ammonium salt of 8- nitros, are stirred, then be passed through hydrogen, 8- nitre
Base 1,3,6- naphthalene trisulfonic acids ammonium salt and hydrogen molar ratio are 1:1.23, at 145 DEG C, reaction pressure exists controlling reaction temperature
3.2Mpa, lower charging, top discharge, using continuous operation；
S2, by reaction mass by top discharge mouth automatic overflow, into filter device in carry out automatic precipitation filtering, filtering
After obtain molecular sieve catalyst and product 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts, molecular sieve catalyst reenters reaction solution
It uses, reduzate pump is delivered to next reaction member.
The final yield for measuring 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts is 98.6%.
Embodiment 3
A kind of H acid monosodium salt continuously hydrogen adding reducing process, comprises the technical steps that：
S1, in reduction reaction kettle sequentially adds and material 8- nitros -1,3,6- naphthalene trisulfonic acids ammonium salt and molecular sieve catalytic
Agent, molecular sieve catalyst account for the mass ratio 7 ‰ of 1,3,6- naphthalene trisulfonic acid ammonium salt of 8- nitros, are stirred, then be passed through hydrogen, 8- nitre
Base 1,3,6- naphthalene trisulfonic acids ammonium salt and hydrogen molar ratio are 1:1.24, at 155 DEG C, reaction pressure exists controlling reaction temperature
3.4Mpa, lower charging, top discharge, using continuous operation；
S2, by reaction mass by top discharge mouth automatic overflow, into filter device in carry out automatic precipitation filtering, filtering
After obtain molecular sieve catalyst and product 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts, molecular sieve catalyst reenters reaction solution
It uses, reduzate pump is delivered to next reaction member.
The final yield for measuring 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts is 98.8%.
Embodiment 4
A kind of H acid monosodium salt continuously hydrogen adding reducing process, comprises the technical steps that：
S1, in reduction reaction kettle sequentially adds and material 8- nitros -1,3,6- naphthalene trisulfonic acids ammonium salt and molecular sieve catalytic
Agent, molecular sieve catalyst account for the mass ratio 8 ‰ of 1,3,6- naphthalene trisulfonic acid ammonium salt of 8- nitros, are stirred, then be passed through hydrogen, 8- nitre
Base 1,3,6- naphthalene trisulfonic acids ammonium salt and hydrogen molar ratio are 1:1.25, at 160 DEG C, reaction pressure exists controlling reaction temperature
3.5Mpa, lower charging, top discharge, using continuous operation；
S2, by reaction mass by top discharge mouth automatic overflow, into filter device in carry out automatic precipitation filtering, filtering
After obtain molecular sieve catalyst and product 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts, molecular sieve catalyst reenters reaction solution
It uses, reduzate pump is delivered to next reaction member.
The final yield for measuring 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts is 99%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality
Example is applied the present invention is described in detail, it for those skilled in the art, still can be to aforementioned each implementation
Technical solution recorded in example modifies or carries out equivalent replacement to which part technical characteristic.All essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (5)
1.H acid mono-sodium salt continuously hydrogen adding reducing process, which is characterized in that comprise the technical steps that：
S1, in reduction reaction kettle sequentially adds and material 8- nitros -1,3,6- naphthalene trisulfonic acids ammonium salt and molecular sieve catalyst, into
Row stirring, then hydrogen is passed through, controlling reaction temperature and reaction pressure, lower charging, top discharge；
S2, by reaction mass by top discharge mouth automatic overflow, into filter device in carry out automatic precipitation filtering, after filtering
To molecular sieve catalyst and product 1- amino -3,6,8- naphthalene trisulfonic acid ammonium salts, molecular sieve catalyst reenters reaction solution use,
Reduzate pump is delivered to next reaction member.
2. H acid monosodium salt continuously hydrogen adding reducing process according to claim 1, which is characterized in that 8- in the step S1
Nitro 1,3,6- naphthalene trisulfonic acids ammonium salt and hydrogen molar ratio are 1:1.21~1.25.
3. H acid monosodium salt continuously hydrogen adding reducing process according to claim 1, which is characterized in that divide in the step S1
The mass ratio that sub- sieve catalyst accounts for 8- nitro 1,3,6- naphthalene trisulfonic acid ammonium salts is 5 ‰~8 ‰.
4. H acid monosodium salt continuously hydrogen adding reducing process according to claim 1, which is characterized in that the step S1 reactions
Temperature is 140~160 DEG C, and reaction pressure is 2.8~3.5Mpa.
5. H acid monosodium salt continuously hydrogen adding reducing process according to claim 1, which is characterized in that the step S1 is connects
Continuous operation.
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| CN201711265614.2A CN108129361A (en) | 2017-12-05 | 2017-12-05 | H acid monosodium salt continuously hydrogen adding reducing process |
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| CN201711265614.2A CN108129361A (en) | 2017-12-05 | 2017-12-05 | H acid monosodium salt continuously hydrogen adding reducing process |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002691A1 (en) * | 1977-12-22 | 1979-07-11 | Bayer Ag | Process for the preparation of 1-amino-naphthaline-3,6,8-trisulfonic acid |
| CN101367753A (en) * | 2008-10-15 | 2009-02-18 | 湖北楚源高新科技股份有限公司 | Novel continuous nitrification denitrating, abstraction, hydrogenation reduction production process for H acid |
| CN101381331A (en) * | 2008-10-27 | 2009-03-11 | 泰兴锦汇化工有限公司 | Method for preparing color-forming intermediate H acids |
| CN103113269A (en) * | 2013-01-23 | 2013-05-22 | 绍兴奇彩化工有限公司 | 1,8-dinitro-3,6-naphthalene disulfonate hydrogenation reduction method |
| CN105665003A (en) * | 2015-11-30 | 2016-06-15 | 浙江科技学院 | Hierarchical pore molecular sieve catalyst and preparation method thereof |
-
2017
- 2017-12-05 CN CN201711265614.2A patent/CN108129361A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002691A1 (en) * | 1977-12-22 | 1979-07-11 | Bayer Ag | Process for the preparation of 1-amino-naphthaline-3,6,8-trisulfonic acid |
| CN101367753A (en) * | 2008-10-15 | 2009-02-18 | 湖北楚源高新科技股份有限公司 | Novel continuous nitrification denitrating, abstraction, hydrogenation reduction production process for H acid |
| CN101381331A (en) * | 2008-10-27 | 2009-03-11 | 泰兴锦汇化工有限公司 | Method for preparing color-forming intermediate H acids |
| CN103113269A (en) * | 2013-01-23 | 2013-05-22 | 绍兴奇彩化工有限公司 | 1,8-dinitro-3,6-naphthalene disulfonate hydrogenation reduction method |
| CN105665003A (en) * | 2015-11-30 | 2016-06-15 | 浙江科技学院 | Hierarchical pore molecular sieve catalyst and preparation method thereof |
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