CN104592063B - A kind of environment-friendly production process of H acid - Google Patents

Abstract

The present invention relates to a kind of environment-friendly production process of H acid, refined naphthalene is after sulfonation, nitrated, the denitration that adds water, nitrobased NPK salt solid is obtained with alkali neutralization, filtration, nitrobased NPK salt produces amino T acid through acidifying again through shortening or iron powder reducing, filter the filtrate after nitrobased NPK through heat treated, neutralize with alkali, through shortening or iron powder reducing, reduced liquid acidifying after concentrated, filters and obtains amino T acid.Obtain amino T soda acid molten production H acid for twice, amino T-acid mother liquor and H acid mother liquor reclaim amino T acid respectively through complexometric extraction, alkali lye back extraction, acidifying and H sour, amino T acid after complexometric extraction and H acid mother liquor are after refining, COD drops to below 100ppm, produces potassium sulfate (or sodium sulfate) with MVR condensing crystal.This technique solves mother liquor in traditional technology and contains plurality of inorganic salt, inorganic mixing salt and large amount of organic and the difficult problem that cannot process.

Description

A kind of environment-friendly production process of H acid

Technical field

The present invention relates to fine-chemical intermediate to produce, particularly relate to a kind of H acid production process of cleanliness without any pollution, belong to technical field of fine.

Background technology

H acid [1-amino-8-naphthol-3.6-disulfonate sodium (or sylvite)] is the important intermediate of producing reactive dyestuffs, the lifting of H acid value lattice decides the lifting of reactive dyestuffs price, and the pollution problem in H acid production process is a great problem of puzzlement enterprise always.At present, it is take refined naphthalene as raw material that H acid is produced, and produce nitrobased NPK through sulfonation, nitrated, denitration, ammonia neutralization, iron powder reducing, the sodium-chlor operation such as to saltout, nitrobased NPK mother liquor contains a large amount of inorganic salt and the large amount of organic such as sulphur ammonium, sodium-chlor.At present, domestic to there is no a business processes up to standard, though have produce sulphur ammonium, sodium-chlor mixing salt through MVR is concentrated, because of should as fixed-end forces containing large amount of organic, H acid product generation solid waste per ton be at more than 7t.H acid annual production is at 6-8 ten thousand tons, and annual generation this solid waste more than 500,000 tons, has enterprise not add process, and directly outer row, causes environment and have a strong impact on, and therefore, a kind of production technique of H acid of clean environment firendly just seems urgent and important.

Summary of the invention

The object of the invention is to overcome above-mentioned deficiency, and a kind of environment-friendly production process of H acid is provided, pollution-free, cost is low.

The technical scheme that the present invention takes is:

An environment-friendly production process for H acid, comprises step as follows:

(1) neutralized by the reaction solution alkali of refined naphthalene after sulfonation, nitrated, denitration, stir 0.5-2 hour at 80 DEG C-100 DEG C, decrease temperature crystalline, isolates nitrobased NPK salt solid; Or add water nitrobased NPK salt all dissolved, filter and remove impurity, filtrate is for subsequent use;

(2) be dissolved in water by nitrobased NPK salt solid, obtain amino T acid through shortening or iron powder reducing, Filtration of catalyst or iron mud, acidifying, filtration, the filtrate be separated after amino T acid is for subsequent use; By the filtrate in step (1) at 130-180 DEG C of heating 3-5 hour, cooling, neutralize pH value 5-6, or filtrate neutralizes with alkali without heat treated, direct alkali; Obtain amino T acid through shortening or iron powder reducing, Filtration of catalyst or iron mud, acidifying, filtration, the filtrate be separated after amino T acid is for subsequent use.

(3) filtrate after being separated amino T acid extracts with complexing extractant, then reclaims amino T acid with alkali back extraction, and the filtrate after complexometric extraction is again through refining removing organism, and MVR condensing crystal reclaims inorganic salt;

(4) by molten for obtained for step (2) the amino T soda acid reclaimed with step (3), acid out, filter and to obtain H acid; The filtrate be separated after H acid solid reclaims H acid after complexometric extraction, and filtrate refining removing organism, MVR condensing crystal reclaims inorganic salt.

Alkali preferred mass concentration described in above-mentioned technique is the potassium hydroxide solution of 48%, or the sodium hydroxide solution of mass concentration 32%.

Step (1) neutralization reaction liquid alkali used is potassium hydroxide or sodium hydroxide.

Shortening described in step (2) is with the catalysis of 3wt% palladium carbon catalyst, is heated to 80 DEG C-120 DEG C reactions, the preferred 800-900:25 of mass ratio of nitrobased NPK salt solid and 3wt% palladium carbon catalyst.

Described iron powder reducing temperature is 95 DEG C-105 DEG C, and in 1-4 hours reaction times, the weight ratio of nitrobased NPK salt and reduced iron powder is 2-4:1.

Complexing extractant described in step (3) is N235 and 200# oil miscible solvent compound, its volume ratio N235:200# solvent oil=1:4.

Alkali fusion described in step (4) is that temperature controls at 180 DEG C-200 DEG C with 48% potassium hydroxide alkali fusion, alkali fusion 3-5 hour.

It is potassium hydroxide that step (4) amino T soda acid melts alkali used.

The present invention compared with prior art has following advantages: with nitrobased NPK reaction solution in being come by the amount controlling potassium hydroxide (or sodium), obtain nitrobased NPK salt solid, filtrate heating hydrolysis after nitrobased NPK salt will be filtered again, four sulfonated bodiess are made to be hydrolyzed to three sulphur things, thus improve yield and the purity of nitrobased NPK, owing to neutralizing with single alkali, a kind of inorganic salt are only had in reaction solution, can by amino to the filtrate channels and collaterals after product separation and extraction and recovery T acid and H sour, after reclaiming amino T acid and H acid, filtrate is through refine and reclaim inorganic salt, solve the difficulty that cannot be separated containing plurality of inorganic salt in filtrate in traditional technology, total recovery can improve 2%-10%, the more former technique of raw material has larger decline, reach processing wastewater zero release.

Embodiment

Following examples further illustrate of the present invention, but the present invention is not limited to this

The environment-friendly production process of embodiment 1 one kinds of H acid:

(1) refined naphthalene is through traditional technology sulfonation, nitrated, denitration, obtain nitrobased NPK reaction solution, get 1000 parts of (weight parts, down together) nitrobased NPK reaction solution adds 1200 parts of 48wt% potassium hydroxide, 80 DEG C of-100 DEG C of insulated and stirred 1 hour, cool to 30 DEG C, filter and obtain nitrobased NPK potassium solid 890 parts, filtrate 1310 parts.

(2) by 890 parts of nitrobased NPK potassium, 1400 parts of water, 3% palladium carbon catalyst 25 parts, is warmed up to 80 DEG C-120 DEG C, and hydrogenation, to terminal, is lowered the temperature, filtered, and sulfuric acid acidation, to pH=1-2, obtains amino T acid solid 560 parts, content 40%, purity 99%; Be separated the filtrate 1310 parts after nitrobased NPK potassium solid, 150 DEG C-160 DEG C insulations 4 hours, cooling, pH=5-6 are neutralized with 48wt% potassium hydroxide, add 15 parts of 3wt% palladium carbon catalysts, hydrogenating reduction at 80 DEG C of-120 DEG C of temperature, the filtrate after hydrogenating reduction, be concentrated to 2/3rds of original volume, sulfuric acid acidation is to PH=1-2, and cooling, filters and obtain amino T acid 76 parts, content 39.6%, purity 95.6%;

(3) filtrate after amino T acid is separated, complexing extractant (N235:20# solvent oil=1:4) 1500 parts extraction, extraction liquid is through 10% potassium hydroxide back extraction, strip liquor through sulfuric acid acidation to pH=1-2, filtration obtains amino T acid 81+31 part, content 38.5%, purity 97.5%.

(4) by above-mentioned amino T acid mixing, with 48wt% potassium hydroxide alkali fusion, temperature controls at 180 DEG C-200 DEG C, alkali fusion 3 hours, blowing, dilute with water, and acidifying obtains H acid, expansion drying, obtains H acid 192 parts, content 98.6%, purity 99.1%; The filtrate be separated after H acid can also obtain H acid 12 parts after complexometric extraction, back extraction, acidifying, purity 97.4%; After product separation, filtrate merges, and through Fenton oxidation, potassium permanganate oxidation process, obtains colourless transparent liquid, and condensing crystal obtains potassium sulfate.

The environment-friendly production process of embodiment 2 one kinds of H acid:

(1) refined naphthalene is through traditional technology sulfonation, nitrated, denitration, obtains nitrobased NPK reaction solution; Get 1000 parts of nitrobased NPK reaction solutions, add the potassium hydroxide of 1000 part 30%, 80 DEG C of-100 DEG C of insulated and stirred 1 hour, drop to 30 DEG C, filter, obtain nitrobased NPK sodium (potassium) solid 760 parts, filtrate 1240 parts.(2), (3), (4) step repeat corresponding operating in embodiment 1, finally obtains H acid 176 parts, content 98.3%, purity 98.7%;

Filtrate after product separation merges, and through Fenton oxidation, potassium permanganate oxidation process obtains colourless transparent liquid, and condensing crystal reclaims anhydrous sodium sulphate.

Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.

Claims (7)

1. an environment-friendly production process for H acid, is characterized in that, comprises step as follows:

(1) neutralized by the reaction solution alkali of refined naphthalene after sulfonation, nitrated, denitration, stir 0.5-2 hour at 80 DEG C-100 DEG C, decrease temperature crystalline, isolates nitrobased NPK salt solid; Or add water nitrobased NPK salt all dissolved, filter and remove impurity, filtrate is for subsequent use;

(2) be dissolved in water by nitrobased NPK salt solid, obtain amino T acid through shortening or iron powder reducing, Filtration of catalyst or iron mud, acidifying, filtration, the filtrate be separated after amino T acid is for subsequent use; By the filtrate in step (1) at 130-180 DEG C of heating 3-5 hour, cooling, neutralize pH value 5-6, or filtrate neutralizes with alkali without heat treated, direct alkali; Obtain amino T acid through shortening or iron powder reducing, Filtration of catalyst or iron mud, acidifying, filtration, the filtrate be separated after amino T acid is for subsequent use;

(3) filtrate after being separated amino T acid extracts with complexing extractant, then reclaims amino T acid with alkali back extraction, and the filtrate after complexometric extraction is again through refining removing organism, and MVR condensing crystal reclaims inorganic salt;

(4) by molten for obtained for step (2) the amino T soda acid reclaimed with step (3), acid out, filter and to obtain H acid; The filtrate be separated after H acid solid reclaims H acid after complexometric extraction, and filtrate refining removing organism, MVR condensing crystal reclaims inorganic salt.

2. the environment-friendly production process of a kind of H acid according to claim 1, is characterized in that, step (1) neutralization reaction liquid alkali used is potassium hydroxide or sodium hydroxide.

3. the environment-friendly production process of a kind of H acid according to claim 1, is characterized in that, the shortening described in step (2) is with the catalysis of 3wt% palladium carbon catalyst, is heated to 80 DEG C-120 DEG C reactions.

4. the environment-friendly production process of a kind of H acid according to claim 3, is characterized in that, the mass ratio of step (2) nitrobased NPK salt solid and 3wt% palladium carbon catalyst selects 800-900:25.

5. the environment-friendly production process of a kind of H acid according to claim 1, is characterized in that, described nitrobased NPK salt and the weight ratio of reduced iron powder are 2-4:1.

6. the environment-friendly production process of a kind of H acid according to claim 1, is characterized in that, the complexing extractant described in step (3) is N235 and 200# oil miscible solvent compound, its volume ratio N235:200# solvent oil=1:4.

7. the environment-friendly production process of a kind of H acid according to claim 1, is characterized in that, it is potassium hydroxide that step (4) amino T soda acid melts alkali used.