CN118439978B - Process for producing H acid by recycling T acid mother liquor - Google Patents
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- 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 76
- 239000012452 mother liquor Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 10
- 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 title claims abstract 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000003513 alkali Substances 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 54
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 49
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 49
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 37
- 230000009615 deamination Effects 0.000 claims abstract description 31
- 238000006481 deamination reaction Methods 0.000 claims abstract description 31
- 230000004927 fusion Effects 0.000 claims abstract description 30
- 239000002585 base Substances 0.000 claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 amino T acid Chemical compound 0.000 claims abstract description 27
- 238000010521 absorption reaction Methods 0.000 claims abstract description 24
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 18
- 239000010413 mother solution Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000006396 nitration reaction Methods 0.000 claims abstract description 11
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000011946 reduction process Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000012768 molten material Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 33
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000003472 neutralizing effect Effects 0.000 description 9
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of H acid preparation, and particularly relates to a process for producing H acid by recycling T acid mother liquor. The process comprises the following steps: s1, separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate; s2, adding alkali and methanol into amino T acid to perform alkali fusion to obtain T acid alkali fusion, heating the T acid alkali fusion, adding T acid mother liquor to perform deamination to obtain alkali fusion neutralization solution, and performing a reduction process of the step S1 by using the denitration solution obtained in the step S1 as ammonia absorption solution during deamination; and S3, acidizing, desulfurizing, cooling and filtering the alkali melt neutralization solution to obtain a filter cake, and washing, filter pressing and drying the filter cake to obtain the H acid. The invention overcomes the defect that sulfite and sulfate remain after H acid-base fusion mother liquor is neutralized with denitration liquid, the ammonia recycling rate can reach 95%, the ammonia consumption is greatly reduced, and the T acid mother liquor is not required to be treated.
Description
Technical Field
The invention belongs to the technical field of H acid preparation, and particularly relates to a process for producing H acid by recycling T acid mother liquor.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
H acid (1-amino-8-naphthol-3, 6-disulfonic acid monosodium salt) is an important intermediate for producing reactive dyes. At present, refined naphthalene is used as a raw material for producing H acid, amino T acid is prepared through the procedures of sulfonation, nitration, denitration, neutralization, reduction, sodium chloride salting out and the like, and then the amino T acid is produced through the procedures of alkali fusion, acidification and the like. However, the mother liquor produced in the process of producing H acid belongs to 'five-high' organic wastewater with high concentration, high acidity, high salinity, high chromaticity and high toxicity, the chemical oxygen demand (Chemical Oxygen Demand-COD) is as high as 8-10 ten thousand, the salinity is as high as 10-20%, the chromaticity is as high as 4000-6000 times, and the 'five-high' organic wastewater is difficult to treat effectively by adopting the traditional biochemical and physicochemical methods; the pretreatment cost is up to thousands yuan by adopting the unconventional extraction, pyrolysis, adsorption and other methods, and the thorough and effective treatment cannot be realized. Although some waste water can be concentrated by MVR to produce mixed salt of ammonium sulfate and sodium chloride, the mixed salt contains a large amount of organic matters, is difficult to purify and can only be treated as solid waste.
In the prior art (patent number ZL201811067656. X), H acid-base fusion mother liquor is used for neutralizing and denitrating reaction liquid, so that ammonia water required for neutralization is saved, the production amount of high-salt wastewater is reduced, inorganic salt in the mother liquor is changed into single salt from mixed salt, and the treatment difficulty and cost of waste liquid are reduced. However, the H acid alkali fusion mother solution contains sodium sulfate and sodium sulfite which cannot be completely removed, the activity of sodium sulfate electrolyte is inferior to that of ammonium sulfate, the reaction speed of iron powder reduction in the neutralized reaction solution is slower, and trace sodium sulfite remained during hydrogenation reduction is easy to cause nickel catalyst poisoning.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a process for producing H acid by recycling T acid mother liquor. The invention uses the T acid mother liquor containing ammonium sulfate to neutralize the alkali melt of amino T acid, and simultaneously uses the denitration liquid as the deamination agent to absorb ammonia gas and neutralize the denitration, thereby overcoming the negative influence of residual sulfite and sulfate after the H acid-base melt mother liquor is neutralized with the denitration liquid, and reducing the ammonia consumption in the preparation process.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, a process for producing H acid by recycling a T acid mother liquor includes the steps of:
S1, separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate;
S2, adding alkali and methanol into amino T acid to perform alkali fusion to obtain T acid alkali fusion, heating the T acid alkali fusion, adding T acid mother liquor to perform deamination to obtain alkali fusion neutralization solution, using the denitration solution obtained in the step S1 as ammonia absorption solution during deamination, and performing the reduction process of the step S1 on the denitration solution after deamination;
and S3, acidizing, desulfurizing, cooling and filtering the alkali melt neutralization solution to obtain a filter cake, and washing, filter pressing and drying the filter cake to obtain the H acid.
In the process, in the process of the invention, since denitration, neutralization and reduction are needed in the process of producing H acid for the first time, amino T acid and a T acid mother solution containing ammonium sulfate are obtained, denitration liquid generated in the following process is neutralized in the process of taking the denitration liquid as ammonia absorption liquid to carry out deamination to obtain alkali melt neutralization liquid, and the denitration liquid with ammonia absorption neutralized after deamination is reduced to obtain the amino T acid and the T acid mother solution containing ammonium sulfate. And ammonia generated by neutralizing and deaminizing the T acid mother liquor and the alkali melt is used for neutralizing the denitration liquid, and the denitration liquid after the neutralization of the T acid mother liquor is reduced, acidified and filtered to obtain the T acid mother liquor, so that the recycling of the T acid mother liquor is realized.
Preferably, in step S1, the neutralization step is performed using ammonia water when the T-acid mother liquor is obtained for the first time. The first production of H acid requires neutralization and deamination, and ammonia water reacts with sulfuric acid in the denitration liquid in the neutralization process to generate ammonium sulfate, so that a T acid mother liquor containing ammonium sulfate is obtained. In the production process of the subsequent batch, the denitration liquid absorbs ammonia to neutralize in the deamination process, and the neutralization reaction is not required to be carried out independently, so that the ammonia water required by neutralizing the denitration liquid is saved.
Preferably, the mass concentration of the ammonium sulfate in the T acid mother liquor is 10% -40%. The concentration of ammonium sulfate can be adjusted by adding ammonium sulfate into the T acid mother liquor or diluting the T acid mother liquor according to the requirement.
Preferably, in step S2, the mass ratio of the unreacted alkali in the T acid-alkali molten material to the ammonium sulfate in the T acid mother liquor is 1: (1.4-1.8). Since ammonia is a weak base, in order to ensure that unreacted alkali is totally neutralized by ammonium sulfate into ammonia and sulfate, it is necessary to ensure that the ammonium sulfate excessively promotes the neutralization reaction to proceed forward relative to the alkali.
Preferably, in step S2, the base includes sodium hydroxide or potassium hydroxide.
Preferably, in step S2, the T-shaped acid-base melting material is heated to 80-90 ℃.
Preferably, in the step S2, the deamination time is 1-3 hours, and the mass fraction of ammonium sulfate in the alkali melt neutralization solution obtained by deamination is less than 0.5%.
Preferably, in the step S2, the pH of the denitration liquid is adjusted to 4 to 5 after deamination. The pH is adjusted to ensure efficient progress of the neutralization reaction.
Preferably, in step S3, dilute sulfuric acid is used to acidify to ph=2.
Preferably, in step S3, the sulfur dioxide removed is absorbed using a base during desulfurization. The alkali absorbing sulfur dioxide can be used for producing sulfite, so that the sulfur dioxide can be prevented from polluting and byproducts with utilization value can be produced.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
According to the invention, the ammonia neutralization and denitration liquid generated by neutralizing the T acid mother liquid with the T acid and the alkali molten material is used, the neutralized denitration liquid is further reduced to produce amino T acid and generate the T acid mother liquid, ammonia in the T acid mother liquid and the T acid mother liquid can be recycled in the continuous production of H acid, the reduction rate of the ammonia consumption of the whole process can reach more than 90%, the treatment capacity of the alkali molten mother liquid is reduced, and the production cost of the product is effectively reduced.
The ammonia generated in the process of neutralizing and deaminizing the alkaline molten material is used for neutralizing the denitration liquid, so that sulfite and sulfate which are directly added in the process of neutralizing the denitration liquid or generated after the neutralization of the alkaline are avoided, the adverse influence of sulfite and sulfate on the subsequent reduction reaction is avoided, the production efficiency of amino T acid is improved, and the overall efficiency of the process is improved.
The process has the advantages of atom economy and environmental protection, nitrogen element is recycled in the recycling process of the T acid mother liquor, and introduced sulfur element is absorbed by alkali in the desulfurization process to prepare sulfite with economic value, so that the nitrogen and sulfur element is prevented from being discharged in the forms of ammonia, sulfur oxide and the like to become pollutants.
Detailed Description
As described in the background art, in the prior art, although the sulfite-containing H acid-base fusion mother liquor is used for neutralizing and denitrating the reaction liquid, the amount of high-salt wastewater generated is reduced while the alkaline neutralizer required to be used in the neutralization is saved, but the efficiency of reducing and generating amino T acid is affected by sodium sulfate and sodium sulfite which cannot be completely removed in the H acid-base fusion mother liquor.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
In the examples, neutralization is required to be performed to obtain a mother solution of T acid and an amino T acid in addition to the first production of H acid, and the denitration solution in the subsequent production lot can be neutralized when it is used as an ammonia absorption solution, without performing a separate neutralization step. The sulfonation, nitration, denitration, neutralization and reduction processes of refined naphthalene are not specifically described with reference to the prior art. The parts in the examples are parts by weight and the percentages are percentages by weight.
Example 1
And (3) separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate. The amino T acid was alkali melted using sodium hydroxide and methanol to obtain a 12.11% alkali melt. 1000 parts of an alkali melt was taken, and the H acid content thereof was measured to be 16.379%, and the residual alkali content (calculated as sodium hydroxide) was 12.11%. 1000 parts of T acid mother liquor is taken, and the ammonium sulfate content is 19.6%. 600 parts of denitration liquid is taken, 200 parts of water is added for dilution, 800 parts of diluted denitration liquid is obtained, and the acidity is 36.2 percent calculated by sulfuric acid.
Heating the T acid-alkali molten material to 80 ℃, gradually adding the T acid mother liquor into 0.5 h, and using the diluted denitration liquid as ammonia absorption liquid for negative pressure deamination 2h to obtain alkali-solution neutralization solution with ammonium sulfate content less than 0.5%. After deamination, the weight of the diluted denitration liquid after ammonia absorption is 918 parts, the acidity is 15.86% calculated by sulfuric acid, the ammonium sulfate content is 20.439%, and the ammonia recovery rate is 95.69%.
Acidifying the alkali fusion neutralization solution to pH=2 by using 30% dilute sulfuric acid, desulfurizing, absorbing the separated sulfur oxide by using sodium hydroxide to produce sodium sulfite, cooling and filtering the desulfurized alkali fusion neutralization solution to obtain a filter cake, washing the filter cake with water, press-filtering, drying to produce 128 parts of H acid finished product, wherein the H acid content is 85.2%, and the chromatographic purity is 98.76%.
Example 2
And (3) separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate. And (3) acid-base melting the amino T by using sodium hydroxide and methanol to obtain the T acid-base melting material. 1000 parts of T acid-base melting stock is taken, the H acid content is 16.37 percent, and the residual alkali content is 12.11 percent (calculated by sodium hydroxide). 800 parts of T acid mother liquor (ammonium sulfate content 24.46%) was taken. 900 parts of the diluted denitration liquid after ammonia absorption in example 1 was taken.
Heating the T acid alkali molten material to 80 ℃, gradually adding the T acid mother liquor into 0.5 h, and taking the diluted denitration liquid after ammonia absorption in example 1 as ammonia absorption liquid for negative pressure deamination 2 h to obtain alkali molten neutralization liquid with ammonium sulfate content less than 0.5%. After deamination is finished, 1146 parts of denitration liquid is diluted, the pH value is 4-5, the ammonium sulfate content is 16.76%, and the ammonia recovery rate is 98.2%.
And reducing the diluted denitration liquid after ammonia absorption, and further separating to obtain amino T acid and a T acid mother solution containing ammonium sulfate.
Acidifying the alkali fusion neutralization solution to pH=2 by using 30% dilute sulfuric acid, desulfurizing, absorbing the separated sulfur oxide by using sodium hydroxide to produce sodium sulfite, cooling and filtering the desulfurized alkali fusion neutralization solution to obtain a filter cake, washing the filter cake with water, press-filtering, drying to produce 132 parts of H acid finished product, wherein the H acid content is 85.62%, and the chromatographic purity is 98.86%.
Example 3
And (3) separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate. And (3) acid-base melting the amino T by using sodium hydroxide and methanol to obtain the T acid-base melting material. 1200 parts of T acid-base melt is taken, the H acid content of which is 15.8 percent and the residual alkali content (calculated by sodium hydroxide) of which is 13.6 percent are measured. 890 parts of T acid mother liquor is taken, and the ammonium sulfate content is 30.2%. 600 parts of denitration liquid is taken, 200 parts of water is added for dilution, 800 parts of diluted denitration liquid is obtained, and the acidity is 31.5 percent calculated by sulfuric acid.
Heating the T acid alkali molten material to 80 ℃, gradually adding the T acid mother liquor into 1 h, and carrying out negative pressure deamination on the T acid mother liquor by using the diluted denitration liquor as ammonia absorption liquid for 3 h to obtain alkali molten neutralization solution, wherein the ammonium sulfate content is less than 0.5%. After deamination, the weight of the diluted denitration liquid after ammonia absorption is 1028 parts, the acidity is 5.78 percent calculated by sulfuric acid, the ammonium sulfate content is 25.23 percent, the ammonia recovery rate is 96.46 percent, and the pH value is further neutralized to 4 to 5 by 20 percent ammonia water. And reducing the diluted denitration liquid after ammonia absorption, and further separating to obtain amino T acid and a T acid mother solution containing ammonium sulfate.
Acidifying the alkali fusion neutralization solution to pH=2 by using 30% dilute sulfuric acid, desulfurizing, absorbing the separated sulfur oxide by using sodium hydroxide to produce sodium sulfite, cooling and filtering the desulfurized alkali fusion neutralization solution to obtain a filter cake, washing the filter cake with water, press-filtering, drying to produce 151 parts of H acid finished product, wherein the H acid content is 85.43%, and the chromatographic purity is 99.03%.
Example 4
And (3) separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate. And (3) acid-base melting the amino T by using sodium hydroxide and methanol to obtain the T acid-base melting material. 1500 parts of T acid-base melting stock are taken, the H acid content of the melting stock is 15.89%, and the residual alkali content (calculated by sodium hydroxide) is 13.6%. 1110 parts of T acid mother liquor is taken, and the ammonium sulfate content is 30.2%. 600 parts of denitration liquid is taken, 200 parts of water is added for dilution, 800 parts of diluted denitration liquid is obtained, and the acidity is 31.5 percent calculated by sulfuric acid.
Heating the T acid alkali molten material to 80 ℃, gradually adding the T acid mother liquor into 1 h, and carrying out negative pressure deamination on the T acid mother liquor by using the diluted denitration liquor as ammonia absorption liquid for 3 h to obtain alkali molten neutralization solution, wherein the ammonium sulfate content is less than 0.5%. After deamination, the weight of the diluted denitration liquid after ammonia absorption is 1086 parts, the acidity is 1.3 percent calculated by sulfuric acid, the ammonium sulfate content is 29.48 percent, the ammonia recovery rate is 96.6 percent, and 20 percent ammonia water is used for further neutralization until the pH value is 4-5. And reducing the diluted denitration liquid after ammonia absorption, and further separating to obtain amino T acid and a T acid mother solution containing ammonium sulfate.
Acidifying the alkali fusion neutralization solution to pH=2 by using 30% dilute sulfuric acid, desulfurizing, absorbing the separated sulfur oxide by using sodium hydroxide to produce sodium sulfite, cooling and filtering the desulfurized alkali fusion neutralization solution to obtain a filter cake, washing the filter cake with water, press-filtering, drying to produce 178 parts of H acid finished product, wherein the H acid content is 85.76%, and the chromatographic purity is 98.89%.
Example 5
And (3) separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate. And (3) acid-base melting the amino T by using sodium hydroxide and methanol to obtain the T acid-base melting material. 1000 parts of T acid-base melting stock are taken, the H acid content of the T acid-base melting stock is 15.55%, and the residual alkali content (calculated by sodium hydroxide) is 12.9%. 850 parts of T acid mother liquor is taken, and the ammonium sulfate content is 27.3%. 600 parts of denitration liquid is taken, 200 parts of water is added for dilution, 800 parts of diluted denitration liquid is obtained, and the acidity is 30.1 percent calculated by sulfuric acid.
Heating the T acid alkali molten material to 80 ℃, gradually adding the T acid mother liquor into 1 h, and carrying out negative pressure deamination on the T acid mother liquor by using the diluted denitration liquor as ammonia absorption liquid for 3h to obtain alkali molten neutralization solution, wherein the ammonium sulfate content is less than 0.5%. After deamination, the weight of the diluted denitration liquid after ammonia absorption is 950 parts, the acidity is 4.68 percent calculated by sulfuric acid, the ammonium sulfate content is 23.44 percent, the ammonia recovery rate is 96.01 percent, and the pH value is further neutralized to 4-5 by 20 percent ammonia water. And reducing the diluted denitration liquid after ammonia absorption, and further separating to obtain amino T acid and a T acid mother solution containing ammonium sulfate.
Acidifying the alkali fusion neutralization solution to pH=2 by using 30% dilute sulfuric acid, desulfurizing, absorbing the separated sulfur oxide by using sodium hydroxide to produce sodium sulfite, cooling and filtering the desulfurized alkali fusion neutralization solution to obtain a filter cake, washing the filter cake with water, press-filtering, drying to produce 127 parts of H acid finished product, wherein the H acid content is 87.43%, and the chromatographic purity is 99.03%.
Example 6
And (3) separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate. And (3) acid-base melting the amino T by using sodium hydroxide and methanol to obtain the T acid-base melting material. 1000 parts of T acid-base melting stock are taken, the H acid content of the T acid-base melting stock is measured to be 15.8%, and the residual alkali content (calculated by sodium hydroxide) is measured to be 12.4%. 625 parts of T acid mother liquor is taken, and the ammonium sulfate content is 27.5%. 600 parts of denitration liquid is taken, 200 parts of water is added for dilution, 800 parts of diluted denitration liquid is obtained, and the acidity is 28.7 percent calculated by sulfuric acid.
Heating the T acid alkali molten material to 80 ℃, gradually adding the T acid mother liquor into 1 h, and carrying out negative pressure deamination on the T acid mother liquor by using the diluted denitration liquor as ammonia absorption liquid for 1 h to obtain alkali molten neutralization solution, wherein the ammonium sulfate content is less than 0.5%. After deamination, the weight of the diluted denitration liquid after ammonia absorption is 820 parts, the acidity is 6.73 percent calculated by sulfuric acid, the ammonium sulfate content is 22.06 percent, the ammonia recovery rate is 95.01 percent, and the pH value is further neutralized to 4 to 5 by 20 percent ammonia water. And reducing the diluted denitration liquid after ammonia absorption, and further separating to obtain amino T acid and a T acid mother solution containing ammonium sulfate.
Acidifying the alkali fusion neutralization solution to pH=2 by using 30% dilute sulfuric acid, desulfurizing, absorbing the separated sulfur oxide by using sodium hydroxide to produce sodium sulfite, cooling and filtering the desulfurized alkali fusion neutralization solution to obtain a filter cake, washing the filter cake with water, press-filtering, drying to produce 121.6 parts of H acid finished product, wherein the H acid content is 88.43%, and the chromatographic purity is 99.03%.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The process for producing H acid by recycling the T acid mother liquor is characterized by comprising the following steps of:
S1, separating refined naphthalene after sulfonation, nitration, denitration, neutralization and reduction to obtain amino T acid and a T acid mother solution containing ammonium sulfate;
S2, adding alkali and methanol into amino T acid to perform alkali fusion to obtain T acid alkali fusion, heating the T acid alkali fusion, adding T acid mother liquor to perform deamination to obtain alkali fusion neutralization solution, using the denitration solution obtained in the step S1 as ammonia absorption solution during deamination, and performing the reduction process of the step S1 on the denitration solution after deamination;
S3, acidizing, desulfurizing, cooling and filtering the alkali melt neutralization solution to obtain a filter cake, and washing, filter pressing and drying the filter cake to obtain H acid;
the mass concentration of ammonium sulfate in the T acid mother liquor is 10% -40%;
in the step S2, the mass ratio of unreacted alkali in the T acid alkali molten material to ammonium sulfate in the T acid mother liquor is 1: (1.4-1.8);
In step S2, the base includes sodium hydroxide or potassium hydroxide;
in the step S2, the deamination time is 1-3 h, and the mass fraction of ammonium sulfate in the alkali melt neutralization solution obtained by deamination is less than 0.5%.
2. The process according to claim 1, wherein in step S1, the neutralization step is performed using ammonia water when the T-acid mother liquor is obtained for the first time.
3. The process of claim 1, wherein in step S2, T acid-base frit is heated to 80-90 ℃.
4. The process according to claim 1, wherein in step S2, the pH of the denitration liquid is adjusted to 4 to 5 after deamination.
5. The process according to claim 1, characterized in that in step S3 dilute sulfuric acid is used for acidification to pH = 2.
6. The process according to claim 1, wherein in step S3, the sulfur dioxide removed is absorbed using a base during desulfurization.
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