阅读说明：本技术 一种溴氨酸清洁生产方法 (Clean production method of bromamine acid ) 是由 时娇娇 李超 于 2021-01-12 设计创作，主要内容包括：本发明涉及一种溴氨酸清洁生产方法,包括：制备1-氨基蒽醌-2-磺酸；制备1-氨基蒽醌-2-磺酸的硫酸溶液；将1-氨基蒽醌-2-磺酸的硫酸溶液的酸度调节至预设值,添加溴化料以制备溴氨酸粗品；静置溴氨酸粗品以去除多余的邻二氯苯溶液；对溴氨酸溶液进行热精制,热精制后使用活性炭吸附溶液内有机物；盐析溶液以得到含有溴氨酸结晶的溶液,压缩溶液,干燥滤饼以得到溴氨酸。本发明通过在制备BAA过程中调节1-氨基蒽醌-2-磺酸的硫酸溶液的酸度,能够有效地降低了难于去除的异构体1-氨基-4-羟基蒽醌并有效降低后续过程中产生的酸氯废水的量,并有效提高制备的BAA滤饼内BAA的含量,从而有效提高了本发明所述方法制备BAA的制备效率。(The invention relates to a clean production method of bromamine acid, which comprises the following steps: preparing 1-aminoanthraquinone-2-sulfonic acid; preparing a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid; adjusting the acidity of a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to a preset value, and adding a brominated material to prepare a crude product of bromamine acid; standing the crude bromamine acid product to remove redundant o-dichlorobenzene solution; performing thermal refining on the bromamine acid solution, and adsorbing organic matters in the solution by using activated carbon after the thermal refining; salting out the solution to obtain a solution containing crystals of bromamine acid, compressing the solution, and drying the filter cake to obtain bromamine acid. The invention can effectively reduce isomer 1-amino-4-hydroxyanthraquinone which is difficult to remove and effectively reduce the amount of acid chloride wastewater generated in the subsequent process by adjusting the acidity of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid in the preparation process of BAA, and effectively improve the BAA content in the prepared BAA filter cake, thereby effectively improving the preparation efficiency of BAA prepared by the method.)

1. A clean production method of bromamine acid is characterized by comprising the following steps:

step a, dissolving 1-AA in an o-dichlorobenzene solvent, adding chlorosulfonic acid to carry out sulfonation reaction to prepare salt, and translocating the salt to generate 1-aminoanthraquinone-2-sulfonic acid;

b, extracting the 1-aminoanthraquinone-2-sulfonic acid generated in the step a and adding the extracted extract into a sulfuric acid solvent to prepare a sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

c, adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid prepared in the step b to enable the acidity to reach a preset value, and adding a brominated material into the adjusted sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to perform bromination reaction to prepare a crude product of bromamine acid;

d, standing and layering the crude bromamine acid prepared in the step c to remove redundant o-dichlorobenzene solution, adding water into the separated o-dichlorobenzene solution for secondary layering, taking out the o-dichlorobenzene solution after layering, distilling and purifying the o-dichlorobenzene solution, and recycling the purified o-dichlorobenzene to the step a;

step e, mixing the bromamine acid solution obtained after primary layering and secondary layering in the step d, carrying out thermal refining on the bromamine acid solution, and adsorbing organic matters in the refined solution and in the neutralized wastewater by using activated carbon after the thermal refining is finished;

step f, adding refined salt into the solution after adsorption in the step e to carry out salting out, obtaining a solution containing bromamine acid crystals after salting out, compressing the solution, taking out a filter cake after compression, and drying the filter cake to obtain bromamine acid;

in the step b, setting the preset acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid as Si, and sequentially establishing a preset excessively low acidity difference matrix delta Sa0, a preset excessively high acidity difference matrix delta Sb0, a preset sulfuric acid solution addition quantity matrix Qa0 and a preset dilution ratio matrix Qb 0;

in said step c, when the preliminary preparation of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is completed, the actual acidity S of the sulfuric acid solution is detected and compared with Si:

if S is less than Si, the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is judged to be too low, the over-acidity difference value Delta Sa of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is calculated, the Delta Sa is compared with parameters in a preset over-acidity difference value matrix Delta Sa0, and the corresponding addition amount of the sulfuric acid solution is selected from the preset addition amount matrix Qa0 according to the comparison result;

if S is larger than Si, judging that the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is too high, calculating an over-high acidity difference value Delta Sb of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, comparing the Delta Sb with parameters in a preset over-high acidity difference value matrix Delta Sb0, selecting a corresponding dilution ratio from a preset dilution ratio matrix Qb0 according to a comparison result, adding water to the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution when Qbj is selected as a preset dilution ratio, and setting the preset ratio of the water in the diluted sulfuric acid solution to the sulfuric acid solution as Qbj;

and if S = Si, judging that the preparation of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is finished, and adding a brominated material into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to carry out bromination reaction on the brominated material and the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid.

2. The method for the clean production of bromamine acid according to claim 1, wherein for the preset excessively low acidity difference matrix Δ Sa0, Δ Sa0 (Δ Sa1, Δ Sa2, Δ Sa3, Δ Sa 4) is set, wherein Δ Sa1 is a first preset excessively low acidity difference, Δ Sa2 is a second preset excessively low acidity difference, Δ Sa3 is a third preset excessively low acidity difference, and Δ Sa4 is a fourth preset excessively low acidity difference, each preset excessively low acidity difference gradually increasing in order; setting Qa0 (Qa 1, Qa2, Qa3 and Qa 4) for the preset sulfuric acid solution addition quantity matrix Qa0, wherein Qa1 is a first preset sulfuric acid solution addition quantity, Qa2 is a second preset sulfuric acid solution addition quantity, Qa3 is a third preset sulfuric acid solution addition quantity, Qa4 is a fourth preset sulfuric acid solution addition quantity, and the preset sulfuric acid solution addition quantities are gradually increased in sequence;

when the actual acidity S of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is less than the preset acidity Si of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, calculating an excessively low acidity difference value delta Sa, setting delta Sa = S-Si, and comparing the delta Sa with parameters in a preset excessively low acidity difference value matrix delta Sa0 after calculation is completed:

when the delta Sa is less than or equal to delta Sa1, a sulfuric acid solution is not added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when delta Sa1 is less than delta Sa and less than delta Sa2, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 1;

when delta Sa2 is less than delta Sa and less than delta Sa3, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 2;

when delta Sa3 is less than delta Sa and less than delta Sa4, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 3;

adding a sulfuric acid solution to a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid and setting the addition amount of the sulfuric acid solution to Qa4 when Δ Sa > [ Δ Sa ] 4;

when a corresponding amount of sulfuric acid solution is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, the acidity value S 'of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected and compared with Si, if S' > Si, the excessively low acidity difference Delta Sa 'is calculated, and Delta Sa' = S '-Si is set, if Delta Sa' >. DELTA. 1, the corresponding amount of sulfuric acid solution is added again until the adjusted acidity value S 'of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is less than or equal to Si or the excessively low acidity difference Delta Sa' < DELTA.Sa 1, and Delta Sa '= S' -Si is set.

3. The clean production method of bromamine acid according to claim 2, wherein when a sulfuric acid solution is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid and the addition amount of the sulfuric acid solution is set to Qai, i =1, 2, 3, 4 is set, and a preset sulfuric acid concentration matrix U0 and a preset sulfuric acid solution addition amount correction coefficient matrix a0 are established; setting U0 (U1, U2, U3 and U4) for the preset sulfuric acid concentration matrix U0, wherein U1 is a first preset sulfuric acid concentration, U2 is a second preset sulfuric acid concentration, U3 is a third preset sulfuric acid concentration, U4 is a fourth preset sulfuric acid concentration, and the preset sulfuric acid concentration values are gradually increased in sequence; setting a0 (a 1, a2, a3 and a 4) for the preset sulfuric acid solution addition quantity correction coefficient matrix a0, wherein a1 is a first preset sulfuric acid solution addition quantity correction coefficient, a2 is a second preset sulfuric acid solution addition quantity correction coefficient, a3 is a third preset sulfuric acid solution addition quantity correction coefficient, a4 is a fourth preset sulfuric acid solution addition quantity correction coefficient, and 0 & lt a1 & lt a2 & lt 1 & lt a3 & lt a4 & lt 2;

when the addition amount of the sulfuric acid solution added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is set as Qai, comparing the sulfuric acid concentration U in the added sulfuric acid solution with the parameters in the preset sulfuric acid concentration matrix U0, and selecting a corresponding preset sulfuric acid solution addition amount correction coefficient from the preset sulfuric acid solution addition amount correction coefficient matrix a0 according to the comparison result to correct the Qai:

when U is less than or equal to U1, selecting a first preset sulfuric acid solution addition quantity correction coefficient a1 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U1 and less than or equal to U2, selecting a second preset sulfuric acid solution addition quantity correction coefficient a2 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U2 and less than or equal to U3, selecting a third preset sulfuric acid solution addition quantity correction coefficient a3 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U3 and less than or equal to U4, selecting a fourth preset sulfuric acid solution addition quantity correction coefficient a4 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when the jth preset sulfuric acid solution addition amount correction coefficient aj is selected to correct the Qai, j =1, 2, 3, 4 is set, and the corrected sulfuric acid solution addition amount is Qai' = Qai × aj is set.

4. The clean production method of bromamine acid according to claim 2, characterized in that for said preset excess acidity difference matrix Δ Sb0, Δ Sb0 (Δ Sb1, Δ Sb2, Δ Sb3, Δ Sb 4) is set, wherein Δ Sb1 is a first preset excess acidity difference, Δ Sb2 is a second preset excess acidity difference, Δ Sb3 is a third preset excess acidity difference, Δ Sb4 is a fourth preset excess acidity difference, each preset excess acidity difference being gradually increased in order; setting a Qb0 (Qb 1, Qb2, Qb3 and Qb 4) for the preset dilution ratio matrix Qb0, wherein Qb1 is a first preset dilution ratio, Qb2 is a second preset dilution ratio, Qb3 is a third preset dilution ratio, Qb4 is a fourth preset dilution ratio, and the ratio of the preset dilution ratios is gradually increased in sequence;

when the actual acidity S of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is greater than the preset acidity Si of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, calculating an overhigh acidity difference value Delta Sb, setting Delta Sb = Si-S, and after the calculation is finished, comparing the Delta Sb with parameters in a preset overhigh acidity difference matrix Delta Sb 0:

when the Delta Sb is less than or equal to the Delta Sb1, the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is not diluted;

when delta Sb1 is less than delta Sb ≦ delta Sb2, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 1;

when delta Sb2 is less than delta Sb ≦ delta Sb3, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 2;

when delta Sb3 is less than delta Sb ≦ delta Sb4, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 3;

adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb4, when Δ Sb > [ Δ Sb ] 4;

when water is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution is set to Qbj, j =1, 2, 3, 4 is set, the acidity value S ' of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected and S ' is compared with Si, if S ' < Si, the excessively high acidity difference Δ Sb ' is calculated, Δ Sb ' = Si-S ' is set, if Δ Sb ' >. DELTA.sb 1, the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected until the acidity value S "≦ Si or the excessively high acidity difference Δ Sb" ≦ Sb1 of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid after dilution, Δ Sb "= Si-S" is set.

5. The clean production method of bromamine acid as claimed in claim 1, wherein, when preparing sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid in said step b, a preset content matrix p0 and a preset acidity matrix S0 are established; setting p0 (p 1, p2, p3 and p 4) for the preset content matrix p0, wherein p1 is a first preset content, p2 is a second preset content, p3 is a third preset content, p4 is a fourth preset content, and the preset contents are gradually increased in sequence; setting S0 (S1, S2, S3 and S4) for the preset acidity matrix S0, wherein S1 is first preset acidity, S2 is second preset acidity, S3 is third preset acidity, S4 is fourth preset acidity, and the preset acidity values are gradually increased in sequence;

when preparing the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, detecting the content p of 1-AA in the 1-aminoanthraquinone-2-sulfonic acid prepared in the step a, comparing the p with the parameters in the preset content matrix p0, and determining the acidity standard of the sulfuric acid solution of the subsequently prepared 1-aminoanthraquinone-2-sulfonic acid according to the comparison result:

when p is less than or equal to p1, selecting first preset acidity S1 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p1 and less than or equal to p2, selecting second preset acidity S2 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p2 and less than or equal to p3, selecting third preset acidity S3 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p3 and less than or equal to p4, selecting fourth preset acidity S4 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when the ith preset acidity Si is selected as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, detecting the actual acidity value S of the primarily prepared sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, comparing the S with the Si, and adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid in a corresponding mode according to the comparison result.

6. The clean production method of bromamine acid as claimed in claim 5, wherein a preset solute critical content B0 is established during the adjustment of the acidity of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, the content B of 1-aminoanthraquinone-2-sulfonic acid in the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is detected in real time while the acidity of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is adjusted, when B < B0, the adjustment of the acidity of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is stopped and a bromide is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to carry out bromination reaction.

7. The clean production method of bromamine acid according to claim 1, wherein the brominated compound comprises sodium bromide and/or sodium bromate.

8. The clean production method of bromamine acid as claimed in claim 5, wherein in said step e, a preset colorimetric variable matrix C0 is established, and C0 (C1, C2, C3, C4) is set, wherein C1 is a first preset colorimetric variable, C2 is a second preset colorimetric variable, C3 is a third preset colorimetric variable, C4 is a fourth preset colorimetric variable, and the values of the preset colorimetric variables are gradually increased in order;

when the activated carbon is used for adsorbing organic matters in the neutralization wastewater, periodically detecting the chromaticity of the neutralization wastewater, determining a preset chromaticity variation standard of the neutralization wastewater in a single period according to a preset acidity standard, setting i =1, 2, 3 and 4 when the preset acidity standard is exactly the ith preset acidity Si, and setting the chromaticity variation standard of the neutralization wastewater in the single detection period as Ci in the process of adsorbing the organic matters in the neutralization wastewater by the activated carbon.

9. The clean production method of bromamine acid according to claim 8, wherein when activated carbon is used for adsorbing and neutralizing organic matters in wastewater, a preset colorimetric variable difference matrix ac 0 and a preset activated carbon addition amount matrix G0 are established; for the preset chromaticity variable difference matrix ac 0, Δ C0 (Δ C1, Δ C2, Δ C3, Δ C4) is set, where Δ C1 is a first preset chromaticity variable difference, Δ C2 is a second preset chromaticity variable difference, Δ C3 is a third preset chromaticity variable difference, and Δ C4 is a fourth preset chromaticity variable difference, and the preset chromaticity variable differences gradually increase in order; for the preset activated carbon addition amount matrix G0, G0 (G1, G2, G3 and G4) is set, wherein G1 is a first preset activated carbon addition amount, G2 is a second preset activated carbon addition amount, G3 is a third preset activated carbon addition amount, G4 is a fourth preset activated carbon addition amount, and the preset activated carbon addition amounts are gradually increased in sequence;

when the standard of the chromaticity variation of the neutralized wastewater in a single detection period is set as Ci, the chromaticity of the neutralized wastewater when the neutralized wastewater enters the adsorption period and the chromaticity of the neutralized wastewater when the adsorption period is finished are respectively detected in a single adsorption period, the chromaticity variable C of the neutralized wastewater in the adsorption period is calculated and compared with Ci, if C is less than Ci, the chromaticity variable difference value Delta C is calculated, the value Delta C = Ci-C is set, and after the calculation is finished, the value Delta C is compared with the parameters in the preset chromaticity variable difference matrix Delta C0:

when the delta C is less than or equal to the delta C1, adding activated carbon into the neutralized wastewater, and setting the addition amount as G1;

when the delta C1 is less than and equal to the delta C2, adding activated carbon into the neutralized wastewater, and setting the addition amount as G2;

when the delta C2 is less than and equal to the delta C3, adding activated carbon into the neutralized wastewater, and setting the addition amount as G3;

when the delta C3 is less than delta C and less than delta C4, activated carbon is added to the neutralized wastewater, and the addition amount is set as G4.

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a clean production method of bromamine acid.

Background

Bromamine acid (BAA) is a red needle crystal with the chemical name of 1-amino-4-bromoanthraquinone-2-sulfonic acid. Is easy to dissolve in water, is orange paste or powder, is mainly used for dye intermediates to prepare acid anthraquinone dyes, and is widely used for preparing anthraquinone raw dyes, acid dyes and disperse dyes. At present, the dyes synthesized by bromamine acid are various in variety, and the demand of domestic and foreign markets for the products is huge. In conclusion, the effect of the bromamine acid and the shortage of research technology on the bromamine acid influence important branch standards related to color light of dyes. The yield in the preparation process is high and low, and the unit cost of the bromamine acid is directly influenced. Therefore, a bromamine acid production mode with high yield, good purity, strong operability and environmental protection is developed, and the method has great economic value and social value.

Bromamine acid is produced by carrying out post-treatment such as sulfonation, bromination reaction and neutralization, refining, drying and the like on 1-aminoanthraquinone, and a sulfuric acid method is adopted in the traditional sulfonation process.

In the prior art, most of o-dichlorobenzene is used as a solvent, and a chlorosulfonic acid sulfonation process reduces sulfonation side reactions and improves sulfonation yield, however, the solvent method BAA production mainly reduces the side reactions of the sulfonation reaction and improves the sulfonation yield, but the waste water discharge in the production process is not reduced basically. There are two types of wastewater discharged: acid-filtered wastewater and neutralized wastewater, wherein the acid-filtered wastewater amount is about 4-5M³Per t product, about 20M of waste water³And t is the product.

Because the waste water contains a large amount of anthraquinone compounds, the chroma is high, the COD is high, and the acid filtration waste water also contains a large amount of sulfuric acid which is far higher than the discharge standard, the prior art can not carry out targeted treatment on the waste water generated in the process of preparing the BAA by a solvent method, thereby reducing the preparation efficiency of the BAA.

Disclosure of Invention

Therefore, the invention provides a clean production method of bromamine acid, which is used for overcoming the problem of low BAA preparation efficiency caused by the fact that waste water generated in the process of preparing BAA by a solvent method cannot be effectively treated in the prior art.

In order to achieve the above object, the present invention provides a method for clean production of bromamine acid, comprising:

step a, dissolving 1-AA in an o-dichlorobenzene solvent, adding chlorosulfonic acid to carry out sulfonation reaction to prepare salt, and translocating the salt to generate 1-aminoanthraquinone-2-sulfonic acid;

b, extracting the 1-aminoanthraquinone-2-sulfonic acid generated in the step a and adding the extracted extract into a sulfuric acid solvent to prepare a sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

c, adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid prepared in the step b to enable the acidity to reach a preset value, and adding a brominated material into the adjusted sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to perform bromination reaction to prepare a crude product of bromamine acid;

d, standing and layering the crude bromamine acid prepared in the step c to remove redundant o-dichlorobenzene solution, adding water into the separated o-dichlorobenzene solution for secondary layering, taking out the o-dichlorobenzene solution after layering, distilling and purifying the o-dichlorobenzene solution, and recycling the purified o-dichlorobenzene to the step a;

step e, mixing the bromamine acid solution obtained after primary layering and secondary layering in the step d, carrying out thermal refining on the bromamine acid solution, and adsorbing organic matters in the refined solution and in the neutralized wastewater by using activated carbon after the thermal refining is finished;

step f, adding refined salt into the solution after adsorption in the step e to carry out salting out, obtaining a solution containing bromamine acid crystals after salting out, compressing the solution, taking out a filter cake after compression, and drying the filter cake to obtain bromamine acid;

in the step b, setting the preset acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid as Si, and sequentially establishing a preset excessively low acidity difference matrix delta Sa0, a preset excessively high acidity difference matrix delta Sb0, a preset sulfuric acid solution addition quantity matrix Qa0 and a preset dilution ratio matrix Qb 0;

in said step c, when the preliminary preparation of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is completed, the actual acidity S of the sulfuric acid solution is detected and compared with Si:

if S is less than Si, the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is judged to be too low, the over-acidity difference value Delta Sa of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is calculated, the Delta Sa is compared with parameters in a preset over-acidity difference value matrix Delta Sa0, and the corresponding addition amount of the sulfuric acid solution is selected from the preset addition amount matrix Qa0 according to the comparison result;

if S is larger than Si, judging that the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is too high, calculating an over-high acidity difference value Delta Sb of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, comparing the Delta Sb with parameters in a preset over-high acidity difference value matrix Delta Sb0, selecting a corresponding dilution ratio from a preset dilution ratio matrix Qb0 according to a comparison result, adding water to the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution when Qbj is selected as a preset dilution ratio, and setting the preset ratio of the water in the diluted sulfuric acid solution to the sulfuric acid solution as Qbj;

and if S = Si, judging that the preparation of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is finished, and adding a brominated material into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to carry out bromination reaction on the brominated material and the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid.

Further, for the preset excessively low acidity difference matrix Δ Sa0, Δ Sa0 (Δ Sa1, Δ Sa2, Δ Sa3, Δ Sa 4) is set, where Δ Sa1 is a first preset excessively low acidity difference, Δ Sa2 is a second preset excessively low acidity difference, Δ Sa3 is a third preset excessively low acidity difference, and Δ Sa4 is a fourth preset excessively low acidity difference, and the preset excessively low acidity differences gradually increase in order; setting Qa0 (Qa 1, Qa2, Qa3 and Qa 4) for the preset sulfuric acid solution addition quantity matrix Qa0, wherein Qa1 is a first preset sulfuric acid solution addition quantity, Qa2 is a second preset sulfuric acid solution addition quantity, Qa3 is a third preset sulfuric acid solution addition quantity, Qa4 is a fourth preset sulfuric acid solution addition quantity, and the preset sulfuric acid solution addition quantities are gradually increased in sequence;

when the actual acidity S of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is less than the preset acidity Si of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, calculating an excessively low acidity difference value delta Sa, setting delta Sa = S-Si, and comparing the delta Sa with parameters in a preset excessively low acidity difference value matrix delta Sa0 after calculation is completed:

when the delta Sa is less than or equal to delta Sa1, a sulfuric acid solution is not added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when delta Sa1 is less than delta Sa and less than delta Sa2, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 1;

when delta Sa2 is less than delta Sa and less than delta Sa3, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 2;

when delta Sa3 is less than delta Sa and less than delta Sa4, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 3;

adding a sulfuric acid solution to a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid and setting the addition amount of the sulfuric acid solution to Qa4 when Δ Sa > [ Δ Sa ] 4;

when a corresponding amount of sulfuric acid solution is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, the acidity value S 'of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected and compared with Si, if S' > Si, the excessively low acidity difference Delta Sa 'is calculated, and Delta Sa' = S '-Si is set, if Delta Sa' >. DELTA. 1, the corresponding amount of sulfuric acid solution is added again until the adjusted acidity value S 'of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is less than or equal to Si or the excessively low acidity difference Delta Sa' < DELTA.Sa 1, and Delta Sa '= S' -Si is set.

Further, when a sulfuric acid solution is added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid and the addition amount of the sulfuric acid solution is set to be Qai, setting i =1, 2, 3, 4, and establishing a preset sulfuric acid concentration matrix U0 and a preset sulfuric acid solution addition amount correction coefficient matrix a 0; setting U0 (U1, U2, U3 and U4) for the preset sulfuric acid concentration matrix U0, wherein U1 is a first preset sulfuric acid concentration, U2 is a second preset sulfuric acid concentration, U3 is a third preset sulfuric acid concentration, U4 is a fourth preset sulfuric acid concentration, and the preset sulfuric acid concentration values are gradually increased in sequence; setting a0 (a 1, a2, a3 and a 4) for the preset sulfuric acid solution addition quantity correction coefficient matrix a0, wherein a1 is a first preset sulfuric acid solution addition quantity correction coefficient, a2 is a second preset sulfuric acid solution addition quantity correction coefficient, a3 is a third preset sulfuric acid solution addition quantity correction coefficient, a4 is a fourth preset sulfuric acid solution addition quantity correction coefficient, and 0 & lt a1 & lt a2 & lt 1 & lt a3 & lt a4 & lt 2;

when the addition amount of the sulfuric acid solution added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is set as Qai, comparing the sulfuric acid concentration U in the added sulfuric acid solution with the parameters in the preset sulfuric acid concentration matrix U0, and selecting a corresponding preset sulfuric acid solution addition amount correction coefficient from the preset sulfuric acid solution addition amount correction coefficient matrix a0 according to the comparison result to correct the Qai:

when U is less than or equal to U1, selecting a first preset sulfuric acid solution addition quantity correction coefficient a1 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U1 and less than or equal to U2, selecting a second preset sulfuric acid solution addition quantity correction coefficient a2 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U2 and less than or equal to U3, selecting a third preset sulfuric acid solution addition quantity correction coefficient a3 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U3 and less than or equal to U4, selecting a fourth preset sulfuric acid solution addition quantity correction coefficient a4 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when the jth preset sulfuric acid solution addition amount correction coefficient aj is selected to correct the Qai, j =1, 2, 3, 4 is set, and the corrected sulfuric acid solution addition amount is Qai' = Qai × aj is set.

Further, for the preset excessively high acidity difference matrix Δ Sb0, Δ Sb0 (Δ Sb1, Δ Sb2, Δ Sb3, Δ Sb 4) is set, where Δ Sb1 is a first preset excessively high acidity difference, Δ Sb2 is a second preset excessively high acidity difference, Δ Sb3 is a third preset excessively high acidity difference, and Δ Sb4 is a fourth preset excessively high acidity difference, and the preset excessively high acidity differences are gradually increased in order; setting a Qb0 (Qb 1, Qb2, Qb3 and Qb 4) for the preset dilution ratio matrix Qb0, wherein Qb1 is a first preset dilution ratio, Qb2 is a second preset dilution ratio, Qb3 is a third preset dilution ratio, Qb4 is a fourth preset dilution ratio, and the ratio of the preset dilution ratios is gradually increased in sequence;

when the actual acidity S of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is greater than the preset acidity Si of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, calculating an overhigh acidity difference value Delta Sb, setting Delta Sb = Si-S, and after the calculation is finished, comparing the Delta Sb with parameters in a preset overhigh acidity difference matrix Delta Sb 0:

when the Delta Sb is less than or equal to the Delta Sb1, the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is not diluted;

when delta Sb1 is less than delta Sb ≦ delta Sb2, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 1;

when delta Sb2 is less than delta Sb ≦ delta Sb3, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 2;

when delta Sb3 is less than delta Sb ≦ delta Sb4, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 3;

adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb4, when Δ Sb > [ Δ Sb ] 4;

when water is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution is set to Qbj, j =1, 2, 3, 4 is set, the acidity value S ' of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected and S ' is compared with Si, if S ' < Si, the excessively high acidity difference Δ Sb ' is calculated, Δ Sb ' = Si-S ' is set, if Δ Sb ' >. DELTA.sb 1, the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected until the acidity value S "≦ Si or the excessively high acidity difference Δ Sb" ≦ Sb1 of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid after dilution, Δ Sb "= Si-S" is set.

Further, when preparing the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid in the step b, establishing a preset content matrix p0 and a preset acidity matrix S0; setting p0 (p 1, p2, p3 and p 4) for the preset content matrix p0, wherein p1 is a first preset content, p2 is a second preset content, p3 is a third preset content, p4 is a fourth preset content, and the preset contents are gradually increased in sequence; setting S0 (S1, S2, S3 and S4) for the preset acidity matrix S0, wherein S1 is first preset acidity, S2 is second preset acidity, S3 is third preset acidity, S4 is fourth preset acidity, and the preset acidity values are gradually increased in sequence;

when preparing the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, detecting the content p of 1-AA in the 1-aminoanthraquinone-2-sulfonic acid prepared in the step a, comparing the p with the parameters in the preset content matrix p0, and determining the acidity standard of the sulfuric acid solution of the subsequently prepared 1-aminoanthraquinone-2-sulfonic acid according to the comparison result:

when p is less than or equal to p1, selecting first preset acidity S1 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p1 and less than or equal to p2, selecting second preset acidity S2 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p2 and less than or equal to p3, selecting third preset acidity S3 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p3 and less than or equal to p4, selecting fourth preset acidity S4 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when the ith preset acidity Si is selected as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, detecting the actual acidity value S of the primarily prepared sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, comparing the S with the Si, and adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid in a corresponding mode according to the comparison result.

Further, in the process of adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, a preset solute critical content B0 is established, when the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is adjusted, the content B of the 1-aminoanthraquinone-2-sulfonic acid in the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is detected in real time, when B is less than B0, the adjustment of the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is stopped, and a brominated material is added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to carry out bromination reaction.

Further, the brominated compound comprises sodium bromide and/or sodium bromate.

Further, in the step e, a preset chromaticity variable matrix C0 is established, and C0 (C1, C2, C3, C4) is set, where C1 is a first preset chromaticity variable, C2 is a second preset chromaticity variable, C3 is a third preset chromaticity variable, C4 is a fourth preset chromaticity variable, and values of the preset chromaticity variables are gradually increased in sequence;

when the activated carbon is used for adsorbing organic matters in the neutralization wastewater, periodically detecting the chromaticity of the neutralization wastewater, determining a preset chromaticity variation standard of the neutralization wastewater in a single period according to a preset acidity standard, setting i =1, 2, 3 and 4 when the preset acidity standard is exactly the ith preset acidity Si, and setting the chromaticity variation standard of the neutralization wastewater in the single detection period as Ci in the process of adsorbing the organic matters in the neutralization wastewater by the activated carbon.

Further, when activated carbon is used for adsorbing and neutralizing organic matters in the wastewater, a preset chromaticity variable difference matrix Delta C0 and a preset activated carbon addition quantity matrix G0 are established; for the preset chromaticity variable difference matrix ac 0, Δ C0 (Δ C1, Δ C2, Δ C3, Δ C4) is set, where Δ C1 is a first preset chromaticity variable difference, Δ C2 is a second preset chromaticity variable difference, Δ C3 is a third preset chromaticity variable difference, and Δ C4 is a fourth preset chromaticity variable difference, and the preset chromaticity variable differences gradually increase in order; for the preset activated carbon addition amount matrix G0, G0 (G1, G2, G3 and G4) is set, wherein G1 is a first preset activated carbon addition amount, G2 is a second preset activated carbon addition amount, G3 is a third preset activated carbon addition amount, G4 is a fourth preset activated carbon addition amount, and the preset activated carbon addition amounts are gradually increased in sequence;

when the standard of the chromaticity variation of the neutralized wastewater in a single detection period is set as Ci, the chromaticity of the neutralized wastewater when the neutralized wastewater enters the adsorption period and the chromaticity of the neutralized wastewater when the adsorption period is finished are respectively detected in a single adsorption period, the chromaticity variable C of the neutralized wastewater in the adsorption period is calculated and compared with Ci, if C is less than Ci, the chromaticity variable difference value Delta C is calculated, the value Delta C = Ci-C is set, and after the calculation is finished, the value Delta C is compared with the parameters in the preset chromaticity variable difference matrix Delta C0:

when the delta C is less than or equal to the delta C1, adding activated carbon into the neutralized wastewater, and setting the addition amount as G1;

when the delta C1 is less than and equal to the delta C2, adding activated carbon into the neutralized wastewater, and setting the addition amount as G2;

when the delta C2 is less than and equal to the delta C3, adding activated carbon into the neutralized wastewater, and setting the addition amount as G3;

when the delta C3 is less than delta C and less than delta C4, activated carbon is added to the neutralized wastewater, and the addition amount is set as G4.

Compared with the prior art, the method has the beneficial effects that the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is adjusted in the BAA preparation process, so that the isomer 1-amino-4-hydroxyanthraquinone which is difficult to remove can be effectively reduced, the acid chloride wastewater amount generated in the subsequent process can be effectively reduced, the BAA content in the prepared BAA filter cake can be effectively increased, and the BAA preparation efficiency of the method for preparing BAA is effectively improved.

Further, when the preparation of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is completed, the preset acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is set as Si, a preset excessively low acidity difference matrix Delta Sa0, a preset excessively high acidity difference matrix Delta Sb0, a preset sulfuric acid solution addition quantity matrix Qa0 and a preset dilution ratio matrix Qb0 are sequentially established, the actual acidity S of the sulfuric acid solution is detected, the S and the Si are compared, the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is adjusted in a corresponding mode according to the comparison result, the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is adjusted in a corresponding mode, and the prepared sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid can be further ensured to reach a preset value, thereby effectively reducing the output of acid filtration wastewater in the subsequent preparation process, improving the BAA content in the prepared BAA filter cake and further improving the preparation efficiency of the BAA prepared by the method.

Further, when the actual acidity S of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is greater than the preset acidity Si of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, calculating an excessively low acidity difference value delta Sa, comparing the delta Sa with the parameters in the preset excessively low acidity difference value matrix delta Sa0, adding a corresponding amount of sulfuric acid solution into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid according to the comparison result, and increasing the actual acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to a preset value by adding a corresponding amount of sulfuric acid solution according to the real-time detection result, so that the output of acid wastewater in the subsequent preparation process can be further reduced, and the preparation efficiency of the BAA prepared by the method provided by the invention is further improved.

Further, when a sulfuric acid solution was added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid and the amount of the added sulfuric acid solution was set to Qai, establishing a preset sulfuric acid concentration matrix U0 and a preset sulfuric acid solution addition quantity correction coefficient matrix a0, comparing the sulfuric acid concentration U in the added sulfuric acid solution with the parameters in the preset sulfuric acid concentration matrix U0, selecting a corresponding preset sulfuric acid solution addition quantity correction coefficient from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 according to the comparison result to correct Qai, the adjustment precision of the acidity of the sulfuric acid solution aiming at the 1-aminoanthraquinone-2-sulfonic acid can be effectively improved by adjusting the amount of the actually added sulfuric acid solution according to the concentration of the sulfuric acid in the added sulfuric acid solution, thereby further reducing the output of acid filtration wastewater in the subsequent preparation process and further improving the preparation efficiency of BAA prepared by the method.

Further, when the actual acidity S of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is greater than the preset acidity Si of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, calculating the over-high acidity difference value delta Sb, comparing the delta Sb with the parameters in the preset over-high acidity difference value matrix delta Sb0, selecting a corresponding dilution ratio according to the comparison result to dilute the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid can be reduced to a preset value by selecting a corresponding dilution ratio to dilute the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, the method further improves the preparation efficiency of BAA prepared by the method while further reducing the output of acid filtration wastewater in the subsequent preparation process.

Further, when preparing a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, establishing a preset content matrix p0 and a preset acidity matrix S0; detecting the content p of 1-AA in the 1-aminoanthraquinone-2-sulfonic acid prepared in the step a, comparing the p with the parameters in the preset content matrix p0, determining the acidity standard of the sulfuric acid solution of the subsequently prepared 1-aminoanthraquinone-2-sulfonic acid according to the comparison result, and determining the acidity standard of the sulfuric acid solution of the subsequently prepared 1-aminoanthraquinone-2-sulfonic acid according to the content p of 1-AA in the 1-aminoanthraquinone-2-sulfonic acid, so that the output of acid filtration wastewater in the subsequent preparation process can be further reduced, the BAA content in the prepared BAA filter cake can be further improved, and the preparation efficiency of BAA prepared by the method provided by the invention is further improved.

Further, in the process of adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, establishing a preset solute critical content B0, detecting the content B of the 1-aminoanthraquinone-2-sulfonic acid in the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid in real time when adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, stopping adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid when B is less than B0, and adding a brominated material into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to carry out bromination reaction; by setting the preset solute critical content B0, the ratio of the solution content to the solvent content can be effectively ensured, so that the resource waste caused by excessive use of sulfuric acid solution or water in the preparation process is avoided, and the preparation efficiency of BAA prepared by the method is further improved.

Further, establishing a preset chromaticity variable matrix C0, a preset chromaticity variable difference matrix Delta C0 and a preset activated carbon addition quantity matrix G0 in the step e; and when the standard of the chromaticity variation of the neutralized wastewater in a single detection period is set as Ci, and in a single adsorption period, the chromaticity of the neutralized wastewater when entering the adsorption period and the chromaticity of the neutralized wastewater when the adsorption period is finished are respectively detected, the chromaticity variable C of the neutralized wastewater in the adsorption period is calculated and compared with Ci, if C is less than Ci, the chromaticity variable difference Delta C is calculated, the Delta C is compared with the parameters in the preset chromaticity variable difference matrix Delta C0, and the addition amount of the activated carbon is adjusted according to the comparison result. By adding a corresponding amount of activated carbon according to the change rate of the chromaticity, the adsorption efficiency of organic matters in the neutralized wastewater can be effectively ensured, and the wastewater discharge amount when the BAA is prepared by using the method disclosed by the invention is effectively reduced.

Drawings

FIG. 1 is a flow chart of the clean production method of bromamine acid according to the present invention.

Detailed Description

In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Please refer to fig. 1, which is a flow chart of the clean production method of bromamine acid according to the present invention. The clean production method of the bromamine acid comprises the following steps:

step a, dissolving 1-AA in an o-dichlorobenzene solvent, adding chlorosulfonic acid to carry out sulfonation reaction to prepare salt, and translocating the salt to generate 1-aminoanthraquinone-2-sulfonic acid;

b, extracting the 1-aminoanthraquinone-2-sulfonic acid generated in the step a and adding the extracted extract into a sulfuric acid solvent to prepare a sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

c, adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid prepared in the step b to enable the acidity to reach a preset value, and adding a brominated material into the adjusted sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to perform bromination reaction to prepare a crude product of bromamine acid;

d, standing and layering the crude bromamine acid prepared in the step c to remove redundant o-dichlorobenzene solution, adding water into the separated o-dichlorobenzene solution for secondary layering, taking out the o-dichlorobenzene solution after layering, distilling and purifying the o-dichlorobenzene solution, and recycling the purified o-dichlorobenzene to the step a;

step e, mixing the bromamine acid solution obtained after primary layering and secondary layering in the step d, carrying out thermal refining on the bromamine acid solution, and adsorbing organic matters in the refined solution and in the neutralized wastewater by using activated carbon after the thermal refining is finished;

step f, adding refined salt into the solution after adsorption in the step e to carry out salting out, obtaining a solution containing bromamine acid crystals after salting out, compressing the solution, taking out a filter cake after compression, and drying the filter cake to obtain bromamine acid;

in the step b, setting the preset acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid as Si, and sequentially establishing a preset excessively low acidity difference matrix delta Sa0, a preset excessively high acidity difference matrix delta Sb0, a preset sulfuric acid solution addition quantity matrix Qa0 and a preset dilution ratio matrix Qb 0;

in said step c, when the preliminary preparation of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is completed, the actual acidity S of the sulfuric acid solution is detected and compared with Si:

if S is less than Si, the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is judged to be too low, the over-acidity difference value Delta Sa of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is calculated, the Delta Sa is compared with parameters in a preset over-acidity difference value matrix Delta Sa0, and the corresponding addition amount of the sulfuric acid solution is selected from the preset addition amount matrix Qa0 according to the comparison result;

if S is larger than Si, judging that the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is too high, calculating an over-high acidity difference value Delta Sb of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, comparing the Delta Sb with parameters in a preset over-high acidity difference value matrix Delta Sb0, selecting a corresponding dilution ratio from a preset dilution ratio matrix Qb0 according to a comparison result, adding water to the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution when Qbj is selected as a preset dilution ratio, and setting the preset ratio of the water in the diluted sulfuric acid solution to the sulfuric acid solution as Qbj;

and if S = Si, judging that the preparation of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is finished, and adding a brominated material into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to carry out bromination reaction on the brominated material and the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid.

Specifically, for the preset excessively low acidity difference matrix Δ Sa0, Δ Sa0 (Δ Sa1, Δ Sa2, Δ Sa3, Δ Sa 4) is set, where Δ Sa1 is a first preset excessively low acidity difference, Δ Sa2 is a second preset excessively low acidity difference, Δ Sa3 is a third preset excessively low acidity difference, and Δ Sa4 is a fourth preset excessively low acidity difference, and the preset excessively low acidity differences gradually increase in order; setting Qa0 (Qa 1, Qa2, Qa3 and Qa 4) for the preset sulfuric acid solution addition quantity matrix Qa0, wherein Qa1 is a first preset sulfuric acid solution addition quantity, Qa2 is a second preset sulfuric acid solution addition quantity, Qa3 is a third preset sulfuric acid solution addition quantity, Qa4 is a fourth preset sulfuric acid solution addition quantity, and the preset sulfuric acid solution addition quantities are gradually increased in sequence;

when the actual acidity S of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is less than the preset acidity Si of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, calculating an excessively low acidity difference value delta Sa, setting delta Sa = S-Si, and comparing the delta Sa with parameters in a preset excessively low acidity difference value matrix delta Sa0 after calculation is completed:

when the delta Sa is less than or equal to delta Sa1, a sulfuric acid solution is not added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when delta Sa1 is less than delta Sa and less than delta Sa2, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 1;

when delta Sa2 is less than delta Sa and less than delta Sa3, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 2;

when delta Sa3 is less than delta Sa and less than delta Sa4, adding a sulfuric acid solution into a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, and setting the addition amount of the sulfuric acid solution as Qa 3;

adding a sulfuric acid solution to a sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid and setting the addition amount of the sulfuric acid solution to Qa4 when Δ Sa > [ Δ Sa ] 4;

when a corresponding amount of sulfuric acid solution is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid, the acidity value S 'of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected and compared with Si, if S' > Si, the excessively low acidity difference Delta Sa 'is calculated, and Delta Sa' = S '-Si is set, if Delta Sa' >. DELTA. 1, the corresponding amount of sulfuric acid solution is added again until the adjusted acidity value S 'of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is less than or equal to Si or the excessively low acidity difference Delta Sa' < DELTA.Sa 1, and Delta Sa '= S' -Si is set.

Specifically, when a sulfuric acid solution is added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid and the addition amount of the sulfuric acid solution is set to be Qai, i =1, 2, 3, 4 is set, and a preset sulfuric acid concentration matrix U0 and a preset sulfuric acid solution addition amount correction coefficient matrix a0 are established; setting U0 (U1, U2, U3 and U4) for the preset sulfuric acid concentration matrix U0, wherein U1 is a first preset sulfuric acid concentration, U2 is a second preset sulfuric acid concentration, U3 is a third preset sulfuric acid concentration, U4 is a fourth preset sulfuric acid concentration, and the preset sulfuric acid concentration values are gradually increased in sequence; setting a0 (a 1, a2, a3 and a 4) for the preset sulfuric acid solution addition quantity correction coefficient matrix a0, wherein a1 is a first preset sulfuric acid solution addition quantity correction coefficient, a2 is a second preset sulfuric acid solution addition quantity correction coefficient, a3 is a third preset sulfuric acid solution addition quantity correction coefficient, a4 is a fourth preset sulfuric acid solution addition quantity correction coefficient, and 0 & lt a1 & lt a2 & lt 1 & lt a3 & lt a4 & lt 2;

when the addition amount of the sulfuric acid solution added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is set as Qai, comparing the sulfuric acid concentration U in the added sulfuric acid solution with the parameters in the preset sulfuric acid concentration matrix U0, and selecting a corresponding preset sulfuric acid solution addition amount correction coefficient from the preset sulfuric acid solution addition amount correction coefficient matrix a0 according to the comparison result to correct the Qai:

when U is less than or equal to U1, selecting a first preset sulfuric acid solution addition quantity correction coefficient a1 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U1 and less than or equal to U2, selecting a second preset sulfuric acid solution addition quantity correction coefficient a2 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U2 and less than or equal to U3, selecting a third preset sulfuric acid solution addition quantity correction coefficient a3 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when U is more than U3 and less than or equal to U4, selecting a fourth preset sulfuric acid solution addition quantity correction coefficient a4 from the preset sulfuric acid solution addition quantity correction coefficient matrix a0 to correct Qai;

when the jth preset sulfuric acid solution addition amount correction coefficient aj is selected to correct the Qai, j =1, 2, 3, 4 is set, and the corrected sulfuric acid solution addition amount is Qai' = Qai × aj is set.

Specifically, for the preset excessively high acidity difference matrix Δ Sb0, Δ Sb0 (Δ Sb1, Δ Sb2, Δ Sb3, Δ Sb 4) is set, where Δ Sb1 is a first preset excessively high acidity difference, Δ Sb2 is a second preset excessively high acidity difference, Δ Sb3 is a third preset excessively high acidity difference, and Δ Sb4 is a fourth preset excessively high acidity difference, and the preset excessively high acidity differences gradually increase in order; setting a Qb0 (Qb 1, Qb2, Qb3 and Qb 4) for the preset dilution ratio matrix Qb0, wherein Qb1 is a first preset dilution ratio, Qb2 is a second preset dilution ratio, Qb3 is a third preset dilution ratio, Qb4 is a fourth preset dilution ratio, and the ratio of the preset dilution ratios is gradually increased in sequence;

when the actual acidity S of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is greater than the preset acidity Si of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, calculating an overhigh acidity difference value Delta Sb, setting Delta Sb = Si-S, and after the calculation is finished, comparing the Delta Sb with parameters in a preset overhigh acidity difference matrix Delta Sb 0:

when the Delta Sb is less than or equal to the Delta Sb1, the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is not diluted;

when delta Sb1 is less than delta Sb ≦ delta Sb2, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 1;

when delta Sb2 is less than delta Sb ≦ delta Sb3, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 2;

when delta Sb3 is less than delta Sb ≦ delta Sb4, adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb 3;

adding water to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and setting the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution to Qb4, when Δ Sb > [ Δ Sb ] 4;

when water is added to the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid to dilute the sulfuric acid solution and the expected ratio of water to sulfuric acid solution in the diluted sulfuric acid solution is set to Qbj, j =1, 2, 3, 4 is set, the acidity value S ' of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected and S ' is compared with Si, if S ' < Si, the excessively high acidity difference Δ Sb ' is calculated, Δ Sb ' = Si-S ' is set, if Δ Sb ' >. DELTA.sb 1, the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is redetected until the acidity value S "≦ Si or the excessively high acidity difference Δ Sb" ≦ Sb1 of the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid after dilution, Δ Sb "= Si-S" is set.

Specifically, when the sulfuric acid solution of 1-aminoanthraquinone-2-sulfonic acid is prepared in the step b, a preset content matrix p0 and a preset acidity matrix S0 are established; setting p0 (p 1, p2, p3 and p 4) for the preset content matrix p0, wherein p1 is a first preset content, p2 is a second preset content, p3 is a third preset content, p4 is a fourth preset content, and the preset contents are gradually increased in sequence; setting S0 (S1, S2, S3 and S4) for the preset acidity matrix S0, wherein S1 is first preset acidity, S2 is second preset acidity, S3 is third preset acidity, S4 is fourth preset acidity, and the preset acidity values are gradually increased in sequence;

when preparing the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, detecting the content p of 1-AA in the 1-aminoanthraquinone-2-sulfonic acid prepared in the step a, comparing the p with the parameters in the preset content matrix p0, and determining the acidity standard of the sulfuric acid solution of the subsequently prepared 1-aminoanthraquinone-2-sulfonic acid according to the comparison result:

when p is less than or equal to p1, selecting first preset acidity S1 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p1 and less than or equal to p2, selecting second preset acidity S2 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p2 and less than or equal to p3, selecting third preset acidity S3 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when p is more than p3 and less than or equal to p4, selecting fourth preset acidity S4 as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid;

when the ith preset acidity Si is selected as the acidity standard of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, detecting the actual acidity value S of the primarily prepared sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, comparing the S with the Si, and adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid in a corresponding mode according to the comparison result.

Specifically, in the process of adjusting the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid, a preset solute critical content B0 is established, when the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is adjusted, the content B of the 1-aminoanthraquinone-2-sulfonic acid in the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is detected in real time, when B is less than B0, the adjustment of the acidity of the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid is stopped, and a brominated material is added into the sulfuric acid solution of the 1-aminoanthraquinone-2-sulfonic acid to carry out bromination reaction.

In particular, the bromide compound comprises sodium bromide and/or sodium bromate.

Specifically, in step e, a preset chromaticity variable matrix C0 is established, and C0 (C1, C2, C3, C4) is set, where C1 is a first preset chromaticity variable, C2 is a second preset chromaticity variable, C3 is a third preset chromaticity variable, C4 is a fourth preset chromaticity variable, and values of the preset chromaticity variables are gradually increased in order;

when the activated carbon is used for adsorbing organic matters in the neutralization wastewater, periodically detecting the chromaticity of the neutralization wastewater, determining a preset chromaticity variation standard of the neutralization wastewater in a single period according to a preset acidity standard, setting i =1, 2, 3 and 4 when the preset acidity standard is exactly the ith preset acidity Si, and setting the chromaticity variation standard of the neutralization wastewater in the single detection period as Ci in the process of adsorbing the organic matters in the neutralization wastewater by the activated carbon.

Specifically, when activated carbon is used for adsorbing and neutralizing organic matters in wastewater, a preset chromaticity variable difference matrix Delta C0 and a preset activated carbon addition quantity matrix G0 are established; for the preset chromaticity variable difference matrix ac 0, Δ C0 (Δ C1, Δ C2, Δ C3, Δ C4) is set, where Δ C1 is a first preset chromaticity variable difference, Δ C2 is a second preset chromaticity variable difference, Δ C3 is a third preset chromaticity variable difference, and Δ C4 is a fourth preset chromaticity variable difference, and the preset chromaticity variable differences gradually increase in order; for the preset activated carbon addition amount matrix G0, G0 (G1, G2, G3 and G4) is set, wherein G1 is a first preset activated carbon addition amount, G2 is a second preset activated carbon addition amount, G3 is a third preset activated carbon addition amount, G4 is a fourth preset activated carbon addition amount, and the preset activated carbon addition amounts are gradually increased in sequence;

when the standard of the chromaticity variation of the neutralized wastewater in a single detection period is set as Ci, the chromaticity of the neutralized wastewater when the neutralized wastewater enters the adsorption period and the chromaticity of the neutralized wastewater when the adsorption period is finished are respectively detected in a single adsorption period, the chromaticity variable C of the neutralized wastewater in the adsorption period is calculated and compared with Ci, if C is less than Ci, the chromaticity variable difference value Delta C is calculated, the value Delta C = Ci-C is set, and after the calculation is finished, the value Delta C is compared with the parameters in the preset chromaticity variable difference matrix Delta C0:

when the delta C is less than or equal to the delta C1, adding activated carbon into the neutralized wastewater, and setting the addition amount as G1;

when the delta C1 is less than and equal to the delta C2, adding activated carbon into the neutralized wastewater, and setting the addition amount as G2;

when the delta C2 is less than and equal to the delta C3, adding activated carbon into the neutralized wastewater, and setting the addition amount as G3;

when the delta C3 is less than delta C and less than delta C4, activated carbon is added to the neutralized wastewater, and the addition amount is set as G4.

Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.

Example one

This example determines the sulfuric acid concentration of brominated feedstock during BAA production by experiment

The concentration interval of sulfuric acid after the current workshop brominated fuels are diluted is 25-30%. In this embodiment, the acid filtration wastewater is first purified to remove anthraquinone compounds, and then the dilute sulfuric acid is concentrated for reuse. Therefore, the diluted acidity should be increased as much as possible, and the energy consumption for concentrating the diluted sulfuric acid should be reduced. This example compares the mass of the acid filter cake at 30%, 40%, 50%, 60% diluted acidity to the composition of the acid filtrate in order to determine the reasonable acidity. The dilution acidity is improved as much as possible on the premise of improving the quality of filter cakes and reducing the loss of BAA.

Tables 1, 2 and 3 show the results of experiments on different dilution acidity of three batches of bromide in a workshop:

as can be seen from tables 1-3, the sulfuric acid contents were 46.76%, 45.23% and 40.27%, respectively, at the highest BAA content in the filter cake,

the lowest BAA content (external standard) in the filtrate was 42.42%, 45.23% and 36.18% -44.65%, respectively.

Comparing the data in the tables 1-3, using 92% 1-AA, the dilution acidity of the sulfuric acid should be controlled at 40% -42%; 98 percent of 1-AA is used, and the dilution acidity of the sulfuric acid is controlled to be 45 to 46 percent.

When the acidity of sulfuric acid dilution is 42% -46%, the BAA content of the filter cake is higher, but the BAA content (external standard) in the filtrate is lower.

When the dilution acidity of the sulfuric acid is more than 50%, the BAA content in a filter cake is high, but the BAA content (external standard) in a filtrate is also high, and the acid filtration wastewater is dark and opaque in appearance, has a lot of solid particle impurities separated out, is not beneficial to purification and impurity removal and needs to be recycled and applied; there was a loss of BAA in the filtrate.

When the acidity of sulfuric acid dilution is below 30%, the BAA content in the filter cake is low, and the BAA content (external standard) in the filtrate is also high.

In conclusion, at present, the dilution acidity of a workshop is unreasonably controlled to be 25-30%, the BAA content in a filter cake is obviously low, and the BAA in a filtrate is lost.

Example two

This example demonstrates the different dilution acidity

Comparative experiment: the same batch of brominated material in a workshop is taken, three groups of parallel experiments are respectively carried out by using 25% -30% and 40% -45% of diluted acidity, and the data of two kinds of diluted acidity are compared, wherein the data are shown in tables 4-5:

as can be seen from Table 4, in the two different sulfuric acid dilution acidity intervals, the difference of BAA content in the filter cake is not large, but the difference of BAA content (external standard) in the filtrate is large, and the BAA content (external standard) in the acid with the sulfuric acid acidity of 25% -30% is 2-4 times of that of the acid with the sulfuric acid acidity of 40% -45%, so that the sulfuric acid dilution acidity is controlled to be 40% -45%.

As can be seen from Table 5, neutralizing the BAA content in the filter cake, the sulphuric acid dilution acidity is between 40% and 45% significantly higher than the sulphuric acid dilution acidity between 25% and 30%, in particular the AQ content is much lower.

In conclusion, the following results can be obtained through comparative experiments: the dilution acidity of the sulfuric acid should preferably be between 40% and 45%.

So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention; various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.