阅读说明：本技术 一种溶剂法生产1-硝基蒽醌的废渣的资源化利用方法 (Resource utilization method of waste residue generated in production of 1-nitroanthraquinone by solvent method ) 是由 叶世森 彭德新 戎永宝 高卫斌 于 2020-05-14 设计创作，主要内容包括：本发明提供一种溶剂法生产1-硝基蒽醌的废渣的资源化利用方法,其包括：S1:将废渣处理成浆料,加亚硫酸钠加热保温反应,过滤水洗,干燥滤饼制得混合硝基蒽醌干粉；S2:将混合硝基蒽醌干粉和蒽醌共同投到混酸(浓硝酸+浓硫酸)中,在35-45℃下进行二硝化反应；S3:反应混合物过滤,抽出母液酸,将滤饼水洗后干燥得到总纯度在92％以上的1,5-二硝基蒽醌和1,8-二硝基蒽醌混合物；S4:母液酸减压蒸馏回收硝酸,蒸馏母液降温、过滤回收混合二硝基蒽醌和二次母液,二次母液循环用到步骤S2中。本发明将溶剂法生产1-硝基蒽醌产生的废渣进行资源化利用,从而实现1-氨基蒽醌和1,5(1,8)-二硝基蒽醌的联产,大大提高了蒽醌一硝化和二硝化反应的原子利用率,使原子经济反应最大化,企业经济效益显著。(The invention provides a resource utilization method of waste residue generated in the production of 1-nitroanthraquinone by a solvent method, which comprises the following steps: s1, processing the waste residue into slurry, adding sodium sulfite, heating, keeping the temperature, reacting, filtering, washing, and drying a filter cake to obtain mixed nitroanthraquinone dry powder; s2, adding the mixed nitroanthraquinone dry powder and anthraquinone into mixed acid (concentrated nitric acid and concentrated sulfuric acid) together, and carrying out dinitration reaction at 35-45 ℃; s3, filtering the reaction mixture, pumping out mother liquor acid, washing a filter cake with water, and drying to obtain a mixture of 1, 5-dinitroanthraquinone and 1, 8-dinitroanthraquinone with the total purity of more than 92%; and S4, distilling the mother liquor acid under reduced pressure to recover nitric acid, cooling the distilled mother liquor, filtering and recovering the mixed dinitroanthraquinone and secondary mother liquor, and recycling the secondary mother liquor to the step S2. The method recycles the waste residues generated in the production of the 1-nitroanthraquinone by the solvent method, thereby realizing the co-production of the 1-aminoanthraquinone and the 1, 5(1,8) -dinitroanthraquinone, greatly improving the atom utilization rate of the anthraquinone mono-nitration reaction and the anthraquinone di-nitration reaction, maximizing the atom economic reaction and having obvious enterprise economic benefit.)

1. A resource utilization method of waste residue generated in the production of 1-nitroanthraquinone by a solvent method is characterized by comprising the following steps:

s1, processing the waste residue to prepare the nitroanthraquinone dry powder, wherein the method comprises the following steps:

adding water into the waste residue produced in the solvent method for producing 1-nitroanthraquinone, grinding, sieving and removing slag to obtain slurry, adding sodium sulfite, heating to 85-95 ℃, preserving heat for 1-10h, filtering, washing a filter cake with hot water until the filtrate is colorless, and drying the filter cake to obtain mixed nitroanthraquinone dry powder;

alternatively, the first and second electrodes may be,

diluting distillation residues obtained after DMF solvent is recovered by vacuum rectification in the process of producing 1-nitroanthraquinone by a solvent method into water under strong stirring to obtain slurry, adding sodium sulfite, heating to 85-95 ℃, preserving heat for 1-10h, filtering the slurry, washing a filter cake with hot water until the filtrate is colorless, and drying the filter cake to obtain mixed nitroanthraquinone dry powder;

s2 dinitration of anthraquinone

Gradually adding the mixed dry powder of nitroanthraquinone and anthraquinone obtained in the step S1 into mixed acid consisting of nitric acid and sulfuric acid at the temperature of 5-15 ℃, heating to 35 +/-5 ℃ for 2-3h after the feeding is finished, and continuously reacting for 2-8h at the temperature of 35-45 ℃;

s3 harvesting dinitroanthraquinone:

after the reaction is finished, filtering the reactant, pumping out mother liquor acid, adding water into a filter cake, pulping, filtering, washing with water, and drying to obtain mixed dinitroanthraquinone, wherein the total purity of the 1, 5-dinitroanthraquinone and the 1, 8-dinitroanthraquinone is more than 92%;

s4, mother liquor acid treatment:

and (4) distilling the mother liquor acid filtered and extracted in the step S3 under reduced pressure to recover nitric acid, cooling and filtering the distilled mother liquor to obtain mixed dinitroanthraquinone and secondary mother liquor, and recycling the secondary mother liquor to the step S2.

2. The resource utilization method according to claim 1, wherein in S1, the temperature of hot water is 80-85 ℃; and the filtrate produced by the filtration in step S1, and the hot water for washing the filter cake are circulated for this step to be used for preparing the slurry.

3. The resource utilization method according to claim 1, wherein in S2, the mass ratio of the mixed nitroanthraquinone dry powder to the anthraquinone is 1: 1-3.

4. The resource utilization method according to claim 1, wherein in S2, the mixed acid is formed by mixing nitric acid with a certain concentration and sulfuric acid with a certain concentration, wherein the mass concentration of the nitric acid is 97-99%, the mass concentration of the sulfuric acid is 98-105%, and the mixing volume of the nitric acid and the sulfuric acid is 4-7: 1-5.

5. The resource utilization method according to claim 4, wherein in S2, the mass ratio of the total mass of the mixed dry powder of nitroanthraquinone to anthraquinone to nitric acid is 1:2-3.5, and the mass ratio of the mixed dry powder of nitroanthraquinone to sulfuric acid is 1: 0.5-2.5.

6. The resource utilization method as claimed in claim 1, wherein in S3, the filter cake is subjected to water adding and pulping, filtering, and the filtrate and the water washing liquid generated after water washing are combined together and are circularly applied to the step for the filter cake pulping.

7. The resource utilization method according to claim 1, wherein in S4, the distillation mother liquor is cooled and filtered to obtain mixed dinitroanthraquinone, and the mixed dinitroanthraquinone is further used as a raw material to produce dispersed ash N or reduced ash M or is processed into a papermaking cooking aid.

Technical Field

The invention relates to the technical field of treatment of waste residues in dye intermediate production, in particular to a resource utilization method of waste residues in 1-nitroanthraquinone production by a solvent method.

Background

Anthraquinone dyes are the dyes with the largest dosage except azo dyes, and have two main advantages that the light fastness is excellent, the bright color can be generated, in the red, purple, blue and other dark dyes, the anthraquinone dyes occupy the important position without substitution, and almost all anthraquinone dyes are derivatives of α -site hydroxyl or amino of anthraquinone, because hydrogen of α -site hydroxyl or amino on an anthraquinone ring forms hydrogen bond with 9, 10-site carbon group, the color system of anthraquinone can generate dark color effect, and the color intensity is improved, wherein nitroanthraquinone (comprising 1-nitroanthraquinone, 1, 5-dinitroanthraquinone, 1, 8-dinitroanthraquinone and mixture of 1, 5-dinitroanthraquinone and 1, 8-dinitroanthraquinone) can be the most important anthraquinone intermediate, and a plurality of important anthraquinone dyes such as C.I. disperse red 60, C.I. disperse blue 56, C.I. disperse blue 73, C.I. disperse blue 77, C.I. disperse blue 60, C.I. disperse blue 54, C.I. disperse blue 19 and the like are synthesized into active blue intermediates.

In the late stage of the last eighties, the solvent method for producing 1-nitroanthraquinone is successfully developed by Zhang-jin pine and the like in China, and the industrial production in scale is realized in the nineties, so that China quickly replaces the production of large companies such as Japan residents, Germany Bayer and the like, and becomes the country which only produces 1-nitroanthraquinone and further produces 1-aminoanthraquinone in the world, the process for producing 1-nitroanthraquinone by the solvent method comprises the steps of carrying out primary nitration reaction on anthraquinone in dichloroethane solvent and mixed acid (consisting of sulfuric acid and nitric acid) to obtain crude 1-nitroanthraquinone with the mass fraction of 1-nitroanthraquinone of more than 82%, drying the crude 1-nitroanthraquinone, separating nitroanthraquinone isomer by using dimethyl formamide (DMF) as solvent to obtain high-purity 1-nitroanthraquinone (HP L C has the purity of 99.8%), reducing 90% of waste water in the original 1-aminoanthraquinone production, but distillation residues obtained after vacuum distillation and recovery of DMF solvent, because of DMF are not well utilized, the waste residues often occupy the important position of the landfill treatment of 1-aminoanthraquinone in dye industry, and the defects of the current production of amino anthraquinone, namely, the reduction of three wastes, and the production of iron powder, the environmental pollution of the production and the production of the amino acid, the production.

Although the solvent method adopted by each domestic 1-aminoanthraquinone producer has the same and different processes, the production scale, process control and production equipment are different, and the composition of waste residue is also different. The mass components of various nitroanthraquinone isomers in the waste residue are approximately: 1.8-9.5% of 1, 8-dinitroanthraquinone, 2.5-8.5% of 1, 5-dinitroanthraquinone, 33.0-68.0% of 1-nitroanthraquinone, 6.5-12.6% of 1, 6(1, 7) -dinitroanthraquinone, 1.0-6.0% of anthraquinone, 1.8-14.5% of 2-nitroanthraquinone and a very small amount of isomers generated in the refining process of crude 1-nitroanthraquinone. Because the 1-nitroanthraquinone is refined by utilizing the different solubility of the nitroanthraquinone isomers in DMF, and the 1, 5-dinitroanthraquinone is an isomer which is difficult to remove, more 1-nitroanthraquinone is lost in the refining process, and the amount of waste residue accounts for about 50 percent of the amount of the obtained refined 1-nitroanthraquinone.

The research (CN1087753C) of utilizing 1-nitroanthraquinone 'waste residue' is firstly developed in China, the waste residue is subjected to mixed acid nitration, sodium sulfide reduction and commercialization to obtain disperse yellow brown E-4BR, and if the waste residue is subjected to bromination after reduction and commercialization, disperse red brown E-2R is obtained; the Wuhan chemical institute (CN1244639C) has also studied the modification of bromination into chlorination and commercialization to obtain the disperse red brown E-3R. Such 'slag' utilization methods have significant drawbacks: because the composition of the waste residue is unstable, the prepared dye is a variegated dye with complex composition, the dyeing performance is poor, the color light is unstable, the commodity utilization value is low, and the using amount is small, so the problem of resource utilization of a large amount of waste residue cannot be solved.

Disclosure of Invention

Technical problem to be solved

In order to solve the problems in the prior art, the invention provides a resource utilization method of waste residue generated in the production of 1-nitroanthraquinone by a solvent method, and particularly relates to a method for preparing 1, 5(1,8) -dinitroanthraquinone by replacing part of anthraquinone (which is blended with anthraquinone to be used as a raw material) after the waste residue is treated by sodium sulfite so as to realize the resource utilization of the waste residue.

(II) technical scheme

In order to achieve the purpose, the invention adopts the main technical scheme that:

a resource utilization method of waste residue generated in the production of 1-nitroanthraquinone by a solvent method comprises the following steps:

s1, processing the waste residue to prepare the mixed nitroanthraquinone dry powder, wherein the method comprises the following steps:

adding water into the waste residue produced in the solvent method for producing 1-nitroanthraquinone, grinding, sieving and removing slag to obtain slurry, adding sodium sulfite, heating to 85-95 ℃, preserving heat for 1-10h, filtering, washing a filter cake with hot water until the filtrate is colorless, and drying the filter cake to obtain mixed nitroanthraquinone dry powder;

alternatively, the first and second electrodes may be,

diluting distillation residues obtained after DMF solvent is recovered by vacuum rectification in the process of producing 1-nitroanthraquinone by a solvent method into water under strong stirring to obtain slurry, adding sodium sulfite, heating to 85-95 ℃, preserving heat for 1-10h, filtering the slurry, washing a filter cake with hot water until the filtrate is colorless, and drying the filter cake to obtain mixed nitroanthraquinone dry powder;

s2 dinitration of anthraquinone

Gradually adding the mixed dry powder of nitroanthraquinone and anthraquinone obtained in the step S1 into mixed acid consisting of nitric acid and sulfuric acid at the temperature of 5-15 ℃, heating to 35 +/-5 ℃ for 2-3h after the feeding is finished, and continuously reacting for 2-8h at the temperature of 35-45 ℃;

s3 harvesting dinitroanthraquinone:

after the reaction is finished, filtering the reactant, pumping out mother liquor acid, adding water into a filter cake, pulping, filtering, washing with water, and drying to obtain dinitroanthraquinone, wherein the total purity of the 1, 5-dinitroanthraquinone and the 1, 8-dinitroanthraquinone is more than 92%;

s4, mother liquor acid treatment:

and (4) distilling the mother liquor acid filtered and extracted in the step S3 under reduced pressure to recover nitric acid, cooling and filtering the distilled mother liquor to obtain mixed dinitroanthraquinone and secondary mother liquor, and recycling the secondary mother liquor to the step S2.

In a preferred embodiment of the present invention, in S1, the temperature of the hot water is 80-85 ℃; and the filtrate produced by the filtration in step S1, and hot water for washing the filter cake are circulated for this step for preparing the slurry.

As a preferred embodiment of the invention, in S2, the mass ratio of the mixed dry powder of nitroanthraquinone to anthraquinone is 1: 1-3.

As a preferred embodiment of the invention, in S2, the mixed acid is formed by mixing nitric acid with a certain concentration and sulfuric acid with a certain concentration, wherein the mass concentration of nitric acid is 97-99%, and the mass concentration of sulfuric acid is 98-105%; the mixing volume of the nitric acid and the sulfuric acid is 4-7: 1-5.

As a preferred embodiment of the invention, in S2, the mass ratio of the total mass of the mixed dry powder of nitroanthraquinone and anthraquinone to the nitric acid is 1:2-3.5, and the mass ratio of the mixed dry powder of nitroanthraquinone to sulfuric acid is 1: 0.5-2.5.

As a preferred embodiment of the invention, in S3, the filter cake is beaten with water, filtered, and the filtrate and water washing liquid produced after water washing are combined together and recycled for use in this step for the water used for beating the filter cake.

In S4, the distillation mother liquor is cooled and filtered to obtain mixed dinitroanthraquinone mainly comprising α -dinitroanthraquinone and α' -dinitroanthraquinone, which is further used for synthesizing disperse dyes or vat dyes, producing disperse ash N or vat ash M and other dye varieties, or processing into papermaking cooking aids.

(III) advantageous effects

The invention has the beneficial effects that:

(1) according to the method, the purity (HP L C) of the prepared 1, 5(1,8) -dinitroanthraquinone is more than 92%, the purity and the composition (the proportion of the 1, 5-dinitroanthraquinone to the 1, 8-dinitroanthraquinone) are just consistent with the composition of the 1, 5(1,8) -dinitroanthraquinone used in the production of the disperse blue 56 at present, and the prepared 1, 5(1,8) -dinitroanthraquinone can be directly used for synthesizing the disperse blue 56 crude dye.

(2) The nitration reaction product of the invention is 1, 5-, 1, 6-, 1, 7-, 1, 8-dinitroanthraquinone and 1-nitroanthraquinone and 2-nitroanthraquinone with extremely small amount, after 1, 5(1,8) -dinitroanthraquinone with purity of more than 92% is obtained by direct filtration and separation, α -dinitroanthraquinone and α' -dinitroanthraquinone are mainly contained in the mixed dinitroanthraquinone recovered by mother liquor acid reduced pressure distillation, temperature reduction, crystallization and filtration, and the nitration reaction product can be further used for synthesizing disperse dyes or reduction dyes, producing dyes such as disperse ash N or reduction ash M and the like, and can be processed into a papermaking cooking auxiliary agent.

(3) According to the method, the mother liquor acid generated by preparing the 1, 5(1,8) -dinitroanthraquinone is subjected to reduced pressure distillation to recover nitric acid and secondary mother liquor, and can be recycled in anthraquinone dinitration reaction to realize recycling. The waste liquid is recycled, the environmental pollution is reduced, the purpose of changing waste into valuable is achieved, good economic benefits and environmental benefits are achieved, and green low-carbon sustainable recycling production is realized; the waste water and the filter cake water washing liquid generated in each step of the process can be respectively collected and combined and used for respective steps such as diluting waste residues to prepare slurry and filter cake pulping water, and the consumption of water purification resources and sewage discharge are reduced.

Drawings

FIG. 1 is a flow chart illustrating a preferred embodiment of the present invention.

Detailed Description

For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.

FIG. 1 shows a flow chart of the preferred embodiment of the present invention. The invention provides a resource utilization method of waste residue generated in the production of 1-nitroanthraquinone by a solvent method, which comprises the following steps:

s1, processing the waste residue into slurry, adding sodium sulfite, heating, preserving heat, reacting, filtering and washing to obtain the mixed nitroanthraquinone dry powder, wherein the process comprises the following steps:

the method comprises the following steps: adding water into the waste residue of the solvent method for producing 1-nitroanthraquinone, grinding, sieving and removing slag to obtain slurry, adding sodium sulfite, heating to 85-95 ℃, keeping the temperature for 1-10h, filtering, washing the filter cake with hot water until the filtrate is colorless, and drying the filter cake to obtain the mixed nitroanthraquinone dry powder.

The second method comprises the following steps: diluting distillation residue obtained after DMF solvent is recovered by vacuum rectification in the process of producing 1-nitroanthraquinone by a solvent method into water under strong stirring to obtain slurry, adding sodium sulfite, heating to 85-95 ℃, preserving heat for 1-10h, filtering the slurry, washing a filter cake with hot water until the filtrate is colorless, and drying the filter cake to obtain mixed nitroanthraquinone dry powder.

S2, putting the mixed nitroanthraquinone dry powder and anthraquinone into mixed acid (formed by mixing concentrated nitric acid and concentrated sulfuric acid), and carrying out dinitration reaction at 35-45 ℃, wherein the specific process comprises the following steps:

and (4) gradually adding the mixed dry powder of the nitroanthraquinone and the anthraquinone obtained in the step (S1) into mixed acid consisting of nitric acid and sulfuric acid at the temperature of 5-15 ℃, heating to 35 +/-5 ℃ for 2-3 hours after the feeding is finished, and then continuously reacting for 2-8 hours at the temperature of 35-45 ℃.

S3, filtering the reaction mixture, pumping out mother liquor acid, washing a filter cake with water, and drying to obtain the dinitroanthraquinone, wherein the specific process comprises the following steps:

after the reaction is finished, the reactant is filtered, mother liquor acid is extracted, a filter cake is added with water and is pulped, filtered, washed and dried to obtain the dinitroanthraquinone, wherein the total purity of the 1, 5-dinitroanthraquinone and the 1, 8-dinitroanthraquinone is more than 92%, and the proportion of the two kinds of the dinitroanthraquinones is exactly the same as the composition of the 1, 5(1,8) -dinitroanthraquinone used in the production of the disperse blue 56, so that the dinitroanthraquinone can be directly used for synthesizing the disperse blue 56 crude dye.

And S4, distilling the mother liquor acid under reduced pressure to recover nitric acid, cooling the distilled mother liquor, filtering and recovering the mixed dinitroanthraquinone and secondary mother liquor, and recycling the secondary mother liquor to the step S2.

Wherein the filtrate produced by the filtration in step S1, and hot water for washing the filter cake are circulated for this step for preparing the slurry.

In step S3, the filtrate from the pulping and filtering of the filter cake with water and the water washing liquid from the washing of the filter cake are combined together and can be recycled for the water used for the pulping of the filter cake in the step.

In step S4, the distillation mother liquor is cooled and filtered to obtain mixed dinitroanthraquinone mainly comprising α -dinitroanthraquinone and α' -dinitroanthraquinone, which is further used for synthesizing disperse dyes or reduction dyes, producing dye varieties such as disperse ash N or reduction ash M and the like, or processing the mixed dinitroanthraquinone into a papermaking cooking aid.

The following are preferred embodiments of the present invention.