Production method of disperse red 60 containing phenol and bromine for recycling

Abstract

The invention provides a production method of disperse red 60 containing phenol and bromine for recycling, which comprises bromination reaction, hydrolysis reaction, condensation reaction, waste liquid recovery and waste gas treatment.The product purity of the disperse red 60 prepared by the production method is increased to 99% or above, the tar content is reduced to 1% or below, the level-dyeing property and the improvement performance are remarkably improved, and the product quality is improved. The requirements of the market on high-quality dyes are met; the phenol and bromine recovery process is added, the phenol recovery rate is 95% or above, the bromine recovery rate reaches 85% or above, and the raw material consumption is remarkably reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of dye chemical industry, in particular to a production method of dispersion red 60 with recycling of phenol and bromine. BACKGROUND

[0002] Dispersion red 60, chemical name 1-amino-2-phenoxy-4-hydroxy anthraquinone, is an important dispersion dye, mainly used for dyeing of polyester and its blended fabrics. Due to its bright color, high dyeing strength, excellent build-up performance, and compatibility with various blue and yellow dyes for over dyeing, it has a wide range of industrial applications, and as one of the three primary colors of dyes, it has an important position. At the same time, as an intermediate, it can be further processed to produce dyes with better performance, such as dispersion red 91, dispersion red 92, etc.

[0003] The existing production process of dispersion red 60 mainly uses 1-aminoanthraquinone as raw material to carry out bromination, hydrolysis and condensation reaction in sulfuric acid medium, and finally prepares dispersion red 60. However, the existing technology has the following problems: (1) serious pollution of "three wastes": a large amount of waste gas (such as bromine tail gas), wastewater and waste liquid are generated during the reaction, and if these wastes are not properly treated, they will cause serious pollution to the environment. (2) Resource waste: the mother liquor contains a large amount of unreacted raw materials (phenol and bromine), the recovery and utilization efficiency is low, which leads to resource waste and rising production cost. (3) Product quality fluctuation: the traditional process has high tar content, the product has insufficient light fastness and sublimation fastness, the dyeing levelness and building power decrease, which is difficult to meet the market demand for high quality products.

[0004] Therefore, it is an urgent problem to develop a dispersion red 60 production technology with low tar content, stable product quality, and reduced "three wastes" pollution, as well as environmental protection production through waste gas recovery, wastewater treatment and waste liquid resource recycling. SUMMARY

[0005] In view of the problems of low efficiency, high pollution and product quality fluctuation in the traditional dispersion red 60 production process, the present application is committed to solving the following technical problems: (1) reducing "three wastes" pollution, realizing environmental protection production through waste gas recovery, wastewater treatment and waste liquid resource recycling; (2) increasing the recovery process of phenol and bromine, realizing efficient resource recycling and reducing raw material consumption; (3) improving product quality, reducing tar content, and improving product levelness, light fastness and building performance, thereby solving the above technical problems.

[0006] The purpose of the present application is to provide a production method of dispersion red 60 with recycling of phenol and bromine, comprising the following steps:

[0007] Step S1, bromination reaction;

[0008] Step S2, hydrolysis reaction;

[0009] Step S3, condensation reaction;

[0010] Step S4, waste liquid recovery and waste gas treatment.

[0011] Further, the specific steps of step S1 bromination reaction are as follows:

[0012] In the configuration kettle, add sulfuric acid with a concentration of 93%~94.5% and an appropriate amount of water, control the concentration of sulfuric acid at 75~78%;

[0013] Stir evenly at 50~60r / min and heat to 95~105℃; add 1-aminoanthraquinone, maintain the reaction for 20~50 minutes, and then transfer the mixture into the bromination reaction kettle;

[0014] Control the temperature to 99℃~102℃, gradually add bromine, and after the addition is completed, react for 1~1.5h to generate a bromination product solution. The generated hydrogen bromide tail gas is collected and treated with water to obtain a hydrobromic acid mother liquor.

[0015] Further, the bromine addition speed is 0.5~1.5kg / min; the mass ratio of 1-aminoanthraquinone to bromine is 1:2~1:1.5.

[0016] Further, the specific steps of step S2 hydrolysis reaction are as follows:

[0017] Add 20~30kg hexamethylenetetramine to the bromination product solution, heat in stages, control the temperature at 95±5℃ in the first stage for 30min, and control the temperature at 102±2℃ in the second stage for 120min to complete the hydrolysis to obtain a hydrolysis product.

[0018] Further, after hydrolysis, the material is cooled to 30~35℃, 1000kg of water is added for dilution, and a plate and frame filter press is used for pressure filtration, then hot water at 80℃ is used for washing until the filtrate is neutral, the washing water is recovered for the next batch, and the generated hydrogen bromide tail gas is collected and treated with water to obtain a hydrobromic acid mother liquor.

[0019] Further, the specific steps of step S3 condensation reaction are as follows:

[0020] In the condensation kettle, add 1200~1800kg phenol, heat to 90℃-95℃, add the hydrolysis product obtained in step S2, dehydrate to a temperature of 150~160℃, then add 1000~1300kg potassium carbonate and maintain for 4.5~5h to complete the condensation reaction; add 1500kg water to the condensation product for dilution, filter with a centrifuge, pump hot water from the centrifuge washing port, and wash until neutral to finally obtain a disperse red 60 filter cake.

[0021] Further, the step S4 waste liquid recovery and waste gas treatment includes phenol recovery, bromine recovery and waste gas treatment.

[0022] Further, the recovery of phenol is completed by layering, distillation and rectification.

[0023] The specific steps of the recovery of phenol are as follows: the hot water washing water after the step S3 condensation reaction, i.e. the phenol washing water containing about 3% phenol, is poured into a recovery pot, a jacket is heated to 110℃, and evaporation and dehydration are performed, the time for a batch of mother liquor to be evaporated and dehydrated is 4-5 hours, phenol water is recovered, and the recovered phenol water is used for subsequent production. After the washing water is evaporated, the remaining phenol brine in the pot is mixed with phenol filter press mother liquor (the filtrate of condensation filtration is phenol filter press mother liquor), and then poured into a layering pot, stirring is started, the stirring rate is 100-300 r / min, about 50% sulfuric acid is slowly added, the drop speed is controlled to be 50-100 drops / min, the pH value is adjusted to 3, and layering is completed after 2 hours of standing, the upper phenol mother liquor is separated and sent to the next process, and the lower layer mainly contains potassium bromide and is used for bromine recovery.

[0024] The phenol mother liquor is poured into a crude distillation kettle, 32% lye is used to adjust the pH to 7, heating is performed to 160℃ under a vacuum condition of 0.04 MPa or above to perform preliminary distillation, after the distillation is completed, the distillation mother liquor is transferred into a distillation residue kettle, heating is performed to below 195℃ to perform further evaporation, after the evaporation is completed in the distillation residue kettle, the bottom distillation residue is sent to an incinerator for treatment, and the bottom distillation residue is sent to an incinerator for treatment. The evaporated low-concentration phenol liquid is sent to a rectification tower, heating rectification is performed, the tower bottom temperature is controlled to be 100℃-120℃, when the tower bottom temperature reaches 120℃, sampling detection of the phenol content is performed, and when the phenol content reaches more than 95%, collection and reuse are performed.

[0025] Further, the specific steps of the recovery of bromine are as follows: after the acidified bromic acid water is introduced into chlorine gas, hydrogen bromide is oxidized into bromine and recovered for use in the next round of production. The hydrogen bromide generated in the bromination and hydrolysis processes is absorbed in the acid water and the phenol recovery condensation layering liquid is poured into a concentration kettle, the concentrated liquid is heated to a potassium bromide content of 20-25%, a 15-18% sodium chlorate solution is slowly added, the temperature is raised to 70-75℃, and bromine is recovered. After the bromine is evaporated, the temperature is lowered (no bromine condensation is generated in the condenser), and the waste water is sent to a wastewater treatment station.

[0026] Compared with the prior art, the present application has the following outstanding features and advantages:

[0027] 1. Resource utilization rate is improved: the recovery processes of phenol and bromine are added, the phenol recovery rate is more than 95%, the bromine recovery rate is more than 85%, and the raw material consumption is significantly reduced.

[0028] 2. Environmental performance is improved: waste gas emission meets the standard, the reuse rate of treated waste water is improved by 30%, and the pollution to the environment is reduced.

[0029] 3. Product quality improvement: product purity increased to over 99%, tar content reduced to below 1%, dyeing evenness and upgrading performance significantly improved, meeting market demand for high-quality dyes.

[0030] 4. Significant economic benefits: through resource recycling and waste treatment optimization, production cost reduced by more than 20%, enhancing market competitiveness. DETAILED DESCRIPTION

[0031] The technical solutions of the present application will be described below in conjunction with examples. Obviously, the described examples are only a part of the embodiments of the present application, rather than all. Based on the examples in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application. The technical solutions of the present application will be further described below in conjunction with examples.

[0032] Example 1

[0033] The present embodiment provides a production method of Disperse Red 60 containing phenol and bromine recycling, comprising the following steps:

[0034] The specific steps of step S1 bromination reaction are as follows:

[0035] Add sulfuric acid and appropriate amount of water in the configuration kettle, control the concentration of sulfuric acid at 76%; 60r / min uniform stirring and heating to 100℃; add 250kg 1-aminoanthraquinone, maintain the reaction for 30 minutes, then transfer the mixture into the bromination reaction kettle;

[0036] Control the temperature to 100℃, gradually add 360kg bromine, the bromine drop adding speed is 1kg / min; after the drop adding is completed, react for 1h to generate bromination product solution.

[0037] The specific steps of step S2 hydrolysis reaction are as follows:

[0038] Add 25kg hexamethylenetetramine into the bromination product solution, heat in stages, the first stage temperature is controlled at 95℃, maintain for 30min, the second stage temperature is controlled at 102℃ and maintain for 120 minutes to complete the hydrolysis to prepare hydrolysis product.

[0039] The specific steps of step S3 condensation reaction are as follows:

[0040] Add 1500kg phenol in the condensation pot, heat to 95℃, add the hydrolysis product prepared in step S2, dehydrate to the temperature of 155℃, then add 1200kg potassium carbonate and maintain for 4.5h to complete the condensation reaction; add 1500kg water in the condensation product to dilute, filter by centrifuge, pump hot water from the centrifuge washing port to wash, finally obtain Disperse Red 60 filter cake.

[0041] The specific steps of the recovery of phenol are as follows: the hot water washing water after the step S3 condensation reaction is poured into a recovery pot, a jacket is heated to 110 DEG C, evaporation and dehydration are performed, the time of evaporation and dehydration is 4 hours, phenol water is recovered, and the recovered phenol water is used for subsequent production. After the evaporation of the washing water, the phenol salt water remaining in the kettle is mixed with phenol filter mother liquor (the filtrate of the condensation filtration is the phenol filter mother liquor), and then is poured into a separation pot, stirring is started, the stirring rate is 200 r / min, 50% sulfuric acid is slowly added, the dropping speed is controlled to be 80 drops / min, the pH value is adjusted to 3, and standing is performed for 2 hours to complete the separation, the upper phenol mother liquor is separated and is sent to the next process, and the lower layer mainly contains potassium bromide and is used for the recovery of bromine.

[0042] The phenol mother liquor is poured into a crude distillation kettle, 32% lye is used to adjust the pH value to 7, heating is performed to 160 DEG C under a vacuum condition of 0.04 MPa or above to perform preliminary distillation, after the distillation is completed, the distillation mother liquor is transferred into a distillation residue kettle, heating is performed to below 195 DEG C to perform further evaporation, after the evaporation is completed in the distillation residue kettle, the bottom distillation residue is sent to an incinerator for treatment, and the bottom distillation residue is sent to an incinerator for treatment. The low-concentration phenol liquid evaporated is sent into a rectification tower, heating rectification is performed, the tower bottom temperature is controlled to be 120 DEG C, when the tower bottom temperature reaches 120 DEG C, sampling detection of the phenol content is performed, when the phenol content reaches 95% or above, collection and reuse are performed. According to calculation, the recovery rate of the phenol is 98%.

[0043] Further, the specific steps of the recovery of bromine are as follows: after the acidification of the bromic acid water, chlorine gas is introduced, hydrogen bromide is oxidized into bromine and is recovered for the next round of production. The hydrogen bromide generated in the bromination and hydrolysis process is absorbed by the acid water and the phenol recovery condensation separation liquid, is poured into a concentration kettle, the concentration liquid is heated to a potassium bromide content of 25%, a dissolved 18% sodium chlorate solution is slowly added, the temperature is raised to 75 DEG C, and the bromine is recovered. After the evaporation of the bromine, the temperature is lowered (no bromine condensation is generated in the condenser), the waste water is sent to a sewage treatment station, and the recovery rate of the bromine reaches 90%.

[0044] The prepared disperse red 60 filter cake is detected and analyzed, and the results are shown in Table 1. As shown in Table 1, the detection results of the product appearance, diffusibility and the like show that the product meets the relevant national product index standard requirements.

[0045] Table 1. Disperse red 60 test parameter comparison table

[0046] Detection standard Detection item Unit Standard requirement Actual measurement result Single item conclusion GB / T 2374-2007 Appearance - Purple red uniform powder or particle Purple red uniform powder Pass GB / T 2374-2006 Strength (with standard product) Min 100±2 100 Pass GB / T 2374-2006 Color light (with standard product) Approximately-micro Approximately Pass GB / T 2374-2013 Spectroscopic intensity Min 100 100 Pass HB / T 3399-2001 Diffusion performance Level ≥4 4 Pass GB / T 9337-2009 Coloring rate % ≥90 95 Pass GB 19601 Harmful aromatic PPM 150 20 Pass GB / T 8427-2008 Light resistance Level 5 5.5 Pass GB / T 2397-2003 Lifting force / level Level B A Pass

[0047] As can be seen from the diffusion performance in Table 1, the disperse red 60 prepared by the application has excellent uniform dyeing performance, and the content of tar harmful aromatic is only 20 PPM. The product purity is improved to more than 99%, the tar content is reduced to less than 1%, the dyeing levelness and upgrading performance are significantly improved, and the market demand for high-quality dyes is met.

[0048] Through resource recycling and waste treatment optimization, the production cost is reduced by more than 20%, and the market competitiveness is enhanced.

[0049] The above-described embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it cannot be understood as limiting the scope of the patent. It should be noted that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of protection of the present application.

Claims

1. A production method of Disperse Red 60 containing phenol and bromine recovery and reuse, characterized by, The method comprises the following steps: Step S1, bromination reaction; Step S2, hydrolysis reaction; Step S3, condensation reaction; Step S4, waste liquid recovery and waste gas treatment.

2. The phenol and bromine recovery and recycling-containing dispersed red 60 production method according to claim 1, characterized in that, The specific steps of step S1, bromination reaction, are as follows: Sulfuric acid and an appropriate amount of water are added into a configured kettle, the concentration of the sulfuric acid is controlled to be 75-78%, and the mixture is uniformly stirred at 50-60 r / min and heated to 95-105°C; 1-aminoanthraquinone is added, the reaction is maintained for 20-50 min, and then the mixture is transferred into a bromination reaction kettle; The temperature is controlled to be 99-102°C, bromine is gradually added dropwise, and after the dropwise addition is completed, the reaction is carried out for 1-1.5 h to generate a bromination product solution.

3. The phenol and bromine recovery and recycling-containing dispersed red 60 production method according to claim 2, characterized in that, The dropwise addition speed of bromine is 0.5-1.5 kg / min, and the mass ratio of 1-aminoanthraquinone to bromine is 1:2-1:1.

5.

4. The phenol and bromine recovery and recycling-containing dispersed red 60 production method according to claim 1, characterized in that, The specific steps of step S2, hydrolysis reaction, are as follows: 20-30 kg of hexamethylenetetramine is added into the bromination product solution, the temperature is gradually increased, the temperature in the first stage is controlled to be 95±5°C and maintained for 30 min, the temperature in the second stage is controlled to be 102±2°C and maintained for 120 min to complete the hydrolysis to generate a hydrolysis product.

5. The phenol and bromine recovery and recycling containing dispersed red 60 production method according to claim 4, characterized in that, After the hydrolysis, the material is cooled to 30-35°C, 1000 kg of water is added for dilution, a plate and frame filter press is used for pressure filtration, hot water at 80°C is used for washing until the filtrate is neutral, the washing water is recovered for use in the next batch, and the generated hydrogen bromide tail gas is collected and treated to obtain a hydrogen bromide mother liquor.

6. The phenol and bromine recovery and recycling containing dispersed red 60 production method according to claim 1, characterized in that, The specific steps of step S3, condensation reaction, are as follows: In a condensation kettle, 1200-1800 kg of phenol is added, the temperature is increased to 90-95°C, the hydrolysis product generated in step S2 is added, dehydration is carried out until the temperature reaches 150-160°C, then 1000-1300 kg of potassium carbonate is added and maintained for 4.5-5 h to complete the condensation reaction; 1500 kg of water is added to the condensation product for dilution, a centrifugal machine is used for filtration, hot water is pumped from the washing port of the centrifugal machine, and finally a disperse red 60 filter cake is obtained.

7. The phenol and bromine recovery and recycling containing dispersed red 60 production method according to claim 1, characterized in that, Step S4, waste liquid recovery and waste gas treatment, includes phenol recovery, bromine recovery and waste gas treatment.

8. The phenol and bromine recovery and recycling-containing dispersed red 60 production method according to claim 7, characterized in that, The recovery of phenol is completed through layering, distillation and rectification.

9. The phenol and bromine recovery and recycling containing dispersed red 60 production method according to claim 7, characterized in that, The specific steps of bromine recovery are as follows: after the bromic acid-containing water is acidified, chlorine gas is introduced, the hydrogen bromide is oxidized to bromine, and the bromine is recovered for use in the next production.