CN114656351A - Method for treating 4-chlorophthalic acid or monosodium salt production wastewater thereof - Google Patents
Method for treating 4-chlorophthalic acid or monosodium salt production wastewater thereof Download PDFInfo
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Abstract
The invention relates to the technical field of industrial wastewater treatment, and particularly discloses a treatment method of 4-chlorophthalic acid or monosodium salt production wastewater thereof. According to the invention, the ruthenium simple substance is immobilized on the silicon-aluminum eight-membered ring molecular sieve, so that the anti-poisoning capacity of the catalyst can be effectively improved, the prepared catalyst has stronger tolerance to chloride ions, high catalytic activity and cyclic utilization of the catalyst in the reaction process are ensured, meanwhile, the silicon-aluminum eight-membered ring molecular sieve has higher selective adsorption to chlorophthalic byproducts in wastewater, and enrichment of the chlorophthalic byproducts with lower concentration in the wastewater is facilitated, so that the chlorophthalic byproducts are fully contacted with the ruthenium catalytic activity center, the chlorophthalic byproducts in the wastewater are fully subjected to dechlorination reduction reaction, a phthalic acid product with higher content and yield is obtained, the resource utilization of production wastewater is realized, and higher economic effect and environmental protection benefit are achieved.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to a method for treating 4-chlorophthalic acid or monosodium salt production wastewater thereof.
Background
4-chlorophthalic acid is an important raw material for preparing 3,3',4,4' -biphenyl tetracarboxylic dianhydride, and 3,3',4,4' -biphenyl tetracarboxylic dianhydride is an important monomer for preparing polyimide, and can be polymerized with various amine substances to generate the polyimide. Polyimide as a special engineering material has the advantages of wide application temperature, chemical corrosion resistance, high strength, flexibility, high variability and the like, and is widely applied to the fields of aviation, aerospace, microelectronics, nano, liquid crystal, separation membranes, laser and the like. In recent years, with the rapid development of flexible display screens, the market of high-end electronic grade polyimide films will be in a rapid expansion period. Therefore, a great deal of key intermediates for the preparation of polyimides will also be facing great market demands.
The industrial synthesis process of 4-chlorophthalic acid or its sodium salt is to introduce chlorine into phthalic anhydride as material to chlorinate 4-chlorophthalic acid or its sodium salt. The synthesis process has low selectivity, only 74 percent of phthalic anhydride participates in chlorination reaction to obtain 4-chlorophthalic acid or monosodium salt thereof, the rest 26 percent of phthalic anhydride generates byproducts, the utilization rate of raw materials is low, and the production wastewater contains more organic byproducts and needs to be further treated.
At present, the treatment method of the 4-chlorophthalic acid or the monosodium salt production wastewater thereof mainly comprises the steps of concentrating by distilled water, then adjusting the pH value of a system to separate out organic matters, centrifugally removing the organic matters, and burning the organic matters as hazardous wastes. Because the organic hazardous waste contains organic chlorine, dioxin is generated in the burning process, and the serious environmental pollution problem is caused. Therefore, a method for treating the wastewater from the production of 4-chlorophthalic acid or its monosodium salt, which can improve the utilization rate of raw materials and does not cause secondary pollution, is urgently needed.
Disclosure of Invention
Aiming at the problems that the raw material utilization rate is low in the existing production process of 4-chlorophthalic acid or monosodium salt thereof, and the wastewater generated in the production process contains more chlorine-containing organic matters, and the method for treating the wastewater can cause secondary pollution to the environment, the invention provides the method for treating the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof, which mainly comprises the step of carrying out dechlorination reduction on the production wastewater by selecting silicon-aluminum eight-membered ring molecular sieve immobilized ruthenium as a catalyst to obtain a phthalic acid product with the content of more than 99%, so that the resource utilization of the production wastewater is realized, and the method has higher economic benefit and environmental benefit.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a treatment method of 4-chlorophthalic acid or monosodium salt production wastewater thereof comprises the following steps:
dissolving soluble ruthenium salt in an alcohol solvent, adding a silicon-aluminum eight-membered ring molecular sieve, uniformly mixing, stirring and immobilizing, adjusting the pH value to be alkaline, adding a first reducing agent to carry out reduction reaction, filtering and drying to obtain a ruthenium immobilized catalyst;
b, adjusting the pH value of the 4-chlorophthalic acid or monosodium salt production wastewater thereof to 11-13, distilling and concentrating, adding an activator and the ruthenium immobilized catalyst, uniformly mixing, then adding a second reducing agent, carrying out heat preservation reaction, and filtering to obtain a reaction solution;
and c, adjusting the pH value of the reaction liquid to 0.5-1.5, cooling, crystallizing, filtering and drying to obtain the phthalic acid.
Compared with the prior art, the method for treating the 4-chlorophthalic acid or the monosodium salt production wastewater thereof selects the elementary substance of ruthenium to be immobilized on the silicon-aluminum eight-membered ring molecular sieve, not only can effectively improve the anti-poisoning capability of the catalyst, but also ensures that the prepared catalyst has stronger tolerance to chloride ions, thereby ensuring high catalytic activity and recycling property of the catalyst in the reaction process, simultaneously, the silicon-aluminum eight-membered ring molecular sieve has higher selective adsorption to the chlorophthalic acid by-products in the wastewater, being beneficial to the enrichment of the chlorophthalic acid by-products with lower concentration in the wastewater, so that the chlorophthalic acid by-product is fully contacted with the ruthenium catalytic active center, and the chlorophthalic acid by-product in the wastewater is fully dechlorinated and reduced to obtain the phthalic acid product with higher content and yield. The method not only reduces the treatment cost of the wastewater, but also obtains the phthalic acid product with higher added value, improves the utilization rate of the raw materials, realizes the resource utilization of the production wastewater, and has higher economic effect and environmental protection benefit and higher practical value.
The chlorophthalic acid by-products mainly contained in the 4-chlorophthalic acid or monosodium salt production wastewater mainly comprise 3-chlorophthalic acid, 3, 4-dichlorphthalic acid, 3, 5-dichlorphthalic acid, 4, 5-dichlorphthalic acid, 3, 6-dichlorphthalic acid and the like.
Optionally, in step a, the soluble ruthenium salt is ruthenium chloride.
Preferably, in the step a, the alcohol solvent is an ethanol aqueous solution with the mass concentration of 50-75%, and the mass ratio of the alcohol solvent to the soluble ruthenium salt is 25-40: 1.
Preferably, in the step a, the particle size of the silicon-aluminum eight-membered ring molecular sieve is 1 mm-2 mm, and the pore size is 410 pm-430 pm.
Illustratively, in step a, the silicon-aluminum eight-membered ring molecular sieve is a 4A molecular sieve of angjek environmental protection adsorption material limited.
Preferably, in the step a, the mass ratio of the silicon-aluminum eight-membered ring molecular sieve to the soluble ruthenium salt is 15-20: 1.
The optimized silicon-aluminum eight-membered ring molecular sieve and the proportion of the optimized silicon-aluminum eight-membered ring molecular sieve to the soluble ruthenium salt can ensure that a ruthenium elementary substance is uniformly loaded on the silicon-aluminum eight-membered ring molecular sieve, avoid the agglomeration of the ruthenium elementary substance, ensure that the prepared ruthenium immobilized catalyst has higher catalytic activity and higher selective adsorption to chlorophthalic acid byproducts, promote the chlorophthalic acid byproducts to be fully converted into phthalic acid, improve the utilization rate of raw materials and realize the resource utilization of production wastewater.
Preferably, in the step a, the first reducing agent is a hydrazine hydrate solution with a mass concentration of 60-80%, and the mass ratio of the hydrazine hydrate solution to the soluble ruthenium salt is 1.1-1.5: 1.
The preferable reducing agent and the addition amount thereof can realize the full reduction of soluble ruthenium salt, so that the grain diameter of ruthenium is uniform, the uniform load of a ruthenium simple substance on the silicon-aluminum eight-membered ring molecular sieve is realized, the excessive reducing agent can be converted into gas in the wastewater treatment process, and other substances cannot be additionally introduced into the wastewater and the prepared phthalic acid product.
Preferably, in the step a, the temperature of the stirring immobilization is 20-30 ℃, and the time of the stirring immobilization is 1-2 h.
The preferable solid-supporting temperature can improve the loading capacity of ruthenium on the silicon-aluminum eight-membered ring molecular sieve and ensure the uniform loading of ruthenium, thereby being beneficial to improving the catalytic activity.
Preferably, in the step a, the alkalinity means that the pH is 9-11.
In the step a, ammonia water is used for adjusting the pH value to 9-11.
Optionally, the ammonia water is industrial ammonia water, namely, an aqueous solution containing 25-28% of ammonia.
Preferably, in the step a, the temperature of the reduction reaction is 60-75 ℃, and the time of the reduction reaction is 1-2 h.
In the step b, sodium hydroxide is adopted to adjust the pH value of the 4-chlorophthalic acid or monosodium salt production wastewater thereof to 11-13.
Preferably, in the step b, the activator is a hydrazine hydrate solution with the mass concentration of 20-80%, and the mass ratio of the hydrazine hydrate solution to the ruthenium-supported catalyst is 0.2-1: 1.
The preferable adding amount of the activating agent and the activating agent can improve the reaction activity of the chlorophthalic acid by-product in the wastewater, thereby promoting the chlorophthalic acid by-product to be fully converted into phthalic acid and improving the yield and the purity of the phthalic acid by-product; meanwhile, the problem of catalyst poisoning can be avoided.
Preferably, in the step b, the mass ratio of the ruthenium-supported catalyst to the 4-chlorophthalic acid or the monosodium salt production wastewater is 0.001-0.005: 1.
The preferable adding amount of the catalyst can also reduce the use cost of the catalyst on the premise of ensuring the catalytic activity.
Preferably, in the step b, the second reducing agent is a sodium formate aqueous solution with the mass concentration of 16-30%, and the mass ratio of sodium formate to the 4-chlorophthalic acid or the monosodium salt production wastewater in the second reducing agent is 0.05-0.1: 1.
Preferably, in the step b, the second reducing agent is hydroxylamine hydrochloride solution with the mass concentration of 16-30%, and the mass ratio of hydroxylamine hydrochloride to the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof in the second reducing agent is 0.05-0.1: 1.
The preferred reducing agent can promote the dechlorination hydrogenation reaction to be fully carried out, and other substances cannot be additionally introduced into the wastewater or the phthalic acid product.
Further, in the step b, the second reducing agent is added in a dropwise manner, and the dropwise adding time is controlled to be 2-3 h.
Preferably, in the step b, the distilled water amount of the distillation concentration is 45-50% of the total mass of the 4-chlorophthalic acid or monosodium salt production wastewater.
In the step b, concentration is carried out by means of atmospheric distillation.
Further, in the step b, the temperature of the atmospheric distillation is 100-105 ℃, and the distillation time is 4-5 h.
Preferably, in the step b, the temperature of the heat preservation reaction is 95-105 ℃, and the time of the heat preservation reaction is 1-2 hours.
In step b, the catalyst obtained after filtration can be recycled as the catalyst for the next dechlorination reduction.
The preferable condition of cooling crystallization is beneficial to improving the yield and purity of phthalic acid by-products.
In the step c, the pH of the reaction solution is adjusted to 0.5-1.5 by using a 30% hydrochloric acid solution.
Preferably, in the step c, the temperature for cooling crystallization is 15-30 ℃, and the time for cooling crystallization is 1-1.5 h.
Illustratively, in step c, the filtrate obtained by filtration is subjected to MVR distillation to obtain a sodium chloride byproduct with the content of more than 98%.
For example, the water distilled out by distillation and concentration in step b and the water distilled out by MVR distillation in step c can be directly discharged.
The method for treating the 4-chlorophthalic acid or the monosodium salt production wastewater thereof has the advantages of simple process operation and low energy consumption, solves the problem that the traditional wastewater treatment process can generate toxic substances such as dioxin and the like to cause secondary pollution to the environment, realizes comprehensive treatment and resource utilization of the wastewater by treating the obtained phthalic acid and sodium chloride byproducts, and has higher economic benefit and environmental benefit and extremely high popularization value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
In the following examples and comparative examples, the wastewater from the production of 4-chlorophthalic acid monosodium salt is produced by introducing chlorine gas into phthalic anhydride as a raw material to chlorinate the phthalic anhydride, thereby obtaining wastewater produced in the technical process of 4-chlorophthalic acid monosodium salt. 2000g of the production wastewater of monosodium 4-chlorophthalate used in the following examples and comparative examples was found to contain 21.4g of phthalic acid, 31g of 4-chlorophthalic acid, 19.1g of 3-chlorophthalic acid, 5.5g of 3, 4-dichlorophthalic acid, 3.1g of 3, 5-dichlorophthalic acid, 10.3g of 4, 5-dichlorophthalic acid, and 4.7g of 3, 6-dichlorophthalic acid.
Example 1
The embodiment provides a method for treating 4-chlorophthalic acid monosodium salt production wastewater, which comprises the following steps:
step one, adding 1g of ruthenium chloride into 25g of 75% ethanol solution, stirring and dissolving, then adding 15g of 4A silicon-aluminum eight-membered ring molecular sieve, stirring and mixing at room temperature for 1h, adding 28wt% ammonia water to adjust the pH value to 9.9, stirring and immobilizing at room temperature for 1h, adding 1.1g of 80% hydrazine hydrate solution, stirring and reacting at 60 ℃ for 2h, filtering to obtain 22.2g of wet catalyst, and drying at 105 ℃ for 2h to obtain 15.5g of ruthenium immobilized catalyst;
adding sodium hydroxide into 2000g of 4-chlorophthalic acid monosodium salt production wastewater, stirring and dissolving, then adjusting the pH to 12.9, evaporating and concentrating at normal pressure and 101 ℃, and distilling off 856g of water; after the water evaporation is finished, keeping the temperature at 101 ℃, adding 5g of 40% hydrazine hydrate, uniformly mixing, adding 5g of the prepared ruthenium-supported catalyst, dropwise adding 600g of hydroxylamine hydrochloride solution (100 g of hydroxylamine hydrochloride and 500g of water) for 2h, keeping the temperature at 101 ℃ after the dropwise adding is finished, reacting for 1h, filtering at 80 ℃, recovering 7.3g of the catalyst, 1791.7g of filtrate, and detecting that the pH value of the filtrate is 10.3;
adding 30% hydrochloric acid solution into the filtrate under the stirring condition to adjust the pH value to 0.6, cooling to 25 ℃, crystallizing for 1h, filtering to obtain 76g of filter cake, drying the filter cake for 4h at 85 ℃ to obtain 71.1g of phthalic acid product, detecting the phthalic acid content by high performance liquid chromatography to be 99.7%, and meeting the quality standard that the phthalic acid content of an enterprise is more than or equal to 99.5%; evaporating the obtained filtrate by MVR, drying to obtain sodium chloride product, and detecting the content of sodium chloride by high performance liquid chromatography to obtain 98.3%.
Example 2
The embodiment provides a method for treating 4-chlorophthalic acid monosodium salt production wastewater, which comprises the following steps:
step one, adding 1g of ruthenium chloride into 30g of 60% ethanol solution, stirring and dissolving, then adding 18g of 4A silicon-aluminum eight-membered ring molecular sieve, stirring and mixing at room temperature for 1h, adding 28wt% ammonia water to adjust the pH value to 10.8, stirring and immobilizing at room temperature for 2h, adding 1.3g of 70% hydrazine hydrate solution, stirring and reacting at 70 ℃ for 1.5h, filtering to obtain 26.7g of wet catalyst, and drying at 105 ℃ for 2h to obtain 18.6g of ruthenium immobilized catalyst;
adding sodium hydroxide into 2000g of 4-chlorophthalic acid monosodium salt production wastewater, stirring and dissolving, then adjusting the pH to 11.3, evaporating and concentrating at the normal pressure and the temperature of 101 ℃, and evaporating 909g of water; after the water evaporation is finished, keeping the temperature at 101 ℃, adding 2.5g of 80% hydrazine hydrate, uniformly mixing, adding 10g of the prepared ruthenium-supported catalyst, dropwise adding 700g of sodium formate solution (200 g of sodium formate and 500g of water), wherein the dropwise adding time is 3h, reacting at 101 ℃ for 2h, filtering at 80 ℃, recovering 12.6g of the catalyst, 1835.9g of filtrate, and detecting that the pH value of the filtrate is 9.9;
adding 30% hydrochloric acid solution into the filtrate under the stirring condition to adjust the pH value to 1.3, cooling to 25 ℃, crystallizing for 1h, filtering to obtain 79g of filter cake, drying the filter cake for 4h at 85 ℃ to obtain 69.1g of phthalic acid product, detecting the phthalic acid content by high performance liquid chromatography to be 99.6%, and meeting the quality standard that the phthalic acid content of an enterprise is more than or equal to 99.5%; evaporating the obtained filtrate by MVR, drying to obtain sodium chloride product, and detecting the content of sodium chloride by high performance liquid chromatography to obtain 98.2%.
Example 3
The embodiment provides a method for treating 4-chlorophthalic acid monosodium salt production wastewater, which comprises the following steps:
step one, adding 1g of ruthenium chloride into 40g of 50% ethanol solution, stirring and dissolving, then adding 20g of 4A silicon-aluminum eight-membered ring molecular sieve, stirring and mixing at room temperature for 1h, adding 28wt% ammonia water to adjust the pH value to 9.2, stirring and immobilizing at room temperature for 1.5h, adding 1.5g of 60% hydrazine hydrate solution, stirring and reacting at 75 ℃ for 1h, filtering to obtain 28.6g of wet catalyst, and drying at 105 ℃ for 2h to obtain 20.5g of ruthenium immobilized catalyst;
adding sodium hydroxide into 2000g of 4-chlorophthalic acid monosodium salt production wastewater, stirring and dissolving, then adjusting the pH to 12.4, evaporating and concentrating at the normal pressure and the temperature of 101 ℃, and obtaining 973g of distilled water; after the water evaporation is finished, keeping the temperature at 101 ℃, adding 3g of 60% hydrazine hydrate, uniformly mixing, adding 6g of the prepared ruthenium-supported catalyst, dropwise adding 650g of hydroxylamine hydrochloride solution (150 g of hydroxylamine hydrochloride and 500g of water) for 2.5h, after the dropwise adding is finished, carrying out heat preservation reaction at 101 ℃ for 1.5h, then filtering at 80 ℃, recovering 8.3g of the catalyst, 1722.7g of filtrate, and detecting the pH value of the filtrate to be 10.2;
adding 30% hydrochloric acid solution into the filtrate under the stirring condition to adjust the pH value to 0.9, cooling to 25 ℃, crystallizing for 1h, filtering to obtain 79.6g of filter cake, drying the filter cake for 4h at 85 ℃ to obtain 75.1g of phthalic acid product, detecting the phthalic acid content by high performance liquid chromatography to be 99.6%, and meeting the quality standard that the phthalic acid content of an enterprise is more than or equal to 99.5%; evaporating the obtained filtrate by MVR, drying to obtain sodium chloride product, and detecting the content of sodium chloride by high performance liquid chromatography to obtain 98.1%.
The catalyst recovered in the second step of the embodiment 1-3 is recycled for 8-10 times, so that the purity of the prepared phthalic acid product can still reach 99.5 percent, and the quality standard that the content of phthalic acid in an enterprise is more than or equal to 99.5 percent is met.
Example 4
This example provides a method for treating wastewater from the production of monosodium 4-chlorophthalic acid, which comprises the same steps and process parameters as those in example 3, except that the 4A silicon aluminum eight-membered ring molecular sieve in example 3 is replaced with a 3A silicon aluminum eight-membered ring molecular sieve.
74.3g of phthalic acid product is finally prepared, the phthalic acid content is detected by high performance liquid chromatography to be 99.6%, and the quality standard that the phthalic acid content of an enterprise is more than or equal to 99.5% is met; evaporating the obtained filtrate by MVR, drying to obtain sodium chloride product, and detecting the content of sodium chloride by high performance liquid chromatography to obtain 98.2%.
The catalyst recovered in the second step of the embodiment 4 is recycled for 5-6 times, so that the purity of the prepared phthalic acid product can still reach 99.5 percent, and the quality standard that the content of phthalic acid in an enterprise is more than or equal to 99.5 percent is met.
The silicon-aluminum eight-membered ring molecular sieves used in the above examples 1 to 3 are 4A molecular sieves of angjesky environment-friendly adsorption material ltd. Example 4 used was a 3A molecular sieve from angjesky environment friendly adsorbent limited.
Comparative example 1
The comparative example provides a treatment method of 4-chlorophthalic acid monosodium salt production wastewater, which comprises the following steps:
adding sodium hydroxide into 2000g of 4-chlorophthalic acid monosodium salt production wastewater, stirring and dissolving, then adjusting the pH value to 12.4, carrying out evaporation concentration at normal pressure and 101 ℃, and obtaining 923g of distilled water; after the water evaporation is finished, keeping the temperature at 101 ℃, adding 3g of 60% hydrazine hydrate, uniformly mixing, adding 6g of 5% palladium carbon catalyst, dropwise adding 650g of hydroxylamine hydrochloride solution (150 g of hydroxylamine hydrochloride and 500g of water) for 2.5h, after the dropwise adding is finished, carrying out heat preservation reaction at 101 ℃ for 1.5h, then filtering at 80 ℃, recovering 11.8g of catalyst, 1792.3g of filtrate, and detecting the pH value of the filtrate to be 10.3;
under the condition of stirring, adding 30% hydrochloric acid solution into the filtrate to adjust the pH value to 1.1, cooling to 25 ℃, crystallizing for 1h, filtering to obtain 77.9g of filter cake, drying the filter cake at 85 ℃ for 4h to obtain 72.1g of phthalic acid product, detecting the content of phthalic acid by high performance liquid chromatography to 96.8%, benzoic acid to 0.9%, and biphenyl tetracarboxylic acid to 2.3%, which do not meet the quality standard that the content of phthalic acid in enterprises is more than or equal to 99.5%.
From experimental results, the palladium-carbon catalyst is used as a hydrogenation catalyst and can complete dechlorination reduction, but the selectivity is poor, benzoic acid and biphenyl tetracarboxylic acid are generated, and the introduction of impurities can influence the synthesis of subsequent products of the biphenyl tetracarboxylic dianhydride.
Comparative example 2
The comparative example provides a treatment method of 4-chlorophthalic acid monosodium salt production wastewater, which comprises the following steps:
step one, taking 1g of palladium chloride, adding 30g of 60% ethanol solution, stirring and dissolving, then adding 15g of 3A silicon-aluminum eight-membered ring molecular sieve, stirring and mixing at room temperature for 1h, adding 28wt% ammonia water to adjust the pH value to 10.8, stirring and immobilizing at room temperature for 2h, adding 1.3g of 70% hydrazine hydrate solution, stirring and reacting at 70 ℃ for 1.5h, filtering to obtain 23.7g of wet catalyst, and drying at 105 ℃ for 2h to obtain 15.6g of palladium immobilized catalyst;
adding sodium hydroxide into 2000g of 4-chlorophthalic acid monosodium salt production wastewater, stirring and dissolving, then adjusting the pH to 11.5, carrying out evaporation concentration at normal pressure and 102 ℃, and evaporating 912g of water; after the water evaporation is finished, keeping the temperature at 102 ℃, adding 2.5g of 80% hydrazine hydrate, uniformly mixing, adding 10g of the prepared palladium-supported catalyst, dropwise adding 700g of sodium formate solution (200 g of sodium formate and 500g of water), wherein the dropwise adding time is 3h, reacting at 102 ℃ for 2h, filtering at 80 ℃, recovering 12.6g of the catalyst, 1837.9g of filtrate, and detecting that the pH value of the filtrate is 9.9;
and step three, under the stirring condition, adding a 30% hydrochloric acid solution into the filtrate to adjust the pH value to 1.3, cooling to 25 ℃, crystallizing for 1h, filtering to obtain 78.5g of filter cake, drying the filter cake for 4h at 85 ℃ to obtain 68.5g of phthalic acid product, and detecting the phthalic acid content by using a high performance liquid chromatography to be 98.6%, wherein the phthalic acid content does not meet the quality standard that the phthalic acid content of an enterprise is more than or equal to 99.5%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A treatment method of 4-chlorophthalic acid or monosodium salt production wastewater thereof is characterized by comprising the following steps:
dissolving soluble ruthenium salt in an alcohol solvent, adding a silicon-aluminum eight-membered ring molecular sieve, uniformly mixing, stirring and immobilizing, adjusting the pH value to be alkaline, adding a first reducing agent to carry out reduction reaction, filtering and drying to obtain a ruthenium immobilized catalyst;
b, adjusting the pH value of the 4-chlorophthalic acid or monosodium salt production wastewater thereof to 11-13, distilling and concentrating, adding an activator and the ruthenium immobilized catalyst, uniformly mixing, then adding a second reducing agent, carrying out heat preservation reaction, and filtering to obtain a reaction solution;
and c, adjusting the pH value of the reaction liquid to 0.5-1.5, cooling, crystallizing, filtering and drying to obtain the phthalic acid.
2. The method for treating the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof as claimed in claim 1, wherein in the step a, the alcohol solvent is an ethanol aqueous solution with a mass concentration of 50-75%, and the mass ratio of the alcohol solvent to the soluble ruthenium salt is 25-40: 1.
3. The method for treating the production wastewater of 4-chlorophthalic acid or monosodium salt thereof according to claim 1, wherein in the step a, the particle size of the silicon-aluminum eight-membered ring molecular sieve is 1 mm-2 mm, and the pore size is 410 pm-430 pm.
4. The method for treating the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof according to claim 1 or 3, wherein in the step a, the mass ratio of the silicon-aluminum eight-membered ring molecular sieve to the soluble ruthenium salt is 15-20: 1.
5. The method for treating the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof as claimed in claim 1, wherein in the step a, the first reducing agent is a hydrazine hydrate solution with a mass concentration of 60-80%, and the mass ratio of the hydrazine hydrate solution to the soluble ruthenium salt is 1.1-1.5: 1.
6. The method for treating the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof according to claim 1, wherein in the step a, the temperature of the stirring immobilization is 20 ℃ to 30 ℃, and the time of the stirring immobilization is 1h to 2 h; and/or
In the step a, the alkalinity refers to that the pH value is 9-11; and/or
In the step a, the temperature of the reduction reaction is 60-75 ℃, and the time of the reduction reaction is 1-2 h.
7. The method for treating the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof according to claim 1, wherein in the step b, the activator is a hydrazine hydrate solution with a mass concentration of 20-80%, and the mass ratio of the hydrazine hydrate solution to the ruthenium-supported catalyst is 0.2-1: 1.
8. The method for treating wastewater from the production of 4-chlorophthalic acid or its monosodium salt according to claim 1, wherein in step b, the mass ratio of the ruthenium-supported catalyst to the wastewater from the production of 4-chlorophthalic acid or its monosodium salt is 0.001-0.005: 1.
9. The method for treating the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof according to claim 1, wherein in the step b, the second reducing agent is a sodium formate aqueous solution with the mass concentration of 16-30%, and the mass ratio of the sodium formate in the second reducing agent to the production wastewater of the 4-chlorophthalic acid or the monosodium salt thereof is 0.05-0.1: 1; or
In the step b, the second reducing agent is hydroxylamine hydrochloride solution with the mass concentration of 16-30%, and the mass ratio of hydroxylamine hydrochloride to 4-chlorophthalic acid or monosodium salt production wastewater thereof in the second reducing agent is 0.05-0.1: 1.
10. The method for treating the waste water from the production of 4-chlorophthalic acid or the monosodium salt thereof as claimed in claim 1, wherein in the step b, the distilled water amount from the distillation and concentration is 45-50% of the total mass of the waste water from the production of 4-chlorophthalic acid or the monosodium salt thereof; and/or
In the step b, the temperature of the heat preservation reaction is 95-105 ℃, and the time of the heat preservation reaction is 1-2 h; and/or
In the step c, the temperature for cooling crystallization is 15-30 ℃, and the time for cooling crystallization is 1-1.5 h.
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