CN104910004B - A kind of method of PTA waste residue resource - Google Patents
A kind of method of PTA waste residue resource Download PDFInfo
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- CN104910004B CN104910004B CN201410088874.7A CN201410088874A CN104910004B CN 104910004 B CN104910004 B CN 104910004B CN 201410088874 A CN201410088874 A CN 201410088874A CN 104910004 B CN104910004 B CN 104910004B
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Abstract
The present invention provides a kind of method of PTA waste residue resource, it relates to chemical field. Described method comprises: step 1: PTA waste residue is dissolved in mixture of sulfuric phosphoric acid completely, adds water, filtering separation filter residue E and mother liquor E; Step 2: add water in mother liquor E, precipitates out filter residue A, separation filter residue A and mother liquor A; Step 3: step 2 gained benzene carboxylic acid is heated to 105-95 DEG C, obtains phenylformic acid and residual residue; Step 4: add water in described residual residue, be heated to 90-100 DEG C, filtering separation filter residue B and mother liquor B; Step 5: mother liquor B is cooled, filtration is got crystal and is obtained O-phthalic acid crystal; Step 6: adding ammoniacal liquor in described mother liquor A, adjust pH, to 0.5-1.5, is filtered to remove residue; Then pH to 6.5-7.5, filtering separation filter residue C and mother solution C is regulated. The inventive method, receipts rate height, it is possible to turn waste into wealth, environmentally friendly.
Description
Technical field
The present invention relates to chemical field, it is specifically related to the novel method of a kind of PTA waste residue resource.
Background technology
Pure terephthalic acid (PTA) is a kind of industrial chemicals extremely important in polyester industrial. Within 2013, its domestic production capacity has reached 3,938 ten thousand tons, produces according to every ton of PTA and produces 5 kilograms of waste residues calculating, produces now 200,000 tons of PTA waste residues every year, if directly filling or burning, pollutes the environment, waste valuable resource; Therefore, the Separation and Recovery recycling of organic carboxyl acid in PTA waste residue had great economy and environment benefit.
According to production process, PTA waste residue being divided into three major types: the oxidation residua that namely oxidation unit produces, the solid residue of the mother that refined unit produces, they are all the by products formed in production process; In addition, for the fouling material removed in pipeline and various equipment, Chang Yaoyong alkali lye washs, a large amount of waste material containing phthalate all discharges in wastewater disposal basin, comprising other waste materials that are on-the-spot and other system run, drip, leak formation also all to enter in wastewater disposal basin, this part waste residue is called as pond waste material. In some producer, three kinds of waste residues often finally mix. Above-mentioned three class waste residues can be referred to as PTA waste residue��1����
Adopt and also it is not quite similar without the PTA waste residue component of patent production technology: even same enterprise, the waste residue that the product of different batches produces also exists difference. Generally speaking, PTA waste residue is often containing certain moisture, and solid phase is based on organic carboxyl acid. Except terephthalic acid, also have phenylformic acid, phthalic acid, m-phthalic acid, and the p-carboxybenzaldehyde of minute quantity, trimellitic acid, trimesic acid, fluorenes ketone and the cobalt-manganese catalyst not reclaimed completely, solvent acetic acid and other mechanical impuritys etc.
Current treatment process mainly contains four kinds of modes:
1, burn. External in order to remove pollution, adopt the method burned. This method only reclaims the energy, but wastes resource. Jinan chemical fibre group company at device internal recovering cobalt-manganese salt, oxidation residua containing cobalt only ten thousand/several, without recovery value, all burn. Nanjing Yang Zi petro-chemical corporation also have passed the technical evaluation of incineration oxidation residue. 2, Call Provision salt[2]. Being compare rare metal due to cobalt, some factory Call Provision salt, such as Liaoyang petro-chemical fiber company, Beijing Yanshan Petrochemical Company, Nanjing Yang Zi petro-chemical corporation, Luoyang Petrochemical company etc. are all like this. Wherein raise the first recovery of acetic acid of residue of son, then Call Provision salt, recycle better. Other organism burn or stack, contaminate environment.
3, organic acid reclaims. The separation method seeing the oxidation residua of document mainly contains three classes:
(1) steam distillation. The steam distillation of pressure 0.2��1Mpa such as DeNadai obtains phenylformic acid, and the phenylformic acid rate of recovery is 97%. But the method consumes a large amount of energy and water resources, therefore it is not suitable for applying at home.
(2) hot water leaching method. DeNadai etc. are that solvothermal leaching oxidation residua makes whole dissolving the such as phenylformic acid and Co, Mn catalyzer enter solution taking water, m-phthalic acid and terephthalic acid stay solid phase, filtered while hot makes material be divided into two portions, from the partially recycled terephthalic acid of solid phase and m-phthalic acid mixture, the rate of recovery is respectively 95% and 98%. Liquid phase part is through cooling phenylformic acid crystallization, more after filtration from liquid phase Call Provision Mn catalyst, solid phase is crude benzol formic acid. Crude benzol formic acid recrystallization in water obtains purified petroleum benzin formic acid, the rate of recovery 94.3%. In the method introduced in current document, the method is relatively good method, but it is many still to there is energy consumption height, operation steps, though the phenylformic acid purity obtained is high but color is not good, range of application is restricted.
(3) acid-precipitation method[3]. First oxidation residua being carried out washing process, the phthalic acid making catalyzer and content very little enters solution. Reclaiming catalyzer from liquid phase, phthalic acid etc. are abandoned because measuring little. Solid phase residual residue use water pull an oar after at 130 DEG C of temperature, adding salt of weak acid adjustment PH value is 4.2��4.5 make it be divided into two-phase. Heng Geer acid-precipitation method principle according to improvement is under having benzoate to exist, and containing benzoate and m-phthalic acid salt in liquid phase, solid phase is the mixture of phenylformic acid and terephthalic acid. Liquid phase acid adding acid out and filtration benzene extracting makes phenylformic acid be separated with m-phthalic acid, solid phase methyl alcohol makes phenylformic acid be separated with terephthalic acid as extraction solvent. Obtain phenylformic acid, terephthalic acid and m-phthalic acid three kinds of compounds so respectively. P-methylbenzoic acid, p-carboxybenzaldehyde etc. lose in sepn process. The method sepn process is loaded down with trivial details, it may also be useful to chemical feedstocks and solvent too much.
In a word, aforesaid method, due to power consumption, the consumption reason such as water or complex process, causes separation costs higher, have impact on the resource utilization of PTA waste residue. If the method that environment for use is friendly, economical and practical, by PTA waste residue resource, isolate phthalic acid, prepare plastic plasticizer[4], unsaturated polyester resin[5], polyester coating etc.[6-9]. To have economic and social benefit.
This project adopts mixture of sulfuric phosphoric acid to be solvent, isolates phenylformic acid, phthalic acid, terephthalic acid and m-phthalic acid by recrystallization method.
Summary of the invention
It is an object of the invention to provide a kind of method that can isolate phenylformic acid, phthalic acid, terephthalic acid and m-phthalic acid from PTA waste residue, receipts rate height, it is possible to turn waste into wealth, environmentally friendly.
The object of the present invention is adopted and is realized with the following method.
A method for PTA waste residue resource, comprises the steps:
Step 1: PTA waste residue is dissolved in mixture of sulfuric phosphoric acid completely, adds water, precipitates out filter residue E, filtering separation filter residue E and mother liquor E, and described filter residue E is terephthalic acid; Described mixture of sulfuric phosphoric acid is the mixture of sulfuric acid and phosphoric acid;
Step 2: add water in the mother liquid obtained E of step 1, precipitates out filter residue A, and described filter residue A is benzene carboxylic acid, filtering separation filter residue A and mother liquor A;
Step 3: step 2 gained benzene carboxylic acid is heated to 105-95 DEG C, obtains phenylformic acid and residual residue;
Step 4: add water in residual residue described in step 3, be heated to 90-100 DEG C, filtering separation filter residue B and mother liquor B, described filter residue B is m-phthalic acid;
Step 5: mother liquid obtained B in step 4 is cooled, crystallize out, filtration is got crystal and is obtained O-phthalic acid crystal;
Step 6: adding ammoniacal liquor in described mother liquor A in step 2, adjust pH, to 0.5-1.5, is filtered to remove residue; Then regulating pH to 6.5-7.5, filtering separation filter residue C and mother solution C, described filter residue C is the oxyhydroxide of cobalt and manganese, obtains the mixture of ammonium sulfate and ammonium phosphate after described mother solution C is concentrated.
The mass percentage of described sulfuric acid is 85%, and the mass percentage of described phosphoric acid is 83%. Heating temperature described in step 3 is 100 DEG C. 95 DEG C it are heated to be described in step 4. In described mixture of sulfuric phosphoric acid, the volume ratio of sulfuric acid and phosphoric acid is 1:0 ~ 0.3, it is preferable to 1:0.15.
China is the big producing country of terephthalic acid (PTA), and the nearly 4,000 ten thousand tons of PTA of annual production, produce every ton of PTA by generation about 5 kilograms of PTA waste residues, annual generation 200,000 tons of waste residues. These waste residues contain phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid, and as catalyzer use cobalt salt and manganese salt. The composition of the PTA waste residue that the present invention measures according to liquid chromatography, atomic absorption spectrum and moisture teller, as shown in table 1.
The PTA waste residue sample of three kinds of different PTA production factories dry after component
The concrete grammar of the present invention is as shown in Figure 1. PTA waste residue adds certain density mixture of sulfuric phosphoric acid. Controlled concentration, crystallization goes out terephthalic acid, regulates concentration phenylformic acid, phthalic acid and m-phthalic acid to be precipitated out, is mainly inorganic salt and a small amount of organic acid in mother liquor. Ammoniacal liquor adjust pH precipitates out organism, cobalt salt, manganese salt successively. Residue raffinate prepares ammonium sulfate and ammonium phosphate. By the mixture heating sublimation of phenylformic acid, phthalic acid, m-phthalic acid, isolate crystal phenylformic acid. Remaining solid is according to 95oUnder C, phthalic acid solubleness in water is 55 times of m-phthalic acid, reaches effective separation. The present invention take mixture of sulfuric phosphoric acid as solvent, by recrystallization successfully by PTA waste residue resource. Therefore, meet environmental protection and green environment requirement. It is expected to the method to be applied on a large scale in suitability for industrialized production from now on.
Accompanying drawing explanation
Fig. 1 is the PTA process for reclaiming route map that the present invention relates to.
Fig. 2 is the infrared spectrum of phenylformic acid.
Embodiment
The present invention is described by the following examples further:
Mixture of sulfuric phosphoric acid is as in the preparation of solvent, the volume ratio of sulfuric acid (85wt%) and phosphoric acid (83wt%) is 1:0 ~ 0.3, being preferably 1:0.15, in following examples, mixture of sulfuric phosphoric acid composition is all the volume ratio of sulfuric acid (85wt%) and phosphoric acid (83wt%) is 1:0.15
Embodiment 1
The recrystallization of step 1. terephthalic acid. Getting 100g sample 1 joins in 195mL mixture of sulfuric phosphoric acid, stirs 1 hour, leaves standstill 1 hour, filters, adds 55mL water in mother liquor, filters, dry, obtains white terephthalic acid solid 46.9g.
The mother liquor of gained in step 1 is added 140mL water by step 2., precipitates out benzene carboxylic acid, filters and be separated with mother liquor by benzene carboxylic acid, dry must mixture 48.9g.
The benzene carboxylic acid 48.9g of gained in step 2 is heated to 100 by step 3.oC distils, and obtains white phenylformic acid crystal 16.3g, residual residue 29.9g. The confirmation of phenylformic acid is as shown in Figure 2.
The residual residue 29.9g of gained in step 3 is added 110mL water by step 4., and heat is to 95oC, filters, dry, obtains m-phthalic acid 15.0g.
The mother liquor of gained in step 4 is cooled by step 5., precipitates out O-phthalic acid crystal, filters, dry, obtains phthalic acid 13.5g.
Step 6. adds ammoniacal liquor adjust pH by mother liquid obtained in step 2, organic detritus 1.7g is filtered out during pH=1, pH=7 filters out the oxyhydroxide 3.8g precipitating out cobalt and manganese, residue mother liquor concentrations obtains the mixture 410g of ammonium sulfate and ammonium phosphate, sharing the strong aqua 478mL removing 28wt%, gained ammonium salt can be used as rare-earth extractant.
Embodiment 2
The recrystallization of step 1. terephthalic acid. Getting 100g sample 1 joins in 201mL mixture of sulfuric phosphoric acid, stirs 1 hour, leaves standstill 1 hour, filters, adds 57mL water in mother liquor, filters, dry, obtains white terephthalic acid solid 42.4g.
The mother liquor of gained in step 1 is added 144mL water by step 2., precipitates out benzene carboxylic acid, filters and be separated with mother liquor by benzene carboxylic acid, dry must mixture 46.7g.
The benzene carboxylic acid 46.7g of gained in step 2 is heated to 100 by step 3.oC distils, and obtains white phenylformic acid crystal 22.8g, residual residue 51.5g.
The residual residue 51.5g of gained in step 3 is added 190mL water by step 4., and heat is to 95oC, filters, dry, obtains m-phthalic acid 25.0g.
The mother liquor of gained in step 4 is cooled by step 5., precipitates out O-phthalic acid crystal, filters, dry, obtains phthalic acid 23.8g.
Step 6. adds ammoniacal liquor adjust pH by mother liquid obtained in step 2, filtering out organic detritus 1.5g during pH=1, pH=7 obtains the mixture 430g of ammonium sulfate and ammonium phosphate without precipitation, residue mother liquor concentrations, sharing the strong aqua 485mL removing 28wt%, gained ammonium salt can be used as rare-earth extractant.
Embodiment 3
The recrystallization of step 1. terephthalic acid. Getting 100g sample 1 joins in 305mL mixture of sulfuric phosphoric acid, stirs 1 hour, leaves standstill 1 hour, filters, adds 90mL water in mother liquor, filters, dry, obtains white terephthalic acid solid 16.8g.
The mother liquor of gained in step 1 is added 215mL water by step 2., precipitates out benzene carboxylic acid, filters and be separated with mother liquor by benzene carboxylic acid, dry must mixture 74.2g.
The benzene carboxylic acid 74.2g of gained in step 2 is heated to 100 by step 3.oC distils, and obtains white phenylformic acid crystal 16.3g, residual residue 29.9g.
The residual residue 29.9g of gained in step 3 is added 110mL water by step 4., and heat is to 95oC, filters, dry, obtains m-phthalic acid 15.0g.
The mother liquor of gained in step 4 is cooled by step 5., precipitates out O-phthalic acid crystal, filters, dry, obtains phthalic acid 13.5g.
Step 6. adds ammoniacal liquor adjust pH by mother liquid obtained in step 2, organic detritus 1.7g is filtered out during pH=1, pH=7 filters out the oxyhydroxide 3.8g precipitating out cobalt and manganese, residue mother liquor concentrations obtains the mixture 620g of ammonium sulfate and ammonium phosphate, sharing the strong aqua 759mL removing 28wt%, gained ammonium salt can be used as rare-earth extractant.
Claims (3)
1. the method for a PTA waste residue resource, it is characterised in that comprise the steps:
Step 1: PTA waste residue is dissolved in mixture of sulfuric phosphoric acid completely, adds water, precipitates out filter residue E, filtering separation filter residue E and mother liquor E, and described filter residue E is terephthalic acid; Described mixture of sulfuric phosphoric acid is the mixture of sulfuric acid and phosphoric acid;
Step 2: add water in the mother liquid obtained E of step 1, precipitates out filter residue A, and described filter residue A is benzene carboxylic acid, filtering separation filter residue A and mother liquor A;
Step 3: step 2 gained benzene carboxylic acid is heated to 105-95 DEG C, obtains phenylformic acid and residual residue;
Step 4: add water in residual residue described in step 3, be heated to 90-100 DEG C, filtering separation filter residue B and mother liquor B, described filter residue B is m-phthalic acid;
Step 5: mother liquid obtained B in step 4 is cooled, crystallize out, filtration is got crystal and is obtained O-phthalic acid crystal;
Step 6: adding ammoniacal liquor in described mother liquor A in step 2, adjust pH, to 0.5-1.5, is filtered to remove residue; Then regulating pH to 6.5-7.5, filtering separation filter residue C and mother solution C, described filter residue C is the oxyhydroxide of cobalt and manganese, obtains the mixture of ammonium sulfate and ammonium phosphate after described mother solution C is concentrated; The mass percentage of described sulfuric acid is 85%, and the mass percentage of described phosphoric acid is 83%; In described mixture of sulfuric phosphoric acid, the volume ratio of sulfuric acid and phosphoric acid is 1:0.15.
2. the method for PTA waste residue resource according to claim 1, it is characterised in that Heating temperature described in step 3 is 100 DEG C.
3. the method for described PTA waste residue resource according to claim 2, it is characterised in that be heated to be 95 DEG C described in step 4.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255107A (en) * | 2008-04-03 | 2008-09-03 | 沈福昌 | Resourceful treatment method of purified terephthalic acid waste residue |
| WO2011119395A2 (en) * | 2010-03-26 | 2011-09-29 | Invista Technologies S.A.R.L. | Recovery of aromatic carboxylic acids and oxidation catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255107A (en) * | 2008-04-03 | 2008-09-03 | 沈福昌 | Resourceful treatment method of purified terephthalic acid waste residue |
| WO2011119395A2 (en) * | 2010-03-26 | 2011-09-29 | Invista Technologies S.A.R.L. | Recovery of aromatic carboxylic acids and oxidation catalyst |
Non-Patent Citations (2)
| Title |
|---|
| PTA装置氧化残渣的回收利用;韦士平;《聚酯工业》;20040630;第17卷(第3期);第13-14、31页 * |
| 精对苯二甲酸残渣的处理现状及综合利用;何小娟 等;《上海环境科学》;20061231;第25卷(第5期);第224-227页 * |
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Effective date of registration: 20171227 Address after: 236000 Economic Development Zone, Taihe County, Fuyang, Anhui Province, B District Patentee after: Wang Biao Address before: No. 213, Fang Cao Road, Industrial Development Zone along the Yangtze River, Nanjing, Jiangsu Province, A8-912 Patentee before: Zhang Chaozhi |
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Application publication date: 20150916 Assignee: Anhui Tingmei environmental protection equipment Co.,Ltd. Assignor: ANHUI HENGYU ENVIRONMENTAL PROTECTION EQUIPMENT MANUFACTURING LIMITED BY SHARE Ltd. Contract record no.: X2022980008544 Denomination of invention: A method of recycling PTA waste residue Granted publication date: 20160601 License type: Common License Record date: 20220623 |
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Denomination of invention: A method of recycling PTA waste residue Effective date of registration: 20221214 Granted publication date: 20160601 Pledgee: China Construction Bank Taihe sub branch Pledgor: ANHUI HENGYU ENVIRONMENTAL PROTECTION EQUIPMENT MANUFACTURING LIMITED BY SHARE Ltd. Registration number: Y2022980027420 |