CN117603041A - Recovery method of benzoic acid in PTA residue - Google Patents
Recovery method of benzoic acid in PTA residue Download PDFInfo
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- CN117603041A CN117603041A CN202311639679.4A CN202311639679A CN117603041A CN 117603041 A CN117603041 A CN 117603041A CN 202311639679 A CN202311639679 A CN 202311639679A CN 117603041 A CN117603041 A CN 117603041A
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- China
- Prior art keywords
- oil
- pta
- benzoic acid
- water
- solvent
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 36
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 235000019198 oils Nutrition 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019476 oil-water mixture Nutrition 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000008247 solid mixture Substances 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims description 12
- -1 alkyl acetate Chemical compound 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 61
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 229960004365 benzoic acid Drugs 0.000 description 22
- 239000002699 waste material Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 13
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 10
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for recovering benzoic acid in PTA (purified terephthalic acid) residues. Fully dissolving and extracting PTA oxidation residues, water and a solvent A in a mixer; filtering and separating the extract, wherein the filtrate is an oil-water mixture, and transferring the mixture to an oil-water separator to obtain filter residues in a solid phase; and drying the filter residue to obtain a solid mixture byproduct taking isophthalic acid as a main component. The oil-water mixture enters an oil-water separator, after being fully mixed, the oil-water separation is carried out, and the oil phase is separated to obtain a solvent A, benzoic acid and PT acid. And (3) distilling and separating the solvent A in the oil phase under reduced pressure, returning the solvent A to the residue mixer for recycling, continuously distilling and separating out benzoic acid in the residual oil phase under reduced pressure, and returning residual PT acid and the like to the oxidation reactor for use. The purity of the separated benzoic acid solid can reach 98.0 percent. The invention not only greatly reduces the environmental-friendly treatment cost of PTA residues, but also recovers organic matters, and has remarkable economic benefit.
Description
Technical Field
The invention relates to the technical field of chemical environment-friendly substance separation, and relates to a recycling method of organic matters in PTA (purified terephthalic acid) production residues.
Background
Refined terephthalic acid (PTA) is an important chemical raw material, and the PTA is mainly produced by a para-xylene (PX) air oxidation method at present, and the production process consists of a PX oxidation unit and a TA hydrofining unit. PX is dissolved in HAC-water solvent, cobalt/manganese/bromine is used as catalyst, PX and oxygen are subjected to oxidation reaction, the reaction temperature is 192-202 ℃, and the pressure is 1.3-1.65 MPa, so that crude Terephthalic Acid (TA) is generated; TA is dissolved in water at 270-290 deg.c, and through catalytic hydrofining, multistage crystallization, solid-liquid separation and other steps, refined terephthalic acid (PTA) product is obtained.
The demand of PTA in China rapidly increases in recent decades, a plurality of large PTA devices (more than 100 ten thousand tons in annual production) are newly built in China, and serious environmental pollution is brought, and particularly the problems of PTA wastewater and waste residues are outstanding.
According to the investigation, a set of large-scale devices producing 200 ten thousand tons of PTA annually can produce about 1.8 ten thousand tons of PTA production waste residue each year, and the total amount of PTA production waste residue (residue) is quite considerable. Because the components of the PTA waste residue are very complex and the content of each component is also changed, a certain technical difficulty is brought to the comprehensive recycling of the PTA waste residue, and the common method for treating the PTA waste residue in European and American developed countries is an incineration method, and then precious metals are recovered from the PTA waste residue. Although the incineration method is a disposal method for thoroughly treating PTA waste residues, a large amount of precious organic carboxylic acid resources in the waste residues are not utilized, and the incineration method is a huge waste.
The nature of PTA slag is determined by its production process. According to the production process, PTA waste residues are divided into three main categories: namely, oxidized residues generated by an oxidation unit and mother solid residues generated by a refining unit, wherein the two waste residues are mainly byproducts generated in the production process; in another type, in order to remove the scaling materials in various equipment and pipelines, the waste water is usually washed with alkali liquor, and a large amount of waste materials containing sodium phthalate salt are discharged and all discharged into a waste water tank, and other waste materials which are run, overflow, drip and leak out of the field and other systems are finally discharged into the waste water tank, and the waste residues are also called as tank bottom materials.
According to investigation, the components of PTA waste residues produced by different technologies are very different, wherein the PTA oxidation residues account for more than 80% of the total amount of the produced waste residues. The main organic components in the PTA oxidation residue include Benzoic Acid (BA), p-methyl benzoic acid (PT acid), terephthalic Acid (TA), isophthalic acid (IPA), phthalic acid (OPA), trimellitic acid (TMA) and the like; wherein the content of Benzoic Acid (BA) is highest, and the mass fraction reaches more than 40%. The conventional incineration and landfill processes treat PTA production residues, which not only cause waste of recyclable organic materials, but also cause serious environmental pollution, so that effective treatment of PTA residues is necessary.
Disclosure of Invention
The invention aims to provide a recovery method of benzoic acid in PTA residues, which can obtain high-purity benzoic acid and other benzene carboxylic acid byproducts, thereby greatly reducing the environmental-friendly treatment cost of PTA residues and recovering organic matter resources.
1. The method for recycling benzoic acid in PTA residues is characterized by comprising the following steps:
(1) Fully dissolving oxidation residues generated in the PTA production process, and fully dissolving and extracting water and a solvent A in a mixer; (2) Filtering and separating the extract by a filter with proper mesh number, wherein the filtrate is an oil-water mixture, and transferring the mixture to an oil-water separator to obtain filter residues in a solid phase; (3) The filter residue is insoluble solid matter, and the solid mixture byproduct taking isophthalic acid as a main component is obtained after the filter residue is dried; (4) The oil-water mixture enters an oil-water separator, is fully mixed, is kept still for layering, is subjected to oil-water separation, and is separated into an oil phase to obtain a solvent A, benzoic acid and PT acid. (5) The solvent A in the oil phase is separated by reduced pressure distillation and returned to the residue mixer for recycling; (6) And the residual oil phase is distilled under reduced pressure to separate out benzoic acid, and the residual PT acid and the like are returned to the oxidation reactor for use.
2. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: the solvent A in the step (1) is alkyl acetate.
3. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: the operation temperature of dissolution and extraction in the step (1) is 30-45 ℃, the mass ratio of the extraction solvent A to water is (2.5-3.5) 1, and the mass ratio of water to dry residue is (1.0-1.3) 1; the dissolution-extraction residence time is 20-35 minutes.
4. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: and (2) adopting a filter with the number of 100-300 meshes.
5. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: and (3) standing the oil-water mixture in the step (4) for 25-45 minutes.
The invention aims to recycle oxidation residues in the PTA production process to obtain high-purity benzoic acid and other benzene carboxylic acid byproducts, wherein the purity of benzoic acid solid can reach 98%. The method not only greatly reduces the environmental-friendly treatment cost of PTA residues, but also recovers organic resources. The method has the advantages of low energy consumption and low investment and operation maintenance cost; the economic benefit is obvious.
Description of the embodiments
Example 1
The PTA residue employed was taken from oxidized residue produced by a large scale plant (210 ten thousand tons of PTA/year) from Jiangsu petrochemical company-batch 1. Fully dissolving oxidized residues, water and a solvent A (alkyl acetate) generated in the PTA production process in a mixer, and extracting, wherein the operation temperature of dissolution-extraction is 35 ℃, the mass ratio of the extraction solvent A to water is 2.5:1, and the mass ratio of water to dry residues is 1.1:1; the dissolution-extraction residence time was 30 minutes. Filtering and separating the extract, wherein the filtrate is an oil-water mixture, and transferring the mixture to an oil-water separator to obtain filter residues in a solid phase; and drying the filter residue to obtain a solid mixture byproduct taking isophthalic acid as a main component. The oil-water mixture enters an oil-water separator, the oil-water mixture is layered for 35 minutes after being fully mixed, the oil-water separation is carried out, and the oil phase is separated to obtain a solvent A, benzoic acid and PT acid. And (3) distilling and separating the solvent A (alkyl acetate) in the oil phase under reduced pressure, returning the solvent A (alkyl acetate) to the residue mixer for recycling, continuously distilling and separating out benzoic acid in the residual oil phase under reduced pressure, and returning residual PT acid and the like to the oxidation reactor for use. The purity of the separated benzoic acid solid can reach 98.0 percent.
Example 2
The PTA residue employed was taken from oxidized residue produced by a large scale plant (210 ten thousand tons of PTA/year) from Jiangsu petrochemical company-batch 2. Fully dissolving oxidized residues, water and a solvent A (alkyl acetate) generated in the PTA production process in a mixer, and extracting, wherein the operation temperature of dissolution-extraction is 40 ℃, the mass ratio of the extraction solvent A to water is 3.0:1, and the mass ratio of water to dry residues is 1.2:1; the dissolution-extraction residence time was 35 minutes. Filtering and separating the extract, wherein the filtrate is an oil-water mixture, and transferring the mixture to an oil-water separator to obtain filter residues in a solid phase; and drying the filter residue to obtain a solid mixture byproduct taking isophthalic acid as a main component. The oil-water mixture enters an oil-water separator, the oil-water mixture is layered for 40 minutes after being fully mixed, the oil-water separation is carried out, and the oil phase is separated to obtain a solvent A, benzoic acid and PT acid. And (3) distilling and separating the solvent A (alkyl acetate) in the oil phase under reduced pressure, returning the solvent A (alkyl acetate) to the residue mixer for recycling, continuously distilling and separating out benzoic acid in the residual oil phase under reduced pressure, and returning residual PT acid and the like to the oxidation reactor for use. The purity of the separated benzoic acid solid can reach 98.2 percent.
Claims (5)
1. The method for recycling benzoic acid in PTA residues is characterized by comprising the following steps:
(1) Fully dissolving and extracting PTA oxidation residues, water and a solvent A in a mixer; (2) Filtering and separating the extract by a filter with proper mesh number, wherein the filtrate is an oil-water mixture, and transferring the mixture to an oil-water separator to obtain filter residues in a solid phase; (3) The filter residue is insoluble solid matter, and the solid mixture byproduct taking isophthalic acid as a main component is obtained after the filter residue is dried; (4) The oil-water mixture enters an oil-water separator, is fully mixed, is kept still for layering, is subjected to oil-water separation, and is separated into an oil phase to obtain a solvent A, benzoic acid and PT acid. (5) The solvent A in the oil phase is separated by reduced pressure distillation and returned to the residue mixer for recycling; (6) And the residual oil phase is distilled under reduced pressure to separate out benzoic acid, and the residual PT acid and the like are returned to the oxidation reactor for use.
2. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: the solvent A in the step (1) is alkyl acetate.
3. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: the operation temperature of dissolution and extraction in the step (1) is 30-45 ℃, the mass ratio of the extraction solvent A to water is (2.5-3.5) 1, and the mass ratio of water to dry residue is (1.0-1.3) 1; the dissolution-extraction residence time is 20-35 minutes.
4. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: and (2) adopting a filter with the number of 100-300 meshes.
5. The method for recovering benzoic acid from PTA residue according to claim 1, wherein: and (3) standing the oil-water mixture in the step (4) for 25-45 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311639679.4A CN117603041A (en) | 2023-12-04 | 2023-12-04 | Recovery method of benzoic acid in PTA residue |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311639679.4A CN117603041A (en) | 2023-12-04 | 2023-12-04 | Recovery method of benzoic acid in PTA residue |
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| Publication Number | Publication Date |
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| CN117603041A true CN117603041A (en) | 2024-02-27 |
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| CN202311639679.4A Pending CN117603041A (en) | 2023-12-04 | 2023-12-04 | Recovery method of benzoic acid in PTA residue |
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| CN (1) | CN117603041A (en) |
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2023
- 2023-12-04 CN CN202311639679.4A patent/CN117603041A/en active Pending
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