CN101513641A - Resource treatment method for fine terephthalic acid waste residue - Google Patents

Resource treatment method for fine terephthalic acid waste residue Download PDF

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Publication number
CN101513641A
CN101513641A CNA2009101305434A CN200910130543A CN101513641A CN 101513641 A CN101513641 A CN 101513641A CN A2009101305434 A CNA2009101305434 A CN A2009101305434A CN 200910130543 A CN200910130543 A CN 200910130543A CN 101513641 A CN101513641 A CN 101513641A
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waste residue
acid
cobalt
terephthalic acid
residue
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CN101513641B (en
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沈福昌
沈建东
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Taixing Fosunny Environmental Technology Co Ltd
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    • 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
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • C07C51/493—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification whereby carboxylic acid esters are formed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Catalysts (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to a resource treatment method for fine terephthalic acid waste residue, which includes steps of heating and separating the fine terephthalic acid waste residue to obtain crude monoacid and dibasic acid; removing light component from the crude monoacid, and rectifying to obtain benzoic acid; adding alcohol and sulfuric acid or titanium series, aluminum series or cobalt series catalyst into the crude dibasic acid to react, using activated carbon to decolor, neutralizing, washing by water and rectifying to obtain terephthalic acid ester product; feeding rectified residue to fuel-free incinerator to burn, and extracting rare metal such as cobalt and manganese from ash generated by burning. By adopting the method to treat fine terephthalic acid waste residue, chemical product such as benzyl acid and terephthalic acid and rare metal such as cobalt and manganese can be extracted; worthless waste residue is burned without any fuel, the waste residue can be used as fuel, and the heat energy generated by burning can be recycled to realize resource, harmlessness and quantitative reduction of chemical waste residue treatment and accord with circular economy requirement and environmental protection requirement.

Description

The recycling processing method of p-phthalic acid's waste residue
Technical field
The present invention relates to a kind of recycling processing method of chemical sludge, be specifically related to a kind of recycling processing method of p-phthalic acid's waste residue.
Background technology
(purified terephthalic acid PTA) is the base stock of producing polyester fiber and PET resin to the p-phthalic acid.P-phthalic acid's residue is the chemical industry discarded object of discharging in p-phthalic acid's production process, its composition more complicated, main component have benzoic acid, terephthalic acid (TPA), to Phenylbenzoic acid, to carboxyl benzaldehyde, phthalic acid, M-phthalic acid, phthalic acid and condensation product etc.External main p-phthalic acid manufacturing enterprise is to handle by burning method to the processing method of p-phthalic acid's waste residue mostly, and employing coal or fuel oil are burnt the organic acid in the waste residue, and such draff processing method all causes significant wastage to resource, the energy; More domestic p-phthalic acid manufacturing enterprises, then be that p-phthalic acid's waste residue is washed processing, wherein cobalt acetate, manganese acetate are reclaimed, and valuable resource has been wasted in waste residue air storage or both environment had been caused severe contamination with big water gaging dilution discharge.
Summary of the invention
The object of the present invention is to provide and a kind ofly both can effectively extract resource, simultaneously the recycling processing method to p-phthalic acid's waste residue of compliance with environmental protection requirements again.
The recycling processing method of a kind of p-phthalic acid's waste residue provided by the invention comprises the following steps:
A. the PTA waste residue is heated to 60～100 ℃, the cut that obtains is thick monoacid;
B. separating step a gained waste residue obtains thick binary acid;
C. the described thick monoacid of step a is controlled at 50～80 ℃ and takes off light component, carry out rectifying and get benzoic acid through 180～280 ℃, negative pressure 0.6～0.95Mpa again;
D. in the thick binary acid input reactor described in the step b, add alcohol and sulfuric acid, titanium series, aluminium series or cobalt catalyst series and react, the control reaction temperature is 60～100 ℃, and the reaction time is 2～10h;
E. the reactant mixture that steps d is obtained is used activated carbon decolorizing under 50～95 ℃ of conditions, and 2～5h holds time;
F. with in the input of the material after the step e decolouring and still, under 50～95 ℃ of conditions, with NaOH or NaHCO 3Neutralize, be cooled to normal temperature then and wash, control pH value is at 5.5～7.0 ℃;
G. with step f gained material input rectifying column, rectifying under 180～280 ℃, negative pressure 0.7～0.98Mpa condition obtains the terephthalic acid (TPA) esters product;
H. with described waste water, the rectified residue that obtains after light of taking off of step c, the described rectified residue of step g is sent into respectively and is exempted from burning disposal in the fuel incinerator;
I. burn from step h gained and extract rare metal cobalt, manganese the lime-ash that produces.
For separating the process of waste residue among the performing step b, adopt plate cabinet filter press or centrifuge.
The alcohols that adds in the steps d can be methyl alcohol or ethanol or octanol or ethylene glycol.
In order to extract rare metal cobalt, manganese, adopt NH 4HCO 3Solution is precipitate cobalt, manganese simultaneously, then with the acetate dissolution of coming, and the repeatedly refining again acetic acid cobalt-manganese salt that finally obtains.
Adopt the recycling processing method of p-phthalic acid's waste residue of the present invention, can extract the p-phthalic acid, the chemical products of terephthalic acid (TPA) etc. and rare metal cobalt, manganese; The waste residue of no value is burning disposal under no need of any fuel condition, waste residue can be done fuel uses, the heat energy recycle that can burn produce again can realize that chemical waste residue handles resource, innoxious, minimizing, meets recycling economy and require and environmental requirement.
Description of drawings
Fig. 1 represents industrial flow chart of the present invention.
The specific embodiment
The PTA waste residue is dropped in the still, be heated to 80 ℃, stir simultaneously, make the benzoic acid dissolving, adopt centrifuge to carry out centrifugal while hot.Gained filtrate is thick monoacid (quality be former slag 43%), and filter residue is thick binary acid (quality be former slag 56%).
In thick monoacid input still, adjusting temperature is 60-70 ℃, with the light component evaporation and be condensed into waste water; Light component is removed the remaining liquid in back be warming up to 200-220 ℃, pressure is controlled at about 0.8Mpa, carries out rectifying, and worth purity is 98.5% benzoic acid.
(acid number is 568.46gKOH/kg with thick binary acid, content is 80%) residue places reactor, add the ethanol (adding ethanol 920 grams in every kg crude binary acid) and the concentrated sulfuric acid (addition be thick binary acid 4%), react 5h under 75-85 ℃ of condition, esterification yield reaches 97%.Drop into active carbon in the honest and kind mixture of reaction, addition is 3/1000ths, is incubated 3h down at 80 ℃.To decolour then in the honest and kind boring input still, add NaOH (addition be thick binary acid quality 1.5%).Be cooled to normal temperature then, the pH value reaches the material input rectifying column after 6.5. will wash after washing, and at 200-210 ℃, rectifying under the 0.74-0.76Mpa obtains terephthalate, and the rate of recovery reaches 99%.
Thick binary acid is taken off waste water, the rectified residue that obtains behind the light component, and thick binary acid rectified residue is sent into respectively and is exempted from burning disposal in the incinerator.In order to reclaim rare metal cobalt manganese, will burn back gained lime-ash and drop into solution NH 4HCO 3Carry out precipitation reaction in the solution.The gained precipitation is adopted the washing of sleeping, use excessive acetate dissolution then, the active carbon of adding 2/1000ths decolours.Adopt the method for filtering to remove this active carbon, add and leave standstill H 2O 2Leave standstill after 3-4h removes iron ion, liquid is carried out evaporative crystallization, obtain the acetic acid cobalt-manganese salt.

Claims (4)

1. the recycling processing method of p-phthalic acid's waste residue, it is characterized in that: take the following step: a. is heated to 60～100 ℃ with the PTA waste residue, and the cut that obtains is thick monoacid;
B. separating step a gained waste residue obtains thick binary acid;
C. the described thick monoacid of step a is controlled at 50～80 ℃ and takes off light component, carry out rectifying and get benzoic acid through 180～280 ℃, negative pressure 0.6～0.95Mpa again;
D. in the thick binary acid input reactor described in the step b, add alcohol and sulfuric acid, titanium series, aluminium series or cobalt catalyst series and react, the control reaction temperature is 60～100 ℃, and the reaction time is 2～10h;
E. the reactant mixture that steps d is obtained is used activated carbon decolorizing under 50～95 ℃ of conditions, and 2～5h holds time; F. with in the input of the material after the step e decolouring and still, under 50～95 ℃ of conditions, with NaOH or NaHCO 3Neutralize, be cooled to normal temperature then and wash, control pH value is at 5.5～7.0 ℃;
G. with step f gained material input rectifying column, rectifying under 180～280 ℃, negative pressure 0.7～0.98Mpa condition obtains the terephthalic acid (TPA) esters product;
H. with described waste water, the rectified residue that obtains after light of taking off of step c, the described rectified residue of step g is sent into respectively and is exempted from burning disposal in the fuel incinerator;
I. burn from step h gained and extract rare metal cobalt, manganese the lime-ash that produces.
2. essence according to claim 1 is characterized in that the recycling processing method of dibenzoic acid waste residue: described step b adopts plate cabinet filter press or centrifuge to separate waste residue.
3. essence according to claim 1 is characterized in that the recycling processing method of dibenzoic acid waste residue: the alcohols that adds in the steps d is methyl alcohol or ethanol or octanol or ethylene glycol.
4. essence according to claim 1 is characterized in that the recycling processing method of dibenzoic acid waste residue: the method for the described extraction rare metal of step I cobalt, manganese is: adopt NH 4HCO 3Solution is precipitate cobalt, manganese simultaneously, then with the acetate dissolution of coming, and the repeatedly refining again acetic acid cobalt-manganese salt that finally obtains.
CN2009101305434A 2008-04-03 2009-03-27 Resource treatment method for fine terephthalic acid waste residue Active CN101513641B (en)

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CNA2008100235548A CN101255107A (en) 2008-04-03 2008-04-03 Resourceful treatment method of purified terephthalic acid waste residue
CN200810023554.8 2008-04-03
CN2009101305434A CN101513641B (en) 2008-04-03 2009-03-27 Resource treatment method for fine terephthalic acid waste residue

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698675A (en) * 2012-06-20 2012-10-03 苏州龙峰钛镍设备有限公司 Recovery tower and recovery process for benzoic acid in pure terephthalic acid (PTA) residues
CN110410800A (en) * 2019-07-31 2019-11-05 王天陆 A method of processing powder class and sludge class waste are cooperateed with using cement kiln
WO2021103337A1 (en) * 2019-11-29 2021-06-03 沈福昌 Method for harmless recovery and incineration treatment of purified terephthalic acid residue
WO2022156624A1 (en) * 2021-01-20 2022-07-28 泰兴市福昌环保科技有限公司 Production process for producing plasticizer from pta oxidation residue

Families Citing this family (10)

* Cited by examiner, † Cited by third party
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
CN104910004B (en) * 2014-03-12 2016-06-01 张超智 A kind of method of PTA waste residue resource
GB201414292D0 (en) * 2014-08-12 2014-09-24 Invista Technologies S.�.R.L. Process
CN107176745A (en) * 2016-03-09 2017-09-19 王仲甫 The method for biologically treating wastewater of polybasic carboxylic acid residue
CN106800669A (en) * 2017-01-09 2017-06-06 青州市瑞鑫再生资源科技有限公司 A kind of method that plasticizer is prepared with PTA residues
CN108358407B (en) * 2018-02-12 2021-08-31 常州德诚环境科技有限公司 PTA oxidation residue and sludge comprehensive utilization system and method
CN109053422A (en) * 2018-09-21 2018-12-21 浙江嘉成化工有限公司 The processing method and equipment of insurance powder waste liquid in sodium hydrosulfite production process
CN109847808B (en) * 2019-01-28 2022-02-08 上海炼升化工股份有限公司 Method for recovering heavy metal catalyst in PTA residues
CN113151686B (en) * 2020-12-08 2022-10-18 南通百川新材料有限公司 Equipment and method for recovering cobalt-manganese mixture in trimellitic anhydride production residues
CN113108291B (en) * 2021-04-22 2022-10-18 红河州现代德远环境保护有限公司 Device for pretreating dichloroethane by pyrogenic process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3037054C2 (en) * 1979-12-14 1983-09-08 Dynamit Nobel Ag, 5210 Troisdorf Process for the recovery and reuse of cobalt or cobalt and manganese compounds from the Witten DMT process
CN1062852C (en) * 1998-02-16 2001-03-07 中国石化辽阳石油化纤公司 Process for recovering cobalt and manganese catalysts from production of terephthalic acid
CN1089365C (en) * 1999-07-05 2002-08-21 沈福昌 Process for treating residual PTA dregs
CN1120893C (en) * 1999-10-19 2003-09-10 中国石化集团洛阳石油化工总厂 Process for recovering Co and Mn Catalyst from oxidized dregs of terephthalic acid
CN101255107A (en) * 2008-04-03 2008-09-03 沈福昌 Resourceful treatment method of purified terephthalic acid waste residue

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698675A (en) * 2012-06-20 2012-10-03 苏州龙峰钛镍设备有限公司 Recovery tower and recovery process for benzoic acid in pure terephthalic acid (PTA) residues
CN110410800A (en) * 2019-07-31 2019-11-05 王天陆 A method of processing powder class and sludge class waste are cooperateed with using cement kiln
CN110410800B (en) * 2019-07-31 2022-12-09 王天陆 Method for cooperatively treating powder and sludge wastes by using cement kiln
WO2021103337A1 (en) * 2019-11-29 2021-06-03 沈福昌 Method for harmless recovery and incineration treatment of purified terephthalic acid residue
WO2022156624A1 (en) * 2021-01-20 2022-07-28 泰兴市福昌环保科技有限公司 Production process for producing plasticizer from pta oxidation residue

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WO2009127117A1 (en) 2009-10-22
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