CN104003453A - Technological method for recovery of oxidation residue solid waste valuable mixture - Google Patents
Technological method for recovery of oxidation residue solid waste valuable mixture Download PDFInfo
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- CN104003453A CN104003453A CN201410152901.2A CN201410152901A CN104003453A CN 104003453 A CN104003453 A CN 104003453A CN 201410152901 A CN201410152901 A CN 201410152901A CN 104003453 A CN104003453 A CN 104003453A
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- carboxylic acid
- ammonium
- acid
- mixed carboxylic
- solid waste
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Abstract
The invention relates to the field of chemical industry, in particular to a technological method for recovery of an oxidation residue solid waste valuable mixture. By means of alkaline hydrolysis, activated carbon filtration and decoloration, acid precipitation, solid-liquid separation, and heating crystallization, a crude benzoic acid filter cake can be obtained. By adopting the technical scheme, the utilization rate of resources is improved, and the pollution to the environment is reduced.
Description
Technical field
The present invention relates to chemical field, refer in particular to and a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture.
Background technology
Developing rapidly of PTA industry, bring serious three-waste pollution problem, especially comparatively outstanding with the problem of PTA waste residue, because the composition of waste residue is very complicated, and the content of each component changes, and this has brought certain technical difficulty to recycling and comprehensive utilization of PTA residue, the universal method of European and American developed countries' treatment PTA waste residue is burning method, and then from wherein reclaiming precious metal, but the shortcoming of burning method is wherein have a large amount of di-carboxylic acid not have effective recycling.
Utilize in addition mixed carboxylic acid and alcohol to carry out esterification, recycling distillation obtains overhead product, obtains highly purified one, di-carboxylic acid product through hydrolysis; This kind of method energy consumption is large, secondary residue treatment complexity at the bottom of tower.
Therefore, the inventor makes further research this, develops a kind ofly to reclaim oxidation residua solid waste and have the processing method of valency mixture, and this case produces thus.
Summary of the invention
The object of the present invention is to provide and a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture, improved the utilization ratio of resource.
To achieve these goals, technical scheme of the present invention is as follows:
Reclaiming oxidation residua solid waste has a processing method for valency mixture, comprises the steps:
(1) with ammonia water as medium, under normal temperature and pressure, residue is carried out to alkaline hydrolysis, obtain cobaltous hydroxide, manganous hydroxide solid and mixed carboxylic acid's ammonium mother liquor;
(2) mixed carboxylic acid's ammonium mother liquor, through pH value adjustment, adds activated carbon decolorizing and obtains the mixed carboxylic acid ammonium mother liquor clear without colour purity;
(3) under agitation add gradually sulfuric acid and mixed carboxylic acid to react and generate mixed carboxylic acid's solid and ammonium sulfate liquor;
(4) ammonium sulfate liquor after solid-liquid separation under agitation adds calcium oxide or calcium hydroxide powder and ammonium sulfate reaction to generate calcium sulfate and ammoniacal liquor, and the ammonia mother liquid after separating calcium sulphate is circulated to (1) step and continues alkaline hydrolysis residue;
(5) mixed carboxylic acid is dropped into water extraction kettle, making beating, adds extraction heat monocarboxylic acid, filter, and binary mixed carboxylic acid's filter cake and hydrothermal solution, hydrothermal solution obtains the crystallization of crude benzol formic acid through cooling, then obtains after filtration crude benzol formic acid filter cake.
Further, the ammonia concn in described step (1) is 2 ~ 3%.
Further, the extraction temperature in described step (5) is 90 °, and insulation continues 1 hour.
Further, in described step (5), mixed carboxylic acid's solid-to-liquid ratio is 1:3.
Further, described cobaltous hydroxide, manganous hydroxide are catalyst cobalt, mn ion and the compounds hydroxy of carrying secretly from residue.
Further, described mixed carboxylic acid comprises: terephthalic acid ammonium, m-phthalic acid ammonium, ammonium phthalate, ammonium benzoate, p-methylbenzoic acid ammonium.
Further, described sulfuric acid is industrial sulphuric acid, and concentration is 20 ~ 30%.
Adopt after such scheme, the present invention compared with prior art, has the following advantages:
1, ammonia reusable edible, engineering application only needs to supplement rational loss;
2, calcium sulfate (gypsum) both can have been sold to make a profit and make up acid out cost, the pollution that has solved again acid group;
3, heavy metal approaches 100% recovery;
4, binary mixed carboxylic acid has got rid of the impact of pigment, is suitable for the esterified prod such as Synolac, TA polyester polyol, PVC softening agent completely;
5, phenylformic acid is through rectifying purity more than 99%;
6, binary mixed carboxylic acid, crude benzol formic acid, the moisture that calcium sulfate (gypsum) filter cake is carried secretly in the time separating is greater than the moisture that residuum feedstocks is brought into, therefore technique of the present invention need be supplemented process water and do not produced waste water, through gac and calcium hydroxide secondary purification, water quality can not worsen.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
The present invention discloses a kind ofly reclaims oxidation residua solid waste and has the processing method of valency mixture, ammoniacal liquor taking NH3 concentration as 2 ~ 3% is as mother liquor, under normal temperature and pressure, add while stirring residue, residue is under the effect of ammonia, alkaline hydrolysis becomes taking mixed carboxylic acid's ammonium as main ammonium salt to be dissolved in mother liquor, simultaneously cobalt, mn ion and hydroxide ion reaction has generated cobaltous hydroxide and manganous hydroxide solid is separated out, reaction end PH > 7, reaction formula is as follows:
∑RCOOH?+?NH
4OH?——?∑RCOONH
4+?H
2O
Co
+?+?2OH
-?——?Co（OH）
2
Mn
+?+?2OH
-?——?Mn（OH）
2
Note: ∑ R represents mixed carboxylic acid's phenyl group.
Reclaim cobaltous hydroxide and manganous hydroxide blended solid through solid-liquid separation, filtrate is moved to decolouring pond under whipped state, with in the dilute sulphuric acid of 30% concentration and residual ammonia, adjust PH=7, then add activity charcoal powder whip attachment half an hour of 3g/l ratio above again through separating, can obtain carboxylic acid ammonium's mother liquor clear without colour purity.
Pure clear carboxylic acid ammonium's mother liquor is moved to acid out pond, add while stirring dilute sulphuric acid and carboxylic acid ammonium's reaction of 30% concentration, make carboxylic acid be solid and separate out, while sulfate ion and ammonium ion are combined into sulfuric acid and are dissolved in mother liquor, reaction end PH≤7, and reaction formula is as follows:
2∑RCOONH
4?+?H
2SO
4——?2∑RCOOH?+?(NH
4)
2SO
4
To mix above mother liquor through solid-liquid separation, obtain mixed carboxylic acid's solid, this mixed carboxylic acid's solid is dropped into water hot extraction's still and be heated to 100 DEG C with the ratio making beating of solid-to-liquid ratio 1:3, be incubated half an hour, filter and obtain binary mixed carboxylic acid's solid and crude benzol formic acid hydrothermal solution, hydrothermal solution obtains the crystallization of crude benzol formic acid through cooling, obtain after filtration again crude benzol formic acid in dissolution kettle with 120 DEG C of dissolvings of >, dewater, rectifying both can obtain the finished product of purity > 99%, can make product and sell after binary mixed carboxylic acid is dry.
The mother liquor separating is above analysed to pond at calcium and add while stirring calcium hydroxide or calcium oxide, make ammonium sulfate reaction generate calcium sulfate (gypsum) and ammoniacal liquor, calcium sulfate is dried and can be sold as finished product through solid-liquid separation, dry containing ammonia steam, being disposed to ammonia absorber reclaims, ammonia mother liquid is introduced the alkaline hydrolysis residue use that circulates in the step starting most, and reaction end is as the criterion with noresidue sulfate radical, and reaction formula is as follows:
（NH
4）
2SO
4?+?Ca（OH）
2?——?CaSO
4?+?2NH
4OH
After charcoal absorption pigment, still have the very large specific surface area use again of can taping the latent power, technique of the present invention is set up a Fenton reagent pond, at PH=3, Fe
+under existence, with hydrogen peroxide, the pigment of charcoal absorption is done to deep oxidation processing, regularly take out neutralization, dry, capable of circulationly use again.
Embodiment mono-
In 1000ml sesame seed cake, add 500ml tap water, the pure bicarbonate of ammonia of 50g (NH3 content 21 ~ 22%), divide secondary to add oxidation residua 50g, alkaline hydrolysis half an hour (having great amount of carbon dioxide gas to discharge when alkaline hydrolysis) under whipped state, static 1 hour again, in dark solution, there is grey black precipitation to generate.
Obtain the blended solid 1.3g of cobaltous hydroxide and manganous hydroxide through suction filtration, filtrate moves to former beaker and continues to stir, the sulfuric acid that drips gradually 30% concentration is adjusted solution PH=7, adds after 1.5g activity charcoal powder in above-mentioned solution, continues to stir half an hour, suction filtration obtains colourless pure clear liquid, this clear liquid, in 1000ml beaker, is dripped to 30% concentration sulfuric acid under whipped state, until PH < 7, stable stirring 10 minutes, obtains lily carboxylic acid mixed solution again.
Embodiment bis-
Above-mentioned ammonium sulfate liquor is moved in 1000ml beaker, under agitation add 10g carbonate-free lime (content is greater than 98%), filtrate is emitted pungency ammonia odor gradually, stable stirring half an hour, and suction filtration obtains alkaline ammonium filtrate PH=12 and calcium sulfate filter cake.
Filtrate is moved in 1000ml beaker under whipped state, and a point secondary adds same oxidation residua sample, obtains dark solution and the grey black precipitation of equifinality, and different is without gaseous emission in alkaline hydrolysis.
Embodiment tri-
Mixed carboxylic acid's filter cake that embodiment bis-is obtained, put into 1000ml beaker and add 300ml tap water, under whipped state, pull an oar, thereafter be heated to 90 DEG C, be incubated half an hour, suction filtration obtains binary mixed carboxylic acid filter cake and hot solution, and hydrothermal solution is cooled to normal temperature, there are a large amount of pure white crystallizations, obtain crude benzol formic acid filter cake and binary mixed carboxylic acid filter cake through suction filtration.
Above are only specific embodiments of the invention, but design concept of the present invention is not limited to this, allly utilizes this design to carry out the change of unsubstantiality to the present invention, all should belong to the behavior of invading protection domain of the present invention.
Claims (7)
1. reclaiming oxidation residua solid waste has a processing method for valency mixture, comprises the steps:
1) with ammonia water as medium, under normal temperature and pressure, residue is carried out to alkaline hydrolysis, obtain cobaltous hydroxide, manganous hydroxide solid and mixed carboxylic acid's ammonium mother liquor;
(2) mixed carboxylic acid's ammonium mother liquor, through pH value adjustment, adds activated carbon decolorizing and obtains the mixed carboxylic acid ammonium mother liquor clear without colour purity;
(3) under agitation add gradually sulfuric acid and mixed carboxylic acid to react and generate mixed carboxylic acid's solid and ammonium sulfate liquor;
(4) ammonium sulfate liquor after solid-liquid separation under agitation adds calcium oxide or calcium hydroxide powder and ammonium sulfate reaction to generate calcium sulfate and ammoniacal liquor, and the ammonia mother liquid after separating calcium sulphate is circulated to (1) step and continues alkaline hydrolysis residue;
(5) mixed carboxylic acid is dropped into water extraction kettle, making beating, adds extraction heat monocarboxylic acid, filter, and binary mixed carboxylic acid's filter cake and hydrothermal solution, hydrothermal solution obtains the crystallization of crude benzol formic acid through cooling, then obtains after filtration crude benzol formic acid filter cake.
2. according to claim 1ly a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture, it is characterized in that: the ammonia concn in described step (1) is 2 ~ 3%.
3. according to claim 1ly a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture, it is characterized in that: the extraction temperature in described step (5) is 90 °, insulation continues 1 hour.
4. according to claim 1ly a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture, it is characterized in that: in described step (5), mixed carboxylic acid's solid-to-liquid ratio is 1:3.
5. according to claim 1ly a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture, it is characterized in that: described cobaltous hydroxide, manganous hydroxide are catalyst cobalt, mn ion and the compounds hydroxy of carrying secretly from residue.
6. according to claim 1ly a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture, it is characterized in that: described mixed carboxylic acid comprises: terephthalic acid ammonium, m-phthalic acid ammonium, ammonium phthalate, ammonium benzoate, p-methylbenzoic acid ammonium.
7. according to claim 1ly a kind ofly reclaim oxidation residua solid waste and have the processing method of valency mixture, it is characterized in that: described sulfuric acid is industrial sulphuric acid, concentration is 20 ~ 30%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844445A (en) * | 2015-03-27 | 2015-08-19 | 中国昆仑工程公司 | Method for recycling acetic acid from blanking residues of PTA (purified terephthalic acid) film evaporator |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106535A (en) * | 1984-10-30 | 1986-05-24 | Mitsubishi Chem Ind Ltd | Recovery of benzoic acid |
| CN1883765A (en) * | 2006-06-06 | 2006-12-27 | 李长康 | Circulation desulfurization technology by ammonia-soda process |
| CN101870648A (en) * | 2010-05-28 | 2010-10-27 | 南京万博丰环保科技有限公司 | Method for recovering benzoic acid from PTA oxidation residue |
| CN102786412A (en) * | 2012-09-03 | 2012-11-21 | 绍兴汉青环保科技有限公司 | Extraction method for extracting benzoic acid, p-toluic acid, terephthalic acid and isophthalic acid from pure terephthalic acid (PTA) oxidation residues |
-
2014
- 2014-04-17 CN CN201410152901.2A patent/CN104003453A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106535A (en) * | 1984-10-30 | 1986-05-24 | Mitsubishi Chem Ind Ltd | Recovery of benzoic acid |
| CN1883765A (en) * | 2006-06-06 | 2006-12-27 | 李长康 | Circulation desulfurization technology by ammonia-soda process |
| CN101870648A (en) * | 2010-05-28 | 2010-10-27 | 南京万博丰环保科技有限公司 | Method for recovering benzoic acid from PTA oxidation residue |
| CN102786412A (en) * | 2012-09-03 | 2012-11-21 | 绍兴汉青环保科技有限公司 | Extraction method for extracting benzoic acid, p-toluic acid, terephthalic acid and isophthalic acid from pure terephthalic acid (PTA) oxidation residues |
Non-Patent Citations (1)
| Title |
|---|
| 任明: "《中国优秀硕士学位论文全文数据库 工程科技I辑》", 15 March 2008, article "PTA生产废渣中苯羧酸的分离回收试验研究", pages: 3-32 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844445A (en) * | 2015-03-27 | 2015-08-19 | 中国昆仑工程公司 | Method for recycling acetic acid from blanking residues of PTA (purified terephthalic acid) film evaporator |
| CN104844445B (en) * | 2015-03-27 | 2017-06-20 | 中国昆仑工程有限公司 | The method of recovery of acetic acid from PTA thin film evaporator blanking residues |
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Application publication date: 20140827 |