CN103922926A - Process for purifying residual solid waste generated after alkali peeling wastewater treatment - Google Patents
Process for purifying residual solid waste generated after alkali peeling wastewater treatment Download PDFInfo
- Publication number
- CN103922926A CN103922926A CN201410154302.4A CN201410154302A CN103922926A CN 103922926 A CN103922926 A CN 103922926A CN 201410154302 A CN201410154302 A CN 201410154302A CN 103922926 A CN103922926 A CN 103922926A
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- CN
- China
- Prior art keywords
- terephthalic acid
- solid waste
- mother liquor
- waste water
- alkali decrement
- Prior art date
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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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of purification of alkali peeling wastewater, and particularly relates to a process for purifying residual solid waste generated after alkali peeling wastewater treatment. Crude terephthalic acid solid waste has a reaction under a condition that amine is over-dose and then is added with active carbon, stirred and separated, a liquid phase is added with sulfuric acid to separate out terephthalic acid and separated again, and generated ammonium sulfate is recycled. By adopting the scheme, consumption of caustic soda is avoided, the reclamation cost is lowered and resources are fully recycled.
Description
Technical field
The present invention relates to alkali decrement waste water field of purification, refer in particular to a kind of alkali decrement waste water residue solid waste after treatment purifying process.
Background technology
The existing method of extracting terephthalic acid from alkali decrement waste water, have in CN200910096512.1, mention with caustic soda (sodium hydroxide) alkaline hydrolysis, although can obtain the terephthalic acid of higher degree, the input cost of caustic soda is higher, and the sodium salt that acid out obtains does not make full use of; CN201110103937 proposes to carry out in the technique of high-temperature digestion, mother liquor purification, recrystallize with polar solvent DMF, ignore the terephthalic acid of alkali decrement waste water output and carried strong acid secretly, pH value is generally 2 ~ 3, strong acid produces hydrolytic action as catalyzer to DMF, make it be hydrolyzed into formic acid and dimethyl amine, DMF solvent is lossy, and production cost is higher.
Therefore, the inventor makes further research this, develops a kind of alkali decrement waste water residue solid waste after treatment purifying process, and this case produces thus.
Summary of the invention
The object of the present invention is to provide a kind of alkali decrement waste water residue solid waste after treatment purifying process, in accomplishing to extract terephthalic acid from alkali decrement waste water, can also realize better economic benefit.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of alkali decrement waste water residue solid waste after treatment purifying process, comprises the steps:
(1) by the crude terephthalic acid reclaiming in alkali decrement waste water under the excessive condition of amine, reaction generates terephthalic acid ammonium, obtains the amine salt solution of pH value >=7;
(2) in amine salt solution, add activity charcoal powder, more than fully stirring half an hour, make gac complete absorption, after being separated by filtration, can obtain the pure clear liquid of amine salt;
(3) by pure the amine salt obtaining clear liquid under whipped state, progressively add sulfuric acid, make terephthalic acid ammonium be reduced into terephthalic acid and separate out, simultaneously sulfate radical and amine reaction generates ammonium sulfate and is dissolved in mother liquor;
(4) by above mother liquor through solid-liquid separation, solid phase terephthalic acid is through pure water circulation flushing, takes ammonium sulfate post-drying out of and pulverizes and be pure terephthalic acid's finished product;
(5) mother liquor after solid-liquid separation is introduced calcification pond, under whipped state, progressively adds calcium oxide or calcium hydroxide, and reaction generates calcium sulfate, restores ammoniacal liquor simultaneously;
(6) after calcium sulfate and mother liquor solid-liquid separation, Tumble Dry and be crushed into terra alba finished product, the steam that dryer produces is introduced absorption tower, reclaims ammonia reuse;
(7) Recycling Mother Solution separating with calcium sulfate is recycled to the first step.
Further, the amine in described step (1) finally can convert NH to
3h
2o or NH
4the nitrogenous compound of OH, (as ammoniacal liquor, bicarbonate of ammonia, urea, thiamines etc.).
Further, the activity charcoal powder in described step (2), can be ature of coal, can be also the mesopore activity carbon powder of plant charcoal.
Further, sulfuric acid is industrial sulphuric acid in described step (3), under mother liquor whipped state, progressively adds, and concentration is reduced to below 30%, reacts fully, and prevents from that terephthalic acid is agglomerating to separate out, and reaction end pH value is 6.5-7.
Further, described step (4) pure water is deionized water.
Further, in described step (5) calcification pond, be one or both in calcium oxide or calcium hydroxide.
Adopt after such scheme, the present invention compared with prior art, has the following advantages:
The consumption of having omitted caustic soda, has reduced cost recovery, and calcium sulfate recoverable makes resource obtain sufficient recycle.
Brief description of the drawings
Fig. 1 is schematic flow sheet of the present invention;
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
Flow process principle of the present invention is as follows:
The present invention is with ammonia mother liquor and terephthaldehyde's acid-respons of 2 ~ 3% concentration, and to obtain the terephthaldehyde's acid ammonium salt that is dissolved in mother liquor, reaction formula is as follows:
C
6H
4(COOH)
2?+?2NH
4 +?——?C
6H
4（COONH
4）
2?+?H
2O
Add activity charcoal powder, by whip attachment slurry, (now mother liquor pH value is in 7 left and right with other impurity, the former compound that is dissolved in waste liquid is all with crystallization), after solid-liquid separation, can obtain limpid pure clear mother liquor, by the terephthalic acid reclaiming in the higher desized wastewater of slurry concentration, available secondary charcoal adsorbs to obtain better effect.
Mother liquor, under the state stirring, progressively adds industrial sulphuric acid and the reaction of terephthalic acid ammonium of 30% concentration, PH terminal 6.5 ~ 7, thus obtain highly purified terephthalic acid and ammonium sulfate, react as follows:
C
6H
4（COONH
4）
2?+?H
2SO
4?——?C
6H
4(COOH)
2?+?（NH
4）
2?SO
4?
By above-mentioned mother liquor, through solid-liquid separation, mother liquor continues under agitation progressively to add calcium hydroxide, makes ammonium sulfate reaction generate calcium sulfate, restores ammoniacal liquor simultaneously, reacts as follows:
（NH
4）
2?SO
4?+CaSO
4?——?CaSO
4+2NH
4OH
After calcium sulfate separates with mother liquor, mother liquor is for recycle again; Isolated calcium sulfate is dried pulverizing, recycle, and the steam producing passes through the recyclable ammonia in absorption tower, and the ammonia after recovery can add in mother liquor again.
Embodiment mono-:
Get 100 grams of crude terephthalic acids that reclaim residue solid waste after printing and dyeing mill alkali decrement waste water is processed, water content 60%, be dissolved in 1000mg containing in the aqueous solution of bicarbonate of ammonia 10%, stirring and dissolving 15 minutes, obtain turbid solution, add 2 grams of active carbon powders, stir half an hour, filtration obtains clear liquid, and under agitation progressively adding 30% sulfuric acid reaction to pH value is 6, and therefore in mother liquor, monoammonium sulfate is excessive, so when acid out, have great amount of carbon dioxide to overflow, reaction ends, and terephthalic acid separates and obtain pure terephthalic acid with mother liquor.
Embodiment bis-:
Go the mother liquor of terephthalic acid to add 15 grams of calcium oxide the above, after agitation and filtration, obtain the basic solution of PH12, add 100 grams of the oxidation residuas (moisture 30%) after phenylformic acid reclaims, stir after 15 minutes, mother liquor after filtering adds 2 grams of gacs, discoloring agent stirs half an hour, in mother liquor after again filtering, add the sulfuric acid of 30% concentration, react to pH value be 7, filter pure whitely di-carboxylic acid solid (containing terephthalic acid, this dioctyl phthalate, adjacent stupid dioctyl phthalate, a small amount of phthalic acid).
Embodiment tri-:
The mother liquor of embodiment bis-filtering di-carboxylic acid is added to 15 grams of calcium oxide, after agitation and filtration, ammonia reduces again, adds printing and dyeing mill's alkali decrement waste water to process in rear 100 grams of solution of crude terephthalic acid that reclaim residue solid waste (water content 70%), obtains equally the result of above embodiment.
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 (6)
1. an alkali decrement waste water residue solid waste after treatment purifying process, comprises the steps:
(1) by the crude terephthalic acid solid waste reclaiming in alkali decrement waste water under the excessive condition of amine, reaction generates terephthalic acid ammonium, obtains the amine salt solution of pH value >=7;
(2) in amine salt solution, add activity charcoal powder, more than fully stirring half an hour, make gac complete absorption, after being separated by filtration, can obtain the pure clear liquid of amine salt;
(3) by pure the amine salt obtaining clear liquid under whipped state, progressively add sulfuric acid, make terephthalic acid ammonium be reduced into terephthalic acid and separate out, simultaneously sulfate radical and amine reaction generates ammonium sulfate and is dissolved in mother liquor;
(4) by above mother liquor through solid-liquid separation, solid phase terephthalic acid is through pure water circulation flushing, takes ammonium sulfate post-drying out of and pulverizes and be pure terephthalic acid's finished product;
(5) mother liquor after solid-liquid separation is introduced calcification pond, under whipped state, progressively adds calcium oxide or calcium hydroxide, and reaction generates calcium sulfate, restores ammoniacal liquor simultaneously;
(6) after calcium sulfate and mother liquor solid-liquid separation, Tumble Dry and be crushed into terra alba finished product, the steam that dryer produces is introduced absorption tower, reclaims ammonia reuse;
(7) Recycling Mother Solution separating with calcium sulfate is recycled to the first step.
2. a kind of alkali decrement waste water according to claim 1 residue solid waste after treatment purifying process, comprises the steps: that the amine in described step (1) finally can convert NH to
3h
2o or NH
4the nitrogenous compound of OH, (as ammoniacal liquor, bicarbonate of ammonia, urea, thiamines etc.).
3. a kind of alkali decrement waste water according to claim 1 residue solid waste after treatment purifying process, comprises the steps: the activity charcoal powder in described step (2), can be ature of coal, can be also the mesopore activity carbon powder of plant charcoal.
4. a kind of alkali decrement waste water according to claim 1 residue solid waste after treatment purifying process, comprise the steps: that in described step (3), sulfuric acid is industrial sulphuric acid, under mother liquor whipped state, progressively add, concentration is reduced to below 30%, react fully, preventing that terephthalic acid is agglomerating separates out, and reaction end pH value is 6.5-7.
5. a kind of alkali decrement waste water according to claim 1 residue solid waste after treatment purifying process, comprises the steps: that described step (4) pure water is deionized water.
6. a kind of alkali decrement waste water according to claim 1 residue solid waste after treatment purifying process, comprises the steps: in described step (5) calcification pond as one or both in calcium oxide or calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410154302.4A CN103922926A (en) | 2014-04-17 | 2014-04-17 | Process for purifying residual solid waste generated after alkali peeling wastewater treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410154302.4A CN103922926A (en) | 2014-04-17 | 2014-04-17 | Process for purifying residual solid waste generated after alkali peeling wastewater treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103922926A true CN103922926A (en) | 2014-07-16 |
Family
ID=51141355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410154302.4A Pending CN103922926A (en) | 2014-04-17 | 2014-04-17 | Process for purifying residual solid waste generated after alkali peeling wastewater treatment |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710300A (en) * | 2015-03-03 | 2015-06-17 | 常州市博洋新材料科技有限公司 | Method for extracting terephthalic acid from terephthalic acid residues |
| CN105085229A (en) * | 2015-09-02 | 2015-11-25 | 刘健 | Method for recovering TPA (terephthalic acid) from polyester alkali deweighting waste residues with limitation on rare earth materials |
| CN105085230A (en) * | 2015-09-02 | 2015-11-25 | 刘健 | Method for recycling terephthalic acid in terylene alkali peeling waste residue using mixed solvent |
| CN105130797A (en) * | 2015-09-02 | 2015-12-09 | 刘健 | Method for recovering terephthalic acid in polyester alkali decrement residues by means of parameter optimizing |
| CN111362840A (en) * | 2020-04-15 | 2020-07-03 | 山东阳谷华泰化工股份有限公司 | Method for recycling ammonia from accelerator DPG mother liquor in production process to synthesize accelerator DPG through recycling |
| CN113214078A (en) * | 2021-05-26 | 2021-08-06 | 宜兴市阳洋塑料助剂有限公司 | Method for recycling and preparing dioctyl terephthalate by utilizing terephthalic acid production waste |
| CN115180698A (en) * | 2022-07-20 | 2022-10-14 | 浙江梅盛新材料有限公司 | Method for treating superfine fiber suedette alkali-reduction splitting wastewater by using calcium lignosulfonate |
Citations (5)
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|---|---|---|---|---|
| US4034005A (en) * | 1975-06-17 | 1977-07-05 | Sun Ventures, Inc. | Process for making aromatic acids |
| WO2005003217A1 (en) * | 2003-07-07 | 2005-01-13 | Roman Sierzant | Method and plant for the recovery of terephthalic acid and ethylene glycol from polyethylene terephthalate wastes |
| CN101121655A (en) * | 2007-08-30 | 2008-02-13 | 洪芳柏 | Technique for purifying crude terephthalic acid |
| CN101691633A (en) * | 2009-10-12 | 2010-04-07 | 湖南广义科技有限公司 | Method for innocent treatment and comprehensive utilization of manganese slag |
| CN102351231A (en) * | 2011-06-28 | 2012-02-15 | 攀枝花市微创科技开发有限公司 | Resource utilization method for titanium white by-product ferrous sulphate |
-
2014
- 2014-04-17 CN CN201410154302.4A patent/CN103922926A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4034005A (en) * | 1975-06-17 | 1977-07-05 | Sun Ventures, Inc. | Process for making aromatic acids |
| WO2005003217A1 (en) * | 2003-07-07 | 2005-01-13 | Roman Sierzant | Method and plant for the recovery of terephthalic acid and ethylene glycol from polyethylene terephthalate wastes |
| CN101121655A (en) * | 2007-08-30 | 2008-02-13 | 洪芳柏 | Technique for purifying crude terephthalic acid |
| CN101691633A (en) * | 2009-10-12 | 2010-04-07 | 湖南广义科技有限公司 | Method for innocent treatment and comprehensive utilization of manganese slag |
| CN102351231A (en) * | 2011-06-28 | 2012-02-15 | 攀枝花市微创科技开发有限公司 | Resource utilization method for titanium white by-product ferrous sulphate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710300A (en) * | 2015-03-03 | 2015-06-17 | 常州市博洋新材料科技有限公司 | Method for extracting terephthalic acid from terephthalic acid residues |
| CN105085229A (en) * | 2015-09-02 | 2015-11-25 | 刘健 | Method for recovering TPA (terephthalic acid) from polyester alkali deweighting waste residues with limitation on rare earth materials |
| CN105085230A (en) * | 2015-09-02 | 2015-11-25 | 刘健 | Method for recycling terephthalic acid in terylene alkali peeling waste residue using mixed solvent |
| CN105130797A (en) * | 2015-09-02 | 2015-12-09 | 刘健 | Method for recovering terephthalic acid in polyester alkali decrement residues by means of parameter optimizing |
| CN111362840A (en) * | 2020-04-15 | 2020-07-03 | 山东阳谷华泰化工股份有限公司 | Method for recycling ammonia from accelerator DPG mother liquor in production process to synthesize accelerator DPG through recycling |
| CN113214078A (en) * | 2021-05-26 | 2021-08-06 | 宜兴市阳洋塑料助剂有限公司 | Method for recycling and preparing dioctyl terephthalate by utilizing terephthalic acid production waste |
| CN115180698A (en) * | 2022-07-20 | 2022-10-14 | 浙江梅盛新材料有限公司 | Method for treating superfine fiber suedette alkali-reduction splitting wastewater by using calcium lignosulfonate |
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Application publication date: 20140716 |