CN103601637A - Treatment method for recovering fumaric acid from phthalic anhydride wastewater - Google Patents
Treatment method for recovering fumaric acid from phthalic anhydride wastewater Download PDFInfo
- Publication number
- CN103601637A CN103601637A CN201310597429.9A CN201310597429A CN103601637A CN 103601637 A CN103601637 A CN 103601637A CN 201310597429 A CN201310597429 A CN 201310597429A CN 103601637 A CN103601637 A CN 103601637A
- Authority
- CN
- China
- Prior art keywords
- mother liquor
- fumaric acid
- treatment process
- phthalic anhydride
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- 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
Abstract
The invention provides a treatment method for recovering fumaric acid from phthalic anhydride wastewater. The treatment method comprises the following steps: 1) recovering fumaric acid from wastewater obtained from the production of the phthalic anhydride by using thiourea, thus obtaining fumaric acid and a mother liquor after the recovery of the fumaric acid; and 2) performing electrolytic treatment on the mother liquor to oxidize the thiourea in the mother liquor into ammonium sulfate, thus obtaining the treated mother liquor. The treatment method for recovering the fumaric acid from the phthalic anhydride wastewater, which is provided by the invention, is characterized in that the electrolytic treatment is performed on the mother liquor to oxidize the thiourea in the mother liquor into the sulfuric acid, and therefore, the COD (Chemical Oxygen Demand) of the mother liquor can be effectively reduced to be below 30000. Tests find that about 10 KWH is consumed to electrolyze the mother liquor to COD15000; in other words, the total cost of recycling the mother liquor per ton is less than 10 Yuan; as a result, the recovery cost is greatly reduced. In addition, the treatment method provided by the invention is simple to operate and high in efficiency.
Description
Technical field
The present invention relates to from the treatment process of phthalic anhydride waste water reclamation fumaric acid.
Background technology
The raw materials for production of phthalic anhydride are o-Xylol or naphthalene, and another raw material is oxygen, in reaction process, can generate the by product of approximately 3% maleic acid, and follow other by products.These by products are sprayed by water in the tail gas tower of phthalic anhydride plant, are phthalic anhydride waste water.
Take thiocarbamide as catalyzer, and the maleic acid in phthalic anhydride waste water can turn to FUMARIC ACID TECH GRADE by isomery, is fumaric acid.Fumaric acid can be used as feed or foodstuff additive, has been widely used.Therefore, proposed to use thiocarbamide from the treatment process of phthalic anhydride waste water reclamation fumaric acid.Yet in the mother liquor after recovery fumaric acid, contain thiocarbamide, maleic acid, fumaric acid, phthalic anhydride, phthalic acid etc., its COD is more than 50000.
At present, industrial use distil process reclaims the water in fumaric acid mother liquor, and as benzoic anhydride tail-gas tower washing water reuse.Mother liquid coming reuse requires below the COD30000 of water, not containing thiocarbamide.Distil process utilizes the difference of water and these impurity boiling points, and water is evaporated to gas, and above-mentioned impurity major part is stayed bottom, realizes the separated of water and impurity.For energy efficient, after upper water condensation, be not back in distiller, small portion impurity gasifies to top, so upper water is aobvious faint yellow, COD10000～15000.For further energy efficient, can adopt economic benefits and social benefits distillation, even triple effect distillation.By the efficiency of current industrial equipments, single-stage distillation, mother liquor per ton consumes approximately 1 ton of steam, double-effect evaporation, mother liquor per ton consumes approximately 0.65 ton of steam, triple effect evaporation, mother liquor per ton consumes approximately 0.5 ton of steam.1 ton of standard coal is produced approximately 6 tons of steam, therefore adopts distil process, and the cost of the water reuse of mother liquor per ton is not less than 75 yuan.Therefore, the higher and processing efficiency of processing cost, production efficiency all have much room for improvement.
Summary of the invention
The essence of electrolysis is catalytic oxidation, anode surface electrophilic, and strong oxidizing property, produces active oxygen and free hydroxyl, the even strong ozone of crossing of this oxidisability, in water, organism is oxidized to small molecules, is further oxidized to CO2 and H2O.The inventor, through research discovery repeatedly, reclaims the organism in the mother liquor after fumaric acid, maleic acid, and fumaric acid, phthalic anhydride, adjacent benzene first diacid, is double bond containing carboxylic acid, is easily by a type organic of electrolysis.The inventor, on the basis of this discovery, has completed the present invention.
The object of the invention is to propose the treatment process from phthalic anhydride waste water reclamation fumaric acid that a kind of cost is low, processing efficiency is high, production efficiency is high.
The treatment process from phthalic anhydride waste water reclamation fumaric acid according to the embodiment of the present invention, comprises the steps: 1) utilize thiocarbamide to reclaim fumaric acid from produce the waste water of described phthalic anhydride, obtain fumaric acid and reclaim the mother liquor after fumaric acid; And 2) described mother liquor is carried out to electrolysis treatment so that thiocarbamide is wherein oxidized to ammonium sulfate, obtain processing rear mother liquor.
According to the treatment process from phthalic anhydride waste water reclamation fumaric acid of the present invention, by mother liquor being carried out to electrolysis treatment so that thiocarbamide is wherein oxidized to sulfuric acid, thereby can effectively the COD of mother liquor be reduced to below 30000.Through test, find, by mother liquor electrolysis, to COD15000, power consumption approximately 10 degree, that is to say and add up to the cost of mother liquid coming reuse per ton below 10 yuan, thereby greatly reduce cost recovery.In addition, the present invention is simple to operate, efficiency is high.
In addition, according to the treatment process from phthalic anhydride waste water reclamation fumaric acid of the present invention, can also comprise following additional technical feature:
According to one embodiment of present invention, the described treatment process from phthalic anhydride waste water reclamation fumaric acid also comprises the steps: 3) washing water by mother liquor described processing as benzoic anhydride tail-gas tower.
Preferably, after described processing, the COD of mother liquor, below 30000, is preferably below 15000.
According to one embodiment of present invention, in described step 2) in, negative and positive the two poles of the earth potential difference is 0.2 ~ 10V, is preferably 1～3V.
According to some embodiments of the present invention, in described step 2) in, current density is 100～10000A/m
2, be preferably 500～3000 A/m
2.
According to some embodiments of the present invention, in described step 2) in, adopt pulsed voltage to carry out electrolysis, the type of pulse is any of square wave, square wave, peaked wave, zigzag wave, choppy sea, bells, trapezoidal wave, staircase waveform.
According to some embodiments of the present invention, the wave amplitude of described pulsed voltage is no more than 10V, is preferably 2～4V.
According to some embodiments of the present invention, in carrying out the electrolyzer of electrolysis treatment, anode comprises base material and coat the coating on described base material, and the material of described base material is titanium.
In examples more of the present invention, the material of described coating comprises iridium and tantalum, preferably also contains platinum.
In other examples of the present invention, the material of described coating comprises ruthenium, preferably also contains rhodium.
The aspect that the present invention is additional and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become from the following description of the accompanying drawings of embodiments and obviously and easily understand, wherein:
Fig. 1 is according to the schema of the treatment process from phthalic anhydride waste water reclamation fumaric acid of the embodiment of the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Below by the embodiment being described with reference to the drawings, be exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, it will be appreciated that, term " on ", orientation or the position relationship of the indication such as D score, " end ", " top ", 'fornt', 'back', " interior ", " outward ", " left side ", " right side " be based on orientation shown in the drawings or position relationship, only the present invention for convenience of description and simplified characterization, rather than indicate or imply that the device of indication or element must have specific orientation, with specific orientation, construct and operation, therefore can not be interpreted as limitation of the present invention.
Below, first by reference to the accompanying drawings to the treatment process explanation from phthalic anhydride waste water reclamation fumaric acid of the present invention.
The treatment process from phthalic anhydride waste water reclamation fumaric acid according to the embodiment of the present invention, comprises the steps: 1) utilize thiocarbamide to reclaim fumaric acid from produce the waste water of described phthalic anhydride, obtain fumaric acid and reclaim the mother liquor after fumaric acid; And 2) described mother liquor is carried out to electrolysis treatment so that thiocarbamide is wherein oxidized to ammonium sulfate, obtain processing rear mother liquor.
According to the treatment process from phthalic anhydride waste water reclamation fumaric acid of the present invention, by mother liquor being carried out to electrolysis treatment so that thiocarbamide is wherein oxidized to sulfuric acid, thereby can effectively the COD of mother liquor be reduced to below 30000.Through test, find, by mother liquor electrolysis, to COD15000, power consumption approximately 10 degree, that is to say and add up to the cost of mother liquid coming reuse per ton below 10 yuan, thereby greatly reduce cost recovery.In addition, the present invention is simple to operate, efficiency is high.
About reclaiming the concrete grammar of fumaric acid in step 1), can adopt the method for this area routine, for example, can be by phthalic anhydride waste water after sedimentation, after supernatant liquor is utilized to activated carbon decolorizing, recycle silicon algae soil decolours, after this supernatant liquor after decolouring is utilized thiocarbamide to carry out isomerization to generate fumaric acid, by solid-liquid separation, obtain fumaric acid and reclaim the mother liquor after fumaric acid.
About above-mentioned steps 2) in electrolysis, preferably, the potential difference at negative and positive the two poles of the earth is controlled at 0.2 ~ 10V, more preferably 1～3V.Potential difference is too low, and electrolysis effectiveness is poor, and the time needing is long; Potential difference is too high, and water is hydrogen and oxygen by electrolysis, and energy consumption increases, electric current service efficiency variation.
In addition, current density is relevant to electrolysis speed, is preferably controlled at 100～10000A/m
2, more preferably at 500～3000A/m
2.Current density is little, and electrolysis speed is slow; Current density is large, and reduce anode life, particularly when current density is greater than 3000 A/m
2time, anode life was lower than 3 years.
In addition, adopt pulsed voltage, the better effects if of electrolysis.The type of pulse can be square wave, square wave, peaked wave, zigzag wave, choppy sea, bells, trapezoidal wave, staircase waveform.Preferably, wave amplitude is no more than 10V, is preferably 2～4V.
Electrolyzer can comprise one or more pairs of anodic-cathodics.Negative electrode belongs to protected electrode, generally seldom damages.Anode belongs to key equipment, and its life-span has determined the maintenance cost of electrolyzer.Fumaric acid mother liquor is strongly-acid, large to common metal material corrosion.Preferably, anode material comprises base material and is coated on the coating on described base material.
Wherein, base material can titanium, and base material thickness can be set as 0.5～5mm, is preferably 1～2mm.
Coating can adopt following two kinds.Take iridium and tantalum as a main raw, and add alternatively other a small amount of metals, as platinum etc.; Another kind of take ruthenium as main raw, and add alternatively other a small amount of metals, as rhodium etc.
In addition, electrolyzer is generally furnished with forced circulation pump.Mother liquid coming is forced-flow between electrode, and circulation, has increased electrolysis effectiveness.
As with, the effect for the treatment of in accordance with the present invention method is described by specific embodiment.
In specific embodiments of the invention 1 ~ 9, anode relates to two kinds, and coating is the called after A of iridium tantalum, the called after B that coating is ruthenium.
Get fumaric acid mother liquor 3L, COD65000 wherein, thiocarbamide 0.8%.
The plate electrode that anode and negative electrode is cut into respectively to 100 * 200mm, adopts 1 pair of electrode, and pump pump circulation, after 3 hours, detects thiocarbamide (chromatography), and tests COD.It the results are summarized in following table 1.
The design parameter of the treatment process of table 1. embodiment 1 ~ 9 and treatment effect
| Embodiment | Anode | Voltage V | Electric current A | Thiocarbamide | COD |
| 1 | A | 2 | 1.4 | Do not detect | 13400 |
| 2 | A | 10 | 13.2 | Do not detect | 2500 |
| 3 | A | 0.2 | 0.15 | Do not detect | 28900 |
| 4 | A | 3 | 2.1 | Do not detect | 10800 |
| 5 | A | 1 | 0.72 | Do not detect | 18700 |
| 6 | A | Pulse, square, 4V | Fluctuation (please provide fluctuation range) | Do not detect | 3100 |
| 7 | A | Pulse, choppy sea, 10V | Fluctuation | Do not detect | 320 |
| 8 | B | 2 | 1.2 | Do not detect | 14800 |
| 9 | B | Pulse, square wave, 2V | Fluctuation | Do not detect | 8600 |
As shown above, according to the treatment process of the embodiment of the present invention 1 ~ 9, can effectively COD be eased down to below 30000, minimumly even can be reduced to 320(embodiment 7), and, in all embodiment, be and detect thiocarbamide.
Although the specific embodiment of the present invention is described in detail with reference to a plurality of illustrative examples of the present invention, but it must be understood that, those skilled in the art can design multiple other improvement and embodiment, and these improve and within embodiment will drop on spirit and scope.Particularly, within the scope of aforementioned open, accompanying drawing and claim, can aspect the layout of component and/or subordinate composite configuration, make rational distortion and improvement, and can not depart from spirit of the present invention.Except modification and the improvement of component and/or layout aspect, its scope is limited by claims and equivalent thereof.
Claims (10)
1. from the treatment process of phthalic anhydride waste water reclamation fumaric acid, its feature for, comprise the steps:
1) utilize thiocarbamide to reclaim fumaric acid from produce the waste water of described phthalic anhydride, obtain fumaric acid and reclaim the mother liquor after fumaric acid; And
2) described mother liquor is carried out to electrolysis treatment so that thiocarbamide is wherein oxidized to ammonium sulfate, obtain processing rear mother liquor.
2. treatment process as claimed in claim 1, is characterized in that, also comprises the steps:
3) washing water as benzoic anhydride tail-gas tower by mother liquor after described processing.
3. treatment process as claimed in claim 1, is characterized in that, after described processing, the COD of mother liquor, below 30000, is preferably below 15000.
4. treatment process as claimed in claim 1, is characterized in that, in described step 2) in, negative and positive the two poles of the earth potential difference is 0.2 ~ 10V, is preferably 1～3V.
5. treatment process according to claim 1, is characterized in that, in described step 2) in, current density is 100～10000A/m
2, be preferably 500～3000 A/m
2.
6. treatment process according to claim 1, it is characterized in that, in described step 2) in, adopt pulsed voltage to carry out electrolysis, the type of pulse is any of square wave, square wave, peaked wave, zigzag wave, choppy sea, bells, trapezoidal wave, staircase waveform.
7. treatment process according to claim 6, is characterized in that, the wave amplitude of described pulsed voltage is no more than 10V, is preferably 2～4V.
8. treatment process according to claim 1, is characterized in that, in carrying out the electrolyzer of electrolysis treatment, anode comprises base material and coat the coating on described base material, and the material of described base material is titanium.
9. treatment process according to claim 8, is characterized in that, the material of described coating comprises iridium and tantalum, preferably also contains platinum.
10. treatment process according to claim 8, is characterized in that, the material of described coating comprises ruthenium, preferably also contains rhodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310597429.9A CN103601637A (en) | 2013-11-22 | 2013-11-22 | Treatment method for recovering fumaric acid from phthalic anhydride wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310597429.9A CN103601637A (en) | 2013-11-22 | 2013-11-22 | Treatment method for recovering fumaric acid from phthalic anhydride wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103601637A true CN103601637A (en) | 2014-02-26 |
Family
ID=50119921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310597429.9A Pending CN103601637A (en) | 2013-11-22 | 2013-11-22 | Treatment method for recovering fumaric acid from phthalic anhydride wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103601637A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211233A (en) * | 2014-09-26 | 2014-12-17 | 昆山美淼环保科技有限公司 | Electrooxidation process for treating water-based ink waste water |
| CN108484384A (en) * | 2018-02-11 | 2018-09-04 | 常熟联邦化工股份有限公司 | The technique for preparing fumaric acid using maleic acid waste water |
-
2013
- 2013-11-22 CN CN201310597429.9A patent/CN103601637A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 程顺国等: "苯酐和邻苯类增塑剂废水处理及综合利用研究", 《广州化工》 * |
| 陈康等: "富马酸废水中提取溴的研究", 《化学工程师》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211233A (en) * | 2014-09-26 | 2014-12-17 | 昆山美淼环保科技有限公司 | Electrooxidation process for treating water-based ink waste water |
| CN108484384A (en) * | 2018-02-11 | 2018-09-04 | 常熟联邦化工股份有限公司 | The technique for preparing fumaric acid using maleic acid waste water |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Treatment of high-salinity reverse osmosis concentrate by electrochemical oxidation on BDD and DSA electrodes | |
| CN106687417B (en) | Method and apparatus for treating industrial waste water using oxidizing agent produced from waste water | |
| Sridhar et al. | Treatment of pulp and paper industry bleaching effluent by electrocoagulant process | |
| Zhang et al. | The energy-saving production of tartaric acid using ion exchange resin-filling bipolar membrane electrodialysis | |
| Gui et al. | Electrochemical degradation of dye on TiO2 nanotube array constructed anode | |
| CN101506105A (en) | Method and integral system for treating water for cooling towers and processess requiring removal of silica from the water | |
| CN109550771B (en) | Method and device for removing organic pollutants in industrial waste salt | |
| CN102701483B (en) | Oily wastewater pretreatment system and high-efficiency oil eliminator arranged in system | |
| Eyvaz et al. | Preventing of cathode passivation/deposition in electrochemical treatment methods–a case study on winery wastewater with electrocoagulation | |
| Zhou et al. | Degradation kinetics of photoelectrocatalysis on landfill leachate using codoped TiO 2/Ti photoelectrodes | |
| Tran et al. | Electrochemical preparation and characterization of polyaniline enhanced electrodes: An application for the removal of cadmium metals in industrial wastewater | |
| CN103553899B (en) | The method reclaiming fumaric acid from phthalic anhydride wastewater | |
| CN103601637A (en) | Treatment method for recovering fumaric acid from phthalic anhydride wastewater | |
| CN109896948A (en) | A method of benzene carboxylic acid is prepared using middle low-order coal as raw material | |
| BR102015030975A2 (en) | effluent treatment from biodiesel washing using electroflotation / electrooxidation and coupled fenton | |
| CN103523869A (en) | Rotary-drum high-voltage pulse electric flocculation device | |
| CN201850163U (en) | Environment friendly technology (EFT) sewage treatment electrolysis equipment | |
| CN104529019A (en) | Electric catalytic combined processing method suitable for high-salinity refractory wastewater | |
| Budiyono et al. | Study on treatment of slaughterhouse wastewater by electro-coagulation technique | |
| CN103755099A (en) | Multidimensional poleless electro-oxidation wastewater treatment method | |
| CN103588266A (en) | Chemical recycling method for treating organic acid in wastewater from electrode foil chemical synthesis | |
| CN108083392B (en) | Device and method for preparing superfine iron oxide and regenerating pickling solution by using pickling waste liquor | |
| CN202170259U (en) | Reverse osmosis system electrolyzing device with high recovery rate | |
| CN107253781B (en) | Method for recycling acidic copper-containing waste liquid | |
| CN201971666U (en) | Adapter board of EFT (environmental friendly technology) inert combined electrode and electrolysis equipment comprising adapter board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140226 |