CN102276017A - Equipment and method for converting acrylic acid (acrylate) into propionic acid (propionate) - Google Patents
Equipment and method for converting acrylic acid (acrylate) into propionic acid (propionate) Download PDFInfo
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- CN102276017A CN102276017A CN2010105473253A CN201010547325A CN102276017A CN 102276017 A CN102276017 A CN 102276017A CN 2010105473253 A CN2010105473253 A CN 2010105473253A CN 201010547325 A CN201010547325 A CN 201010547325A CN 102276017 A CN102276017 A CN 102276017A
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Abstract
The invention discloses an electrocatalytic reduction equipment and an electrocatalytic reduction method for converting acrylic acid (acrylate) into propionic acid (propionate). The equipment comprises a tank body, a plurality of cathodes, a plurality of anodes and a plurality of ion exchange diaphragms, wherein the plurality of ion exchange diaphragms divide the tank body into a plurality of independent regions, different electrodes are arranged in two adjacent regions, the anodes are arranged in anode chambers and cathodes are arranged in cathode chambers; the anode chambers each have a liquid inlet and a liquid outlet; and the cathode chambers each have a water inlet and a water outlet. The electrocatalytic reduction method disclosed by the invention comprises: connecting the positive and negative poles of a power supply with the anodes and cathodes of the equipment respectively; allowing a water sample to be treated to flow through the cathode chambers from bottom up and solution in the anode chambers to flow through the anode chambers from bottom up; and discharging treated water from equipment. The equipment and the method, which are disclosed by the invention, are suitable for waste water from production of acrylic acid (acrylate) with high salt content and can obviously reduce toxicity of the waste water from the production of acrylic acid (acrylate).
Description
Technical field
The present invention relates to vinylformic acid (salt) is converted into the Apparatus for () and method therefor of propionic acid (salt).
Background technology
Can produce a large amount of waste water that contains higher concentration vinylformic acid or acrylate in the production process of vinylformic acid and ester etc. thereof.Because vinylformic acid and salt pair microorganism thereof have certain toxicity, directly carry out biochemical treatment, problems such as sludge loss, treat effluent water quality instability often occur.Contain acrylic acid wastewater at present adopts technologies such as heating power burning method, biological process to handle more.After the heating power burning process is about to contain the acrylic acid waste water of high density and concentrates through gas stripping column, under combustion-supporting compressed-air actuated help, be the vaporific waster water incinerator that sprays into, fuel gas or oil fuel also enter the roasting kiln burning simultaneously, the burning gas temperature can reach 950 ℃, under 950 ℃ high temperature, organism complete reaction in the waste water becomes carbonic acid gas and water, and processing efficiency is very high.But heating power burning process initial cost is big, consumes a large amount of fuel gas or oil fuel, energy consumption and running cost height, and the sodium salt that contains high density in the waste water such as acrylate usually, cause the corrosion of incinerator easily, stove brick etc. need periodic replacement, have further increased running cost.Vinylformic acid is biodegradable organic, but because the toxicity of vinylformic acid (salt), biological treatment needs to contain vinylformic acid (salt) waste water usually to carry out handling behind the Macrodilution with sanitary sewage, water coolant etc. again, its shortcoming is a large amount of water coolant of wastewater dilution waste, the bioprocess technology floor space is big, operational management requires high, fluctuation of service etc.Therefore the processing that contains vinylformic acid (salt) waste water is the difficult problem in Industrial Wastewater Treatment field always.Wait treatment process to compare with burning, biological treatment is low to equipment and operational management requirement, and initial cost and running cost are economized.Toxicity in the waste water if can be converted into the less material of toxicity by bigger vinylformic acid,, promptly reduce the toxicity of waste water as propionic acid, adopt biological treatment to handle then, to improve the unitary efficient of subsequent biological treatment greatly, save diluting water, and reduce to take up an area of and processing cost.
At present domesticly mainly contain " electrolysis-biochemical process " (CN 1948189A), " electrodialysis-biochemistry-extraction-rectification method " (CN 101269899A), " reverse osmosis-rectification method " (CN 1903738A) etc. at the patent that contains the acrylic acid waste water treatment.The method that patent CN1948189A announces has only been carried out conventional electrolysis treatment to waste water, is conceived to the oxidation of pollutent; The method that CN 1903738A announces is carried out rectifying after waste water reverse osmosis is concentrated, and reclaims wherein vinylformic acid, toluene and acetate, and this method is more suitable for the low acrylic acid production waste water of saltiness; The method that patent CN 101269899A announces adopts traditional electrodialysis that waste water is concentrated, and carries out extraction-rectification after concentrating, and reclaims acetate wherein, and this method is more suitable for the low acrylic acid production waste water of saltiness.
Summary of the invention
The purpose of this invention is to provide high vinylformic acid (ester) factory effluent of a kind of suitable saltiness, can significantly reduce the electrical catalyze reduction Apparatus for () and method therefor that vinylformic acid (salt) is converted into propionic acid (salt) that contains vinylformic acid (salt) wastewater toxicity.
Provided by the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction equipment of propionic acid (salt), comprises pond body, some negative electrodes, some anodes and some ion exchange membranes; Some ion exchange membranes are divided into some distinct area with the pond body, and two adjacent areas are provided with different electrodes, form utmost point chamber; It is the anolyte compartment that anodic is set, and the cathode compartment that is of negative electrode is set; The anolyte compartment is provided with fluid inlet that enters for anolyte compartment's solution and the leakage fluid dram of discharging for anolyte compartment's solution; Cathode compartment be provided with the water-in that enters for pending water sample and handle after the water water port of discharging.
Of the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction equipment of propionic acid (salt), wherein: described fluid inlet is arranged on the bottom of described anolyte compartment, and described leakage fluid dram is arranged on top, described anolyte compartment.
Of the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction equipment of propionic acid (salt), wherein: described water-in is arranged on the bottom of described cathode compartment, and described water port is arranged on described cathode compartment top.
Of the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction equipment of propionic acid (salt), wherein: described ion exchange membrane is a cationic exchange membrane.
Of the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction equipment of propionic acid (salt), wherein: described anode is titanium coated electrode, Graphite Electrodes or platinum electrode.
Of the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction equipment of propionic acid (salt), wherein: described negative electrode is that foam nickel electrode, nickel foam are coated with palladium or silver layer electrode, carbon fiber electrode, stainless steel electrode or titanium coated electrode.
The electrical catalyze reduction method that vinylformic acid (salt) is converted into propionic acid (salt) provided by the present invention, be that positive and negative electrode with power supply links to each other with negative electrode with the anode of described electrical catalyze reduction equipment respectively, pending water sample flows through cathode compartment from bottom to top, anolyte compartment's solution flows through the anolyte compartment from bottom to top, and the water after the processing is discharged from described electrical catalyze reduction equipment.
Of the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction method of propionic acid (salt), wherein: described anolyte compartment solution is sulphuric acid soln.
Of the present invention vinylformic acid (salt) is converted into the electrical catalyze reduction method of propionic acid (salt), wherein: described method comprises expression of first degree conversion process, circulating conversion process, the circulating conversion process of part or multistage continous way conversion process.
The waste water of the vinylformic acid (salt) of lower concentration during the expression of first degree conversion process is suitable for containing is meant and adopts separate unit that the device processes waste water that vinylformic acid (salt) is converted into propionic acid (salt) is reached acrylic acid conversion requirement, can adopt the installation form of multistage multistage.
Circulating operating process is suitable on a small scale, high density contains vinylformic acid (salt) waste water, is meant that pending water sample is vinylformic acid (salt) being converted into the equipment internal recycle processing of propionic acid (salt), until reaching acrylic acid conversion requirement.
The circulating conversion process of part is meant that the water sample after the device processes through vinylformic acid (salt) being converted into propionic acid (salt) partly turns back to the water-in that vinylformic acid (salt) is converted into the equipment of propionic acid (salt), thereby reduce water inlet vinylformic acid (salt) concentration, reduce required sum of series hop count.
Multistage continous way conversion process is meant pending water sample, through many single-stages or many multistage multistages are placed in-line vinylformic acid (salt) is converted into the equipment of propionic acid (salt) after, once transform and reach processing requirements.
Vinylformic acid (salt) is meant the mixture of vinylformic acid or acrylate or vinylformic acid and acrylate.
The electrical catalyze reduction method that vinylformic acid (salt) is converted into propionic acid (salt) of the present invention, be fit to above vinylformic acid (ester) factory effluent of saltiness 500mg/L, utilization is converted into vinylformic acid (salt) the electrical catalyze reduction equipment of propionic acid (salt), can significantly reduce the toxicity that contains vinylformic acid (salt) waste water, improve the unitary operation stability of subsequent biological treatment and handle load, reduce the scale and the occupation of land of waste water disposal facility, reduce initial cost.
Description of drawings
Fig. 1 is the equipment sectional view that vinylformic acid (salt) is converted into propionic acid (salt) of the present invention.
Embodiment
The device structure synoptic diagram that employing electrical catalyze reduction mode of the present invention is converted into propionic acid (salt) with vinylformic acid (salt) as shown in Figure 1.
The electrical catalyze reduction equipment that vinylformic acid is converted into propionic acid of the present invention comprises pond body 5, some negative electrodes 8, some anodes 6, some ion exchange membranes 7.Some ion exchange membranes 7 are divided into some distinct area with pond body 5, and two adjacent areas are provided with different electrodes, form utmost point chamber, as shown in Figure 1, the anolyte compartment that is of anode 6 are set, and the cathode compartment that is of negative electrode 8 is set.The anolyte compartment is provided with fluid inlet 3 that enters for anolyte compartment's solution and the leakage fluid dram 1 of discharging for anolyte compartment's solution, and fluid inlet 3 is arranged on the bottom of anolyte compartment, and leakage fluid dram 1 is arranged on the top, anolyte compartment.Cathode compartment be provided with the water-in 4 that enters for the pending water sample that contains vinylformic acid (salt) and handle after the water water port 2 of discharging, water-in 4 is arranged on the bottom of cathode compartment, water port 2 is arranged on the cathode compartment top.Wherein, ion exchange membrane 7 is a cationic exchange membrane, and anode 6 can adopt stabilized electrodes such as titanium coated electrode, Graphite Electrodes, platinum electrode; Negative electrode 8 can adopt foam nickel electrode, nickel foam coated electrode (being coated with palladium, silver etc.), carbon fiber electrode, stainless steel electrode, titanium coated electrode etc.Anolyte compartment's solution is sulphuric acid soln.
The positive and negative electrode of power supply links to each other with negative electrode with anode respectively, and cathode compartment and anolyte compartment's solution flow through cathode compartment and anolyte compartment from bottom to top under the driving of pump, and in water sample and process that negative electrode contacts, vinylformic acid generates propionic acid in cathode surface generation reductive action.
CH
2＝CHCOOH+2H
2O+2e
-→CH
3-CH
2COOH+2OH
-
Water generates oxygen in anode generation oxygenizement, and the hydrogen ion of additional cathode consumption.
2H
2O→O
2+4H
++4e
-
Embodiment 1: handle intermediate concentration acrylate waste water
Employing is converted into the equipment of propionic acid (salt) with vinylformic acid (salt), and being coated with ruthenium electrode with titanium is anode, and foam nickel electrode is a negative electrode, with 0.1M H
2SO
4Be anolyte, adopt circulating operation flow processes to contain the sodium acrylate water sample that propylene acid group concentration is 5000mg/L, electric current is 1A, constant current operation, behind the processing 0.5h, the vinylformic acid transformation efficiency reaches 79.5%, propylene acid group concentration is reduced to 1025mg/L in the water sample, and propionate concentration reaches 4087mg/L.
Embodiment 2: handle high density acrylate waste water
Employing is converted into the equipment of propionic acid (salt) with vinylformic acid (salt), and being coated with ruthenium electrode with titanium is anode, and foam nickel electrode is a negative electrode, with 0.1M H
2SO
4Be anolyte, adopt circulating operation flow processes to contain the butyl acrylate factory effluent that propylene acid group concentration is 40000mg/L, electric current is 1A, constant current operation, after handling 3.0h, the vinylformic acid transformation efficiency reaches 93.8%, and propylene acid group concentration is reduced to 2480mg/L in the water sample, and propionate concentration reaches 38577mg/L.
Embodiment 3: handle high density acrylate waste water
Employing is converted into the equipment of propionic acid (salt) with vinylformic acid (salt), and being coated with ruthenium electrode with titanium is anode, and being coated with silver-colored foam nickel electrode is negative electrode, with 0.1M H
2SO
4Be anolyte, adopt circulating operation flow processes to contain the sodium acrylate water sample that propylene acid group concentration is 32000mg/L, electric current is 2.5A, constant current operation, behind the processing 1.5h, the vinylformic acid transformation efficiency reaches 97.0%, propylene acid group concentration is reduced to 960mg/L in the water sample, and propionate concentration reaches 31914mg/L.
Above embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (9)
1. vinylformic acid (salt) is converted into the electrical catalyze reduction equipment of propionic acid (salt), it is characterized in that: comprise pond body (5), some negative electrodes (8), some anodes (6) and some ion exchange membranes (7); Some ion exchange membranes (7) are divided into some distinct area with pond body (5), and two adjacent areas are provided with different electrodes, form utmost point chamber; The anolyte compartment that is of anode (6) is set, the cathode compartment that is of negative electrode (8) is set; The anolyte compartment is provided with fluid inlet (3) that enters for anolyte compartment's solution and the leakage fluid dram (1) of discharging for anolyte compartment's solution; Cathode compartment be provided with the water-in (4) that enters for pending water sample and handle after the water port (2) of water discharge.
2. electrical catalyze reduction equipment according to claim 1 is characterized in that: described fluid inlet (3) is arranged on the bottom of described anolyte compartment, and described leakage fluid dram (1) is arranged on top, described anolyte compartment.
3. electrical catalyze reduction equipment according to claim 1 and 2 is characterized in that: described water-in (4) is arranged on the bottom of described cathode compartment, and described water port (2) is arranged on described cathode compartment top.
4. electrical catalyze reduction equipment according to claim 3 is characterized in that: described ion exchange membrane (7) is a cationic exchange membrane.
5. electrical catalyze reduction equipment according to claim 4 is characterized in that: described anode (6) is titanium coated electrode, Graphite Electrodes or platinum electrode.
6. electrical catalyze reduction equipment according to claim 5 is characterized in that: described negative electrode (8) is that foam nickel electrode, nickel foam are coated with palladium or silver layer electrode, carbon fiber electrode, stainless steel electrode or titanium coated electrode.
7. vinylformic acid (salt) is converted into the electrical catalyze reduction method of propionic acid (salt), be with the positive and negative electrode of power supply respectively with claim 1～6 in the anode of arbitrary described electrical catalyze reduction equipment link to each other with negative electrode, pending water sample flows through cathode compartment from bottom to top, anolyte compartment's solution flows through the anolyte compartment from bottom to top, and the water Accessory Right after the processing requires arbitrary described electrical catalyze reduction equipment discharge in 1～6.
8. electrical catalyze reduction method according to claim 7 is characterized in that: described anolyte compartment solution is sulphuric acid soln.
9. electrical catalyze reduction method according to claim 7 is characterized in that: described method comprises expression of first degree conversion process, circulating conversion process, the circulating conversion process of part or multistage continous way conversion process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105473253A CN102276017A (en) | 2010-11-16 | 2010-11-16 | Equipment and method for converting acrylic acid (acrylate) into propionic acid (propionate) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105473253A CN102276017A (en) | 2010-11-16 | 2010-11-16 | Equipment and method for converting acrylic acid (acrylate) into propionic acid (propionate) |
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|---|---|
| CN102276017A true CN102276017A (en) | 2011-12-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105473253A Pending CN102276017A (en) | 2010-11-16 | 2010-11-16 | Equipment and method for converting acrylic acid (acrylate) into propionic acid (propionate) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968002A (en) * | 2016-05-06 | 2016-09-28 | 中国环境科学研究院 | Method for producing acrylic acid ester with low pollutant discharge amount |
| CN108046378A (en) * | 2017-11-20 | 2018-05-18 | 广东沃杰森环保科技股份有限公司 | Electroreduction sewage disposal device and technique |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083871A (en) * | 1993-05-31 | 1994-03-16 | 华东化工学院 | Frame type fixed bed electrode electrolyzer and industrial application thereof |
| CN1275535A (en) * | 2000-01-24 | 2000-12-06 | 黄君礼 | Acid/alkali electrolytic separator |
| CN101306855A (en) * | 2007-11-07 | 2008-11-19 | 傅叶明 | Plate type electro-deionization device |
-
2010
- 2010-11-16 CN CN2010105473253A patent/CN102276017A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083871A (en) * | 1993-05-31 | 1994-03-16 | 华东化工学院 | Frame type fixed bed electrode electrolyzer and industrial application thereof |
| CN1275535A (en) * | 2000-01-24 | 2000-12-06 | 黄君礼 | Acid/alkali electrolytic separator |
| CN101306855A (en) * | 2007-11-07 | 2008-11-19 | 傅叶明 | Plate type electro-deionization device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968002A (en) * | 2016-05-06 | 2016-09-28 | 中国环境科学研究院 | Method for producing acrylic acid ester with low pollutant discharge amount |
| CN105968002B (en) * | 2016-05-06 | 2019-02-26 | 中国环境科学研究院 | A kind of acrylate production method that pollutant discharge amount is low |
| US10526217B2 (en) | 2016-05-06 | 2020-01-07 | Chinese Research Academy Of Environmental Sciences | Method for producing acrylic ester with low pollutant discharge |
| CN108046378A (en) * | 2017-11-20 | 2018-05-18 | 广东沃杰森环保科技股份有限公司 | Electroreduction sewage disposal device and technique |
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Application publication date: 20111214 |