CN101312914B - Method for treating wastewater - Google Patents
Method for treating wastewater Download PDFInfo
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- CN101312914B CN101312914B CN2006800439224A CN200680043922A CN101312914B CN 101312914 B CN101312914 B CN 101312914B CN 2006800439224 A CN2006800439224 A CN 2006800439224A CN 200680043922 A CN200680043922 A CN 200680043922A CN 101312914 B CN101312914 B CN 101312914B
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- sulfide
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- propenoate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Abstract
Disclosed is a method for treating wastewater containing a water-soluble polymerizable organic acid or a polymerization product thereof and polyvalent metal ions. Specifically, a sulfide and/or hydrosulfide of an alkali metal is added into the wastewater, thereby converting the polyvalent metal ions into a sulfide, and then a flocculating agent or a filer aid is added thereinto for forming a sludge containing the sulfide of the polyvalent metal. After that, the sludge is dehydrated by a solid-liquid separator, thereby separating the sulfide of the polyvalent metal from the waster water.
Description
Technical field
The present invention relates to a kind of; At the organic acid that contains water miscible polymerizability at least and/or its polymkeric substance; With add vulcanizing agent in the waste water of polyvalent metal ion; As the wastewater treatment method of sulfide removal polyvalent metal ion, and the method for manufacture that makes up the propenoate or the methacrylic ester of this method of wastewater treatment.
Background technology
Generally, the ester of vinylformic acid or methylacrylic acid (below, both are abbreviated as (methyl) vinylformic acid) is in the presence of strongly acidic catalysts such as sulfuric acid, p-toluenesulphonic acids, methanesulfonic, pure and mild (methyl) vinylformic acid condensation manufacturing to be formed.This reaction is the by product condensation water that generates to be removed carry out outside carrying out system.After reaction finishes,, reaction solution is washed through buck, salt solution, zero(ppm) water etc. in order to remove remaining catalyzer and (methyl) vinylformic acid.
Contain a large amount of water-soluble organic compounds in the washes that the washing of reaction solution produces, (COD) is higher for COD.So after the water-soluble organic compounds combustion oxidation disaggregating treatment that contains in the washes, treated water is discharged in the rivers and creeks.
During the condensation reaction of (methyl) vinylformic acid and alcohol,, in reaction solution, add metallic compound sometimes as stopper in order to prevent (methyl) polymerizing acrylic acid.When using the stopper of metallic compound composition, this metals ion of dissolving in above-mentioned washes.At this moment, can not carry out wastewater treatment through burning, discharging.Copper compound is more in the metallic compound that adds as stopper, and concrete have cupric chloride, copper sulfate.
Copper compounds etc. prevent the environmental standard defined of method by water pollution, only carry out burn processing and be being difficult to making the waste water of burning back discharging to meet below the statutory standards of this metal concentration.
As the prior art of from the waste water that contains metallic compound, removing metal, for example corrode the treatment technology of waste water.In patent documentation 1, disclose, used oxygenant will contain after cupric ion in corrosion waste water becomes oxide compound, reclaimed the method for oxide compound roughly.In addition, in patent documentation 2, disclose, used sodium sulphite, reclaimed the treatment process of the corrosion waste liquid of cupric sulfide.
But, in these documents, do not put down in writing in the above-mentioned corrosion waste liquid and contain water-soluble organic compounds.The treatment process of putting down in writing in these documents is applicable in the washes of (methyl) propenoate formation reaction liquid etc. be difficult.The organic acid and/or its polymkeric substance that contain polymerizability in these washess.Its result, MOX and sulfide exist with dispersive state stably in washed draining, these are precipitated from washes, to separate be difficult.
Patent documentation 1: the spy opens 2003-213346 communique (claim 1)
Patent documentation 2: the spy opens flat 6-16421 communique (claim 1)
Summary of the invention
The problem that invention will solve
In the waste water that contains water miscible polymerizability organic acid etc., the oxide compound of polyvalent metal ion and the solids of sulfide exist with dispersion state stably in waste water.So, in this wastewater treatment, be difficult to from waste water, remove this polyvalent metal ion.
The object of the present invention is to provide a kind of; At least containing water miscible polymerizability organic acid and/or its polymkeric substance; With remove the wastewater treatment method of polyvalent metal ion effectively in the waste water of polyvalent metal ion, and the method for manufacture that makes up (methyl) propenoate of this method of wastewater treatment.
The method of dealing with problems
The inventor etc. will develop a kind of, in the waste water that contains water miscible polymerizability organic acid and polyvalent metal ion at least, reclaim polyvalent metal and the method for the waste water burn processing after the polyvalent metal recovery has been carried out meticulous research as purpose.Its result makes polyvalent metal ion become sulfide and does not dissolve if find vulcanizing agent is added in the waste water, can be simply from the waste water of the organic acid of the water miscible polymerizability that contains these polyvalent metals etc., separate.And when in the waste water of this interpolation over cure agent, adding flocculation agent or filtration adjuvant, discovery can precipitate and isolate the slurry that contains polyvalent metal sulfide from waste water.Because it is lower to isolate the concentration of the polyvalent metal ion that contains in the waste water of slurry in this way, so, can directly discharge with after this waste water burn processing.The present invention accomplishes according to foregoing.
The present invention who addresses the above problem is like following record.
(1) a kind of wastewater treatment method that contains water miscible polymerizability organic acid and/or its polymkeric substance and polyvalent metal ion; After it is characterized in that in above-mentioned waste water, adding the sulfide and/or sulfhydrate of basic metal, separate the sulfide of the above-mentioned polyvalent metal that generates.
(2) according to (1) described wastewater treatment method, wherein the sulfide of basic metal and/or sulfhydrate are sodium sulphite and/or sodium sulfhydrate.
(3) according to (1) described wastewater treatment method, wherein water miscible polymerizability organic acid is vinylformic acid or methylacrylic acid.
(4) according to (1) described wastewater treatment method, wherein polyvalent metal ion is a cupric ion.
(5) according to (4) described wastewater treatment method, wherein the addition of the sulfide of basic metal and/or sulfhydrate with respect to cupric ion be wait mole more than.
(6) according to (1) described wastewater treatment method, wherein make the redox potential of waste water become sulfide and/or the sulfhydrate that 0mV adds basic metal followingly.
(7) according to (1) described wastewater treatment method, wherein make the pH value of waste water be adjusted at 7～13.
(8) a kind of wastewater treatment method that contains organic acid and/or its polymkeric substance and the polyvalent metal ion of water miscible polymerizability; After sulfide and/or the sulfhydrate that it is characterized in that in above-mentioned waste water adding basic metal becomes sulfide with polyvalent metal ion; Add the slurry that flocculation agent or filtration adjuvant form the sulfide that contains above-mentioned polyvalent metal, afterwards above-mentioned slurry is isolated the sulfide of above-mentioned polyvalent metal through the solid-liquid separating machine dehydration from waste water.
(9) according to (8) described wastewater treatment method, wherein flocculation agent is the organic flocculation agent of nonionic and/or anionic property.
(10) method of manufacture of a kind of propenoate or methacrylic ester; Comprising following operation: make in the presence of the cupric ion of vinylformic acid or methylacrylic acid and alcohol strongly acidic catalyst and the stopper in solvent and react, obtain containing the operation of the reaction solution of propenoate or methacrylic ester; With above-mentioned reaction solution is washed with washing water, separate into the organic layer that contains propenoate or methacrylic ester and the operation that contains the washes of cupric ion; With above-mentioned washes treatment procedures; Wherein above-mentioned washes treatment procedures is; The sulfide and/or the sulfhydrate that in above-mentioned washes, add basic metal generate after the cupric sulfide, add flocculation agent, make the operation of the slurry agglomeration separation that contains cupric sulfide.
(11) method of manufacture of a kind of propenoate or methacrylic ester; Comprising following operation: make in the presence of the cupric ion of vinylformic acid or methylacrylic acid and alcohol strongly acidic catalyst and the stopper in solvent and react, obtain containing the operation of the reaction solution of propenoate or methacrylic ester; With above-mentioned reaction solution is washed with washing water, separate into the organic layer that contains propenoate or methacrylic ester and the operation that contains the washes of cupric ion; With with above-mentioned washes treatment procedures; Wherein above-mentioned washes treatment procedures is; The sulfide and/or the sulfhydrate that in above-mentioned washes, add basic metal generate after the cupric sulfide, add filtration adjuvant, make the isolating operation of slurry co-precipitation that contains cupric sulfide.
(12), wherein from washes, isolate the processing waste water that the slurry that contains cupric sulfide will obtain and carry out burn processing according to (10) the perhaps method of manufacture of (11) described propenoate or methacrylic ester.
The effect of invention
According to the method for the invention, through in the waste water of the organic acid that contains water miscible polymerizability and/or its polymkeric substance and polyvalent metal ion, adding the sulfuration agent, can from waste water, will remove simply as the polyvalent metal ion of sulfide.In aforesaid method, if when vulcanizing agent and flocculation agent or filtration adjuvant used together, can make the sulfide cohesion of dispersive polyvalent metal in the waste water, separate as slurry, can easily from waste water, polyvalent metal ion be removed.
According to the method for the invention, can the polyvalent metal ion that contain in the waste water be reclaimed as sulfide, utilize again.
Description of drawings
The process chart of the method for manufacture of Fig. 1 shows (methyl) of the present invention propenoate.
Description of reference numerals
2 reaction process
4 neutralizations, washing procedure
6 refining steps
10 wastewater troughs
12 sulfidizing operations
14 solid-liquid separation process
16 waste water burning operation
Embodiment
The present invention is the wastewater treatment method that contains water miscible polymerizability organic acid and/or its polymkeric substance and polyvalent metal ion.
Water miscible polymerizability organic acid and/or its polymkeric substance of the various ratios that the present invention goes in waste water, containing.If during (methyl) vinylformic acid of polymerizability, the whole organism carbon elements that convert as (methyl) sodium acrylate (below be called TOC) can be suitable for and contain 1～15 quality % in the preferably draining.
Organic acid as polymerizability; Can enumerate (methyl) vinylformic acid, oxalic acid, methylene-succinic acid, toxilic acid, Ba Dousuan, styracin, 2-phenylacrylic acid, fumaric acid, methylfumaric acid, citraconic acid, equisetic acid, propene dicarboxylic acid etc., and these polymerizability organic acid modified by polyacid thing etc.The present invention, in these, containing (methyl) acrylic acid waste water is preferably to be applicable to present method.
As polyvalent metal ion, can enumerate cupric ion, iron ion, cadmium ion, lead ion, mercury ion, zine ion etc.The present invention, the waste water that in these, contains cupric ion is preferably to go for present method.
In the present invention, use the sulfide and/or the sulfhydrate of basic metal as vulcanizing agent.As basic metal, preferred sodium and potassium.As concrete compound, can enumerate sodium sulphite, sodium sulfhydrate, potassium sulphide etc.Can separately or the combination more than 2 kinds be used.
The addition of vulcanizing agent as the total amount of each vulcanizing agent, contains in the preferred waste water and metals ion etc. more than the mole, more preferably 1.0～2.0 times of molar weights.In addition, the vulcanizing agent that adds in the waste water is no matter be that the aqueous solution or solid can use.
When not knowing the metal concentration that contains in the waste water, the addition of vulcanizing agent is preferably managed by redox potential.At this moment, for polyvalent metal ion fully is transformed to sulfide, preferably add the sulfide and/or the sulfhydrate of basic metal, till the redox potential of waste water changes to below the 0mV.
In order to prevent to produce hydrogen sulfide, the pH value of waste water preferably is adjusted at 7～13 in advance before adding vulcanizing agent, more preferably 8～12.
In the above-mentioned waste water, add after the vulcanizing agent, can from waste water, separate the sulfide of polyvalent metal ion through using known method such as filtration, cf-separation.
At the waste water of the organic acid that contains water miscible polymerizability and/or its polymkeric substance, compare with the waste water that does not contain these, the particle of metallic sulfide more stably is colloidal and disperses.In such waste water, make the metallic sulfide deposition from waste water, separate sometimes relatively difficulty.At this moment, through using flocculation agent, can form the flocks of metallic sulfide.Perhaps, through use filtration adjuvant make metallic sulfide particle and filtration adjuvant co-precipitation after, can from waste water, separate as slurry.
As flocculation agent, can enumerate that for example Tai-Ace S 150, POLY ALUMINIUM CHLORIDE, iron(ic)chloride, many iron(ic)chloride etc. are inorganic is flocculation agent; The anionic property organic system flocculation agent that gathers (methyl) sodium acrylate and (methyl) vinylformic acid and (methyl) acrylic acid amides co-polymer etc.; The nonionic organic system flocculation agent of SEPIGEL 305 etc.As nonionic organic system flocculation agent, also can in (methyl) acrylic amide, there be (methyl) vinylformic acid of a small amount of (5 moles below the %) to carry out copolymerization.
In these, see, preferably use anionic property or nonionic organic system flocculation agent from the excellent point of coherency.Cationic organic system flocculation agent in addition, the coherency of comparing with anionic property or nonionic organic system flocculation agent is relatively poor.
As the addition of organic system flocculation agent, preferably 1～100mg/L, more preferably 2～30mg/L.
The molecular weight of organic system flocculation agent, preferably 500,000～3,000 ten thousand, more preferably 1,000,000～2,000 ten thousand.
Flocculation agent can use the thing of peddling on the market, can enumerate the for example anionic property organic system flocculation agent of ARONFLOC A-101, ARONFLOC A-104, ARONFLOC A-106 (above is Toagosei Co., Ltd's manufacturing), DIAFLOC AP350M, DIAFLOC AP825B, DIAFLOC AP825C, DIAFLOC AP784, DIAFLOC AP805C, DIAFLOC AP410C, DIAFLOC AP771C (above is the dianitrix manufactured) etc.; The nonionic organic system flocculation agent of ARONFLOC N-101, ARONFLOC N-107, ARONFLOC N-207 (above is that Toagosei Co., Ltd makes), DIAFLOC NP800 (above is the dianitrix manufactured) etc.
As filtration adjuvant, can enumerate the for example diatom soil series filtration adjuvant of radiolight (clear and chemical company makes), Celite (Jhons-Manille manufactured) etc.; The pearl series of rocks filtration adjuvant of rokahelp (manufacturing of industrial of Mitsui Metal Co., Ltd.) etc. etc.
The attenuating effect of the copper concentration in the filtrating is, and is taller when ratio uses filtration adjuvant when using anionic property or nonionic organic system flocculation agent.Therefore, when processing contains the waste water of water miscible polymerizability organic acid or its polymkeric substance and polyvalent metal ion, preferably use anionic property or nonionic organic system flocculation agent.
The concentration that is dispersed in water miscible polymerizability organic acid or its polymkeric substance in the waste water of metallic sulfide does particle-stabilisedly, about about 0.5～200g/L.
Below, an example of the method for manufacture of (methyl) propenoate through having made up method of wastewater treatment of the present invention describes with reference to the process chart of Fig. 1.
Among Fig. 1, at reaction process 2, (methyl) vinylformic acid and raw alcohol carry out condensation reaction.On the reactor drum that (methyl) vinylformic acid and alcohol react, well heater and stirrer are installed preferably.
Be equipped with in advance inside at reactor drum: (methyl) vinylformic acid of raw material, raw alcohol, catalyzer, reaction solvent (toluene), stopper, Hypophosporous Acid, 50 and/or sodium hypophosphite, activated carbon etc.Catalyzer has p-methyl benzenesulfonic acid and sulfuric acid, and stopper has cupric chloride or copper sulfate.Contain the reaction solution of these compositions, heat by well heater while the machine that is stirred stirs.
Raw alcohol has, for example the monohydroxy-alcohol of the alkyl oxide of methyl alcohol, ethanol, propyl alcohol, butanols, octanol, 2-Ethylhexyl Alcohol, aklylene glycol, alkylene oxide modified phenol, alkylene oxide modification nonylphenol, alkylene oxide modification p-cumylphenol, alkylene oxide modification 2-Ethylhexyl Alcohol etc.; Terepthaloyl moietie; Ucar 35; Polyoxyethylene glycol; W 166; Tetramethylolmethane; Dipentaerythritol; TriMethylolPropane(TMP); Ditrimethylolpropane; Three (2-hydroxyethyl) isocyanuric acid ester; The tristane methylol; Glycerine; Glycerol dimer; Alkylene oxide modified bisphenol S; Alkylene oxide modified bisphenol F; The alkylene oxide modified bisphenol A; The alkylene oxide modified glycerol; Alkylene oxide modification Glycerol dimer; Alkylene oxide modification TriMethylolPropane(TMP); Alkylene oxide modification ditrimethylolpropane; Alkylene oxide modification tetramethylolmethane; Alkylene oxide modification dipentaerythritol; Alkylene oxide modification NSC 6366; Polyvalent alcohols such as polyester.As above-mentioned alkylene oxide, can enumerate oxyethane, propylene oxide.
(methyl) vinylformic acid is heated in the presence of catalyst in reactor with alcohol and carries out dehydrating condensation, generates (methyl) propenoate.(methyl) vinylformic acid and the water byproduct that pure condensation reaction generates are discharged from the top of solvent toluene azeotropic from reactor drum, are sent to rectifying tower.Afterwards, on one side rectifying is on one side risen in rectifying tower, distillate from the cat head of rectifying tower.
Be sent to condensing surface from the cat head distilled azeotropic gas (water and toluene) of rectifying tower, in condensing surface by condensing.The mixed solution of condensing water and toluene is delivered to separator from condensing surface.Because water and toluene are indissoluble each other, so in separator, be separated into two-layer.
The toluene on separated upper strata in separator is got back to the cat head side reflux of rectifying tower and is gone in the rectifying tower.The water of separated lower floor takes out from the bottom of separator in separator, flows into wastewater trough 10.
After reaction finishes, contain the reaction solution of (methyl) propenoate in the reactor drum, be sent to neutralization, washing procedure 4.
At neutralization, washing procedure 4, add alkaline water in the reaction solution in neutralizing well and stir.With this operation, when (methyl) vinylformic acid that contains in the reaction solution, catalyzer etc. were neutralized, dimeric (methyl) vinylformic acid decomposed.Afterwards, the solution in the neutralizing well is left standstill.Leave standstill operation through this, the solution in the neutralizing well is separated into organic layer that contains toluene, (methyl) propenoate and the alkaline water layer that contains (methyl) sodium acrylate, raw alcohol, cupric ion, catalyzer salt etc.Afterwards, alkaline water layer therefrom is discharged from the lower end of groove, in wastewater trough 10, stores as washes.
The washes that in wastewater trough 10, is stored is sent to sulfidizing operation 12 with the water in the separated lower floor of the separator of above-mentioned reaction process.In the sulfidizing operation, interpolation sodium sulphite and/or sodium sulfhydrate stir in the water of washes and lower floor.Through this operation, the cupric ion that contains in the washes is transformed into sulfide.
Afterwards, add flocculation agent or filtration adjuvant as required, after stirring, make the slurry deposition that contains the cupric sulfide particulate.
At solid-liquid separation process 14, the slurry that has precipitated is delivered to solid-liquid separating machine, carry out processed.
Contain (methyl) sodium acrylate, raw alcohol etc. organic cpds slurry supernatant liquid and, from the liquid effluent that solid-liquid separating machine 16 is discharged, be sent to waste water burning operation 16.The organic cpds that contains in the liquid effluent is in the burning of waste water roasting kiln, oxidized disaggregating treatment.
On the other hand, at neutralization, washing procedure 4 and the isolating organic layer of alkaline water layer, be sent to refining step 6.At refining step 6, organic layer carries out desolventizing to be handled, filters, and obtains (methyl) propenoate.
In addition, in above-mentioned explanation, represented that the azeotropic solvent that generates water as by product uses the situation of toluene, but replaced toluene to use other and water is insoluble or the solvent of indissoluble and water formation azeotropic mixture are also passable.Solvent as such has for example: benzene, YLENE, hexanaphthene, normal hexane, normal heptane, trichloroethane, zellon, trichloroethane, Di Iso Propyl Ether etc.
The solid-liquid separating machine that uses during as the processed of slurry can be enumerated vacuum filter, pressure filter, band extruder, screw extrusion press, centrifuge etc.In order to keep high dehydration rate simply, the dehydration of slurry that contains metallic sulfide is the most suitable with pressure filter, band extruder.
In above-mentioned explanation, use the situation of alkaline water to be illustrated to the washing of reaction solution, but when the washing of reaction solution, also can use zero(ppm) water, NaCl solution etc. as example.The processing of the waste water that produces when using these to wash equally in the time of also can be with alkaline water be adopted same processing.
As (methyl) propenoate that uses method of wastewater treatment of the present invention to make, can enumerate: for example tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, tetramethylolmethane five (methyl) propenoate, tetramethylolmethane six (methyl) propenoate, NSC 65881 three (methyl) propenoate, dipentaerythritol three (methyl) propenoate, dipentaerythritol four (methyl) propenoate, dipentaerythritol five (methyl) propenoate, dipentaerythritol six (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, TriMethylolPropane(TMP) four (methyl) propenoate, ditrimethylolpropane three (methyl) propenoate, ditrimethylolpropane four (methyl) propenoate, alkylene oxide modification trimethylolpropane tris (methyl) propenoate, alkylene oxide modified bisphenol A two (methyl) propenoate, alkylene oxide modification nonylphenol list (methyl) propenoate, alkylene oxide modification right-isopropyl-phenol list (methyl) propenoate, polyester (methyl) propenoate etc.These (methyl) propenoate produce each waste water when making, can separately or mix and carry out sulfidizing operation, solid-liquid separation process, waste water burning operation.
Embodiment
Make the propenoate of record on embodiment 1～4 and the comparative example 1,2, the reaction solution that washing obtains obtains each washes (pH value 8～10) of following formation.For each washes, carry out the wastewater treatment that embodiment 1～4 and comparative example 1,2 are put down in writing.
[formation of washes]
TOC (sodium acrylate conversion) 5～7 quality %
Cupric chloride 0.1～0.4 quality %
Sodium sulfate 8～14 quality %
Sodium hydroxide 0.5～1.0 quality %
The flocculation agent A or the B that use are experiment products, and its details are described below.The negatively charged ion that (flocculation agent A) is made up of the acrylic amide sodium acrylate copolymer is a flocculation agent, and sodium acrylate is 27 quality %, and molecular-weight average is about 1,300 ten thousand, and white powder, volume weight are 0.65g/cc.The nonionic that (flocculation agent B) is made up of the acrylic amide sodium acrylate copolymer is a flocculation agent, and sodium acrylate is 3 quality %, and molecular-weight average is about 1,100 ten thousand, and white powder, volume weight are 0.65g/cc.
Embodiment 1
After carrying out dehydration condensation (esterification) with the method for being put down in writing in following (1) and (2), reaction solution neutralization, washing have been carried out.
(1) use tetramethylolmethane 29 mass parts (being designated hereinafter simply as " part "), 73 parts in vinylformic acid, as 2 parts in the sulfuric acid of catalyzer, as 0.4 part of the cupric chloride of stopper, 70 parts of use toluene are as organic solvent, making the reaction solution gross weight is 15t.Reacting by heating liquid carries out esterification, obtains mixtures tetramethylolmethane, triacrylate, tetraacrylate, five propenoate and six propenoate.
(2) use 36 parts of NSC 65881s, 73 parts in vinylformic acid, as 3 parts in the sulfuric acid of catalyzer, as 0.8 part of the cupric chloride of stopper, use 60 parts of toluene as organic solvent, making the reaction solution gross weight is 15t.Reacting by heating liquid carries out esterification, obtains mixtures dipentaerythritol, triacrylate, tetraacrylate, five propenoate and six propenoate.
The reaction solution that contains various propenoate mixtures that obtains is washed with washings, obtain each washes respectively.Washings has used the aqueous sodium hydroxide solution of 100g/L, and tap water.
As the washes after neutralization, the washing, the washes 20 quality % that used the reaction of (1) to obtain, and the washes 80 quality % blended liquid that obtain of the reaction of (2).
With the above-mentioned washes 1L (Cu that obtains; 5mmol～25mmol ※ reacts at each, and the processing water yield of the cupric chloride of use has domain of walker, so and because these values of derivation asynchronism(-nization) of waste water have certain domain of walker, generation changes.) to process 20 quality %pH values be 12 aqueous sodium hydroxide solution.Afterwards, adding the 4.5 about 30ml of quality % sodium sulfhydrate solution (25mmol), to make the redox potential of waste water be 0mV.And then, add the aqueous solution of flocculation agent A, make content with respect to wastewater solid shape part become 30mg/L after, leave standstill.The SV30 of the waste water of this moment (leaving standstill the volume of 30 minutes solid shape parts afterwards) is 20%.
Afterwards, (5C) carries out suction strainer to waste water with filter paper, will consolidate shape and partly separate.Filterableness is good, does not find the SS (outstanding absurd creature matter) of cupric sulfide in the filtrating, and the copper concentration in the filtrating is 1mg/L.
In addition, when making an experiment property testing (washes 200L) with this condition, pressure filter, band extruder have all been obtained good result.The copper concentration that has obtained filtrating is that 0.5mg/L, water cut are 50% good cupric sulfide slurry.
Embodiment 2
After carrying out esterification with the method for following (1) and (2), reaction solution neutralization, washing have been carried out.
(1) use 32 parts of TriMethylolPropane(TMP)s, 73 parts in vinylformic acid, as 2 parts of the p-toluenesulphonic acidss of catalyzer, as 0.1 part of the cupric chloride of stopper, use 100 parts of toluene as organic solvent, making the reaction solution gross weight is 15t.Reacting by heating liquid carries out esterification, obtains the propenoate of TriMethylolPropane(TMP).
(2) use 63 parts of ditrimethylolpropanes, 80 parts in vinylformic acid, as 5 parts of the p-toluenesulphonic acidss of catalyzer, as 0.2 part of the cupric chloride of stopper, use 80 parts of toluene as organic solvent, making the reaction solution gross weight is 15t.Reacting by heating liquid carries out esterification, obtains the triacrylate of ditrimethylolpropane and the mixture of tetraacrylate.
The reaction solution that contains various propenoate mixtures that obtains is washed with washings, obtain washes.Washings has used the aqueous sodium hydroxide solution of 100g/L, and tap water.
As the washes after neutralization, the washing, the washes 40 quality % that used the reaction of (1) to obtain, and the washes 60 quality % blended liquid that obtain of the reaction of (2).
For the above-mentioned washes that obtains, carry out same wastewater treatment with embodiment 1 except having used the flocculation agent B.The SV30 of waste water is 17%.
Afterwards, (5C) carries out suction strainer to waste water with filter paper, will consolidate shape and partly separate.Filterableness is good, does not find the SS of cupric sulfide in the filtrating.Copper concentration in the filtrating is 2mg/L.
Embodiment 3
Use 120 parts of alkylene oxide modification TriMethylolPropane(TMP)s, 100 parts in vinylformic acid, as 6 parts of the p-toluenesulphonic acidss of catalyzer, as 0.2 part of the cupric chloride of stopper, use 200 parts of toluene as organic solvent, making the reaction solution gross weight is 15t.Reacting by heating liquid carries out esterification, makes after the propenoate of alkylene oxide modification TriMethylolPropane(TMP), with reaction solution neutralization, washing, obtains washes.Washings has used the aqueous sodium hydroxide solution of 50g/L, and tap water.
As the washes after neutralization, the washing, the washes 100 quality % that used above-mentioned reaction to obtain.
To the above-mentioned washes that obtains, add 8.3 quality % sodium sulfide solutions with the ratio that every L waste water adds about 25ml, make the redox potential of waste water be-30mV.
Add flocculation agent A, make content become 30mg/L, mix and leave standstill with respect to wastewater solid shape part.SV30 is 20%.
Afterwards, (5C) carries out suction strainer to waste water with filter paper, will consolidate shape and partly separate.Filterableness is good, does not find the SS of cupric sulfide in the filtrating.Copper concentration in the filtrating is 2mg/L.
Embodiment 4
Identical with embodiment 1 with washes 1L (Cu; It is 12 aqueous sodium hydroxide solution that 5mmol～25mmol) processes 20 quality %pH values.Afterwards, adding the 4.5 about 30ml of quality % sodium sulfhydrate solution (25mmol), to make the redox potential of waste water be 0mV.
The waste water that contains cupric sulfide that obtains is carried out the mensuration of SV30, is 70%, and supernatant also has a large amount of SS to suspend.
When carrying out the solid-liquid separation of waste water with filter paper (5C), filterableness is not that embodiment 1～3 the sort of rank is still good.Residual SS in a large number in the filtrating.Copper concentration in the filtrating is 320mg/L.
Add 0.1% filtration adjuvant and (clearly make containing the waste water that contains cupric sulfide after the sulfidizing with chemical company; Radiolight#200), after the stirring, through filtering with the filtration adjuvant after separating; Do not find the SS in the filtrating, the copper concentration in the filtrating is 7mg/L.
Comparative example 1
With embodiment 1 identical use sulfuric acid washes being adjusted to the pH value is after 7, in waste water 1L, has added the about 80ml of sodium hydrogen carbonate solution of 8 quality %.Afterwards, in order to promote the generation of verditer, be warmed to 70 ℃ and placed one hour.
Solution after the processing becomes the solution of the SS that contains a large amount of glaucous verditers.
Then add flocculation agent A, make content become 30mg/L, after stirring, leaving standstill with respect to wastewater solid shape part to this liquid.The SV30 of this moment 100% does not find have deposition to produce.
Afterwards, with filter paper (5C) the above-mentioned washes that has added flocculation agent is tried to have carried out solid-liquid separation.But filterableness is too poor, and in the filtrating that obtains, has also found green SS.Measure the copper concentration in the filtrating, be 420mg/L.
As polymer coagulant; Using positively charged ion respectively is that (Toagosei Co., Ltd makes polymer coagulant ARONFLOC C-512L; Molecular-weight average is about 3,500,000), (Toagosei Co., Ltd makes ARONFLOC C-525L; Molecular-weight average is about 5,000,000) carried out same operation, with the situation of flocculation agent A be same result, be difficult to lower the copper concentration in the filtrating.
Comparative example 2
Coexist mutually among the waste water 1L that obtains with embodiment 1, add the aqueous sodium hypochlorite solution 50ml of 12 quality %, make cupric ion become cupric oxide as oxygenant.Make the viscosity of waste water rise owing to add oxygenant.Can not condense even add flocculation agent A cupric oxide yet, and become heavy-gravity solution.
The mensuration of SV30 is not found precipitation threshold.(5C) carried out suction strainer with filter paper, but can't carry out solid-liquid separation.
Claims (10)
1. wastewater treatment method that contains vinylformic acid or methylacrylic acid and/or its polymkeric substance and polyvalent metal ion; After sulfide and/or the sulfhydrate that it is characterized in that in above-mentioned waste water adding basic metal becomes sulfide with polyvalent metal ion; Add the slurry that flocculation agent or filtration adjuvant form the sulfide that contains above-mentioned polyvalent metal; Afterwards above-mentioned slurry is passed through solid-liquid separation, from waste water, isolate the sulfide of above-mentioned polyvalent metal.
2. wastewater treatment method according to claim 1, wherein the sulfide of basic metal and/or sulfhydrate are sodium sulphite and/or sodium sulfhydrate.
3. wastewater treatment method according to claim 1, wherein polyvalent metal ion is a cupric ion.
4. wastewater treatment method according to claim 3, wherein the addition of the sulfide of basic metal and/or sulfhydrate is etc. more than the mole with respect to cupric ion.
5. wastewater treatment method according to claim 1 wherein makes the redox potential of waste water become sulfide and/or the sulfhydrate that 0mV adds basic metal followingly.
6. wastewater treatment method according to claim 1 wherein makes the pH value of waste water be adjusted at 7～13.
7. wastewater treatment method according to claim 1, wherein flocculation agent is the organic flocculation agent of nonionic and/or anionic property.
8. the method for manufacture of propenoate or methacrylic ester; Comprising following operation: make in the presence of the cupric ion of vinylformic acid or methylacrylic acid and alcohol strongly acidic catalyst and the stopper in solvent and react, obtain containing the operation of the reaction solution of propenoate or methacrylic ester; With above-mentioned reaction solution is washed with washing water, separate into the organic layer that contains propenoate or methacrylic ester and the operation that contains the cupric ion washes; With with above-mentioned washes treatment procedures; Wherein above-mentioned washes treatment procedures is; The sulfide and/or the sulfhydrate that in above-mentioned washes, add basic metal generate after the cupric sulfide, add flocculation agent, make the operation of the slurry agglomeration separation that contains cupric sulfide.
9. the method for manufacture of propenoate or methacrylic ester; Comprising following operation: make in the presence of the cupric ion of vinylformic acid or methylacrylic acid and alcohol strongly acidic catalyst and the stopper in solvent and react, obtain containing the operation of the reaction solution of propenoate or methacrylic ester; With above-mentioned reaction solution is washed with washing water, separate into the organic layer that contains propenoate or methacrylic ester and the operation that contains the washes of cupric ion; With with above-mentioned washes treatment procedures; Wherein above-mentioned washes treatment procedures is; The sulfide and/or the sulfhydrate that in above-mentioned washes, add basic metal generate after the cupric sulfide, add filtration adjuvant, make the isolating operation of slurry co-precipitation that contains cupric sulfide.
10. according to Claim 8 or the method for manufacture of 9 described propenoate or methacrylic ester, wherein from washes, isolate the processing waste water that the slurry that contains cupric sulfide will obtain and carry out burn processing.
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| JP2010234205A (en) * | 2009-03-30 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Method for treating waste hydrofluoric acid |
| CN102010086B (en) * | 2010-12-01 | 2013-01-09 | 新疆天业（集团）有限公司 | Method for treating mercury-containing wastewater with three-section continuous process |
| JP6269960B2 (en) * | 2014-10-30 | 2018-01-31 | 住友金属鉱山株式会社 | Cadmium-containing wastewater treatment method |
| JP6555182B2 (en) * | 2016-04-22 | 2019-08-07 | 住友金属鉱山株式会社 | Wastewater treatment method |
| KR101717126B1 (en) * | 2016-06-28 | 2017-03-17 | 효림산업주식회사 | Soil Treatment System Using Nanobubble and Multi-Stage Washing of Organic Acid |
| CN108342575A (en) * | 2018-02-22 | 2018-07-31 | 中国恩菲工程技术有限公司 | The method of enriching Cu from copper-containing solution |
| CN112390451A (en) * | 2020-11-26 | 2021-02-23 | 瑞昌荣联环保科技有限公司 | Waste water treatment process generated in waste acrylic regeneration and recovery process |
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| CN1291606A (en) * | 1999-10-12 | 2001-04-18 | 株式会社日本触媒 | Method for preparing acrylic ester and methylacrylate |
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| JPWO2007074751A1 (en) | 2009-06-04 |
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| TWI441782B (en) | 2014-06-21 |
| TW200738570A (en) | 2007-10-16 |
| WO2007074751A1 (en) | 2007-07-05 |
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