CN102633314A - Low-concentration formaldehyde wastewater resource recycling process - Google Patents
Low-concentration formaldehyde wastewater resource recycling process Download PDFInfo
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- CN102633314A CN102633314A CN2012100843747A CN201210084374A CN102633314A CN 102633314 A CN102633314 A CN 102633314A CN 2012100843747 A CN2012100843747 A CN 2012100843747A CN 201210084374 A CN201210084374 A CN 201210084374A CN 102633314 A CN102633314 A CN 102633314A
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Abstract
The invention discloses a low-concentration formaldehyde wastewater resource recycling process. The low-concentration formaldehyde wastewater resource recycling process includes rectifying low-concentration formaldehyde wastewater; and separating the rectified low-concentrate formaldehyde wastewater into two flows of liquid. One flow of liquid is high-purity 5-9% aqueous formaldehyde solution, the other flow of liquid is wastewater containing other impurities, and the low-concentration formaldehyde wastewater is glyphosate production wastewater. The low-concentration formaldehyde wastewater resource recycling process is an effective, environment-friendly and energy-saving low-concentration production process by the aid of the formaldehyde wastewater, formaldehyde in the wastewater is recycled into the high-purity 5-9% aqueous formaldehyde solution (with the minimum formaldehyde recovery rate of 99%), widely applied urotropine is extracted as a chemical byproduct, or high-concentration aqueous formaldehyde is further extracted or prepared to be used for synthesizing pmida in a glyphosate production process, and the purposes of comprehensive resource utilization and circular economy are achieved.
Description
Technical field
The present invention relates to a kind of low concentration formaldehyde waste water reclaiming and reclaim technology.
Background technology
N-((phosphonomethyl)) glycocoll is that a kind of weedicide of the hypersorption mode of action efficiently is commonly called as Glyphosate 62 IPA Salt and is widely used on the agricultural; It can be removed 1 year and perennial weeds and algae kind; Along with changeing constantly applying of glyphosate gene crop; Glyphosate 62 IPA Salt is also increasing as its consumption of herbicides special; So the advantage of scale cost advantage of production Glyphosate 62 IPA Salt seems to the enterprise that makes this product and be even more important that continuing to optimize with the by-product comprehensive utilization of resources of its compound method also more and more is much accounted of simultaneously, the Glyphosate 62 IPA Salt of IDA method production at present is higher more than 2% than glycine method because of the former powder master of Glyphosate 62 IPA Salt content; It is high more than 12% that the phosphor resource utilization ratio is produced Glyphosate 62 IPA Salt than glycine method, the production technique that advantages such as the relatively little and easy processing of factory effluent amount are had an optimistic view of by personage in the industry both at home and abroad.
IDA method glyphosate production mainly contains three big steps:
(1) the synthetic and pair product 5-18% ammoniacal liquor of iminodiethanoic acid (being called for short IDA)
The principal reaction formula:
NH(CH
2CN)
2+2NaOH+2H
2O---NH(CH
2COONa)
2+2NH
3
NH(CH
2COONa)
2+2HCl---NH(CH
2COOH)
2+2NaCl
(2) pmida98 (being called for short PMIDA) is synthetic
The principal reaction formula:
NH(CH
2COOH)
2+H
3PO
3+CH
2O---(HO)
2P(O)CH
2N(CH
2COOH)
2+H
2O
(3) Glyphosate 62 IPA Salt (being called for short PMG) is synthetic
Principal reaction:
(HO)
2P(O)CH
2N(CH
2COOH)
2+1/2O
2---
(HO)
2P(O)CH
2NHCH
2CO
2H+CO
2+HCOH
This building-up reactions is that the pmida98 aqueous solution makes pmida98 or its salt carry out the three-phase oxidation reaction with oxygen-containing gas (preferred air) in the presence of catalyzer; And warp obtains the title product Glyphosate 62 IPA Salt effective the separation; But also just to some extent but produced low concentration formaldehyde waste water inevitably according to the difference of selecting catalyst and the different and processing compound of separation method; This method of wastewater treatment is also received much attention, and simultaneously resource utilization 1-5% contains the formaldehyde glyphosate waste water and becomes a reality and also more go up a step for the energy-conserving and emission-cutting technology of IDA method production Glyphosate 62 IPA Salt technology.
The lower concentration glyphosate waste water produces and compositional characteristic: generally in the glyphosate production process method processing Glyphosate 62 IPA Salt oxidation synthesis mother liquid, its composition of generation aldehyde-containing sewage after reclaiming Glyphosate 62 IPA Salt fully such as separates through multistage membrane sepn or ionic adsorption exchange: 1-5% formaldehyde, 0.02-1% formic acid,＜200PPM Glyphosate 62 IPA Salt and homologue (in P) thereof,＜1000PPM Cl-
Though degree way or raising separation accuracy through the controlled oxidation reaction go to influence the sight visitor existence that changes the foreign matter content in the final glyphosate waste water but can not eradicate its impurity; Extremely low when seem except that formaldehyde foreign matter content with this waste water; But bring negative impact very important when formaldehyde in the waste water is carried out resource, also must not make this wastewater treatment complicacy that becomes directly to go direct processing just because of the existence of formaldehyde obviously it harmlessness disposing if do not reclaim formaldehyde in addition with the cheap biochemical method of expense.
Summary of the invention
The object of the present invention is to provide a kind of low concentration formaldehyde waste water reclaiming that can effectively realize containing the recycling of formaldehyde glyphosate waste water to reclaim technology.
Technical solution of the present invention is:
A kind of low concentration formaldehyde waste water reclaiming reclaims technology, it is characterized in that: low concentration formaldehyde waste water is carried out rectifying, separate into two strands of liquid, and the one, high purity 5-9% formalin (formic acid content＜10PPM) wherein, the 2nd, contain other impurity waste water; Said low concentration formaldehyde waste water is for producing the waste water of Glyphosate 62 IPA Salt.
Contain formaldehyde content＜300PPM in other impurity waste water.
During distillation operation, get into rectifying tower behind the condensed heat transfer fluid of the cat head compressed vapour that the formaldehyde waste water of 1-5% concentration and falling-film evaporator come out, the formalin steam of rectifying tower cat head 5-9% gets into vapour compressor compression back and improves temperature, as the tower bottom heating thermal source.
Concrete rectification step is: with low concentration formaldehyde waste water warp first interchanger, after the heat exchange of bottoms material; Again through second interchanger, the overhead condensation liquid heat exchange of coming out with falling-film evaporator; After vapor preheater gets into rectifying tower after being preheated to certain temperature; The steam that rectifying tower top rises is behind the vapour liquid separator separatory; The compressor that formalin steam the gets into matching Design intensification of boosting, the amplitude of boosting after compression 150-300KP, 15-30 ℃ of intensification amplitude; The shell side that the steam of compressor outlet gets into above-mentioned falling-film evaporator adds thermal material; The material of condensation is collected in after preheated feed in the water-soluble flow container of rich aldehyde; Obtain high purity 5-9% formalin, part is seen off out-of-bounds, part is delivered to above-mentioned recovery cat head reflux by reflux pump; Part is sent into the above-mentioned compressor cooling and is used; At the bottom of tower still waste water part was delivered to above-mentioned falling-film evaporator top and produced vapour phase and return tower by recycle pump, part was seen off out-of-bounds by waste water pump after first interchanger and charging heat exchange are lowered the temperature.
The by-product 5-18% ammoniacal liquor of seeing part off out-of-bounds high purity 5-9% formalin and glyphosate production process system iminodiethanoic acid generation by reflux pump reacts; Temperature of reaction 40-70 ℃; PH8-10; Get rare urotropine solution, get the dense urotropine solution of 12-20%, use raw material as chemical industry with multistage membrane-concentrated method; Or carrying operating units such as dense, crystallization, centrifugal, drying through dehydration by evaporation again gets 99% urotropine product; Or adopt the energy-conservation evaporation of MVR, crystallization method directly to make liquid concentrator or 99% urotropine the above-mentioned rare urotropine solution; Membrane sepn water outlet in the above process or steam and absorb ammonia system ammoniacal liquor when water all can be used in the glyphosate production system iminodiethanoic acid.
Directly high purity 5-9% formalin is carried through the compression rectification secondary dense to being used for the pmida98 building-up process more than 30%, or with high density 50% formaldehyde or Paraformaldehyde 96 allotment to be suitable for＞30% formaldehyde is used for synthetic pmida98.
The present invention is the production technique of the effective environmental protection and energy saving of a kind of low concentration formaldehyde waste water; After the formaldehyde in the waste water is recycled into high purity 5-9% formalin, choose in (the formaldehyde recovery is more than 99%) urotropine with extensive use pay as chemical industry produce carry dense once more or prepare high dense water beetle aldehyde be used for the glyphosate production process pmida98 synthetic in, reach the purpose of comprehensive utilization of resources and recycling economy.
It is the English abbreviation (Mechanical Vapor Recompression) of mechanical steam recompression that conservation measures of the present invention the most important thing is to adopt in the rectifying MVR.Its ultimate principle is: the secondary steam to producing in the evaporative process recompresses through machinery, improves the temperature and the heat content of secondary steam, utilizes again, to reach energy-conservation purpose.
Below in conjunction with embodiment the present invention is described further.
Embodiment
A kind of low concentration formaldehyde waste water reclaiming reclaims technology, and low concentration formaldehyde waste water is carried out rectifying, separates into two strands of liquid, and the one, high purity 5-9% formalin (formic acid content＜10PPM) wherein, the 2nd, contain other impurity waste water; Said low concentration formaldehyde waste water is for producing the waste water of Glyphosate 62 IPA Salt.
Contain formaldehyde content＜300PPM in other impurity waste water.
Concrete rectification step is: with low concentration formaldehyde waste water warp first interchanger, after the heat exchange of bottoms material; Again through second interchanger, the overhead condensation liquid heat exchange of coming out with falling-film evaporator; After vapor preheater gets into regenerating column after being preheated to certain temperature, reclaim steam (the formalin steam that promptly contains 7-8%) that cat head rises behind the vapour liquid separator separatory, formalin steam gets into the compressor intensification of boosting.The shell side that the steam of compressor outlet (being saturated formalin steam) gets into above-mentioned falling-film evaporator adds thermal material; The material of condensation is collected in after preheated feed in the water-soluble flow container of rich aldehyde; Obtain high purity 4-8% formalin, part is seen off out-of-bounds, part is delivered to above-mentioned recovery cat head reflux by reflux pump; Part is sent into the above-mentioned compressor cooling and is used; At the bottom of tower still waste water part was delivered to above-mentioned falling-film evaporator top and produced vapour phase and return tower by recycle pump, part was seen off out-of-bounds by waste water pump after first interchanger and charging heat exchange are lowered the temperature.
The by-product 5-18% ammoniacal liquor of seeing part off out-of-bounds high purity 4-8% formalin and glyphosate production process system iminodiethanoic acid generation by reflux pump reacts; Temperature of reaction 40-70 ℃; PH8-10; Get rare urotropine solution, get the dense urotropine solution of 12-20%, use raw material as chemical industry with multistage membrane-concentrated method; Or carrying operating units such as dense, crystallization, centrifugal, drying through dehydration by evaporation again gets 99% urotropine product; Or adopt the energy-conservation evaporation of MVR, crystallization method directly to make liquid concentrator or 99% urotropine the above-mentioned rare urotropine solution; Membrane sepn water outlet in the above process or steam and absorb ammonia system ammoniacal liquor when water all can be used in the glyphosate production system iminodiethanoic acid.
Directly high purity 4-8% formalin is carried through the compression rectification secondary dense to being used for the pmida98 building-up process more than 30%, or with high density 50% formaldehyde or Paraformaldehyde 96 allotment to be suitable for＞30% formaldehyde is used for synthetic pmida98.
Claims (6)
1. a low concentration formaldehyde waste water reclaiming reclaims technology, it is characterized in that: low concentration formaldehyde waste water is carried out rectifying, separate into two strands of liquid, and the one, high purity 5-9% formalin, the 2nd, contain other impurity waste water; Said low concentration formaldehyde waste water is for producing the waste water of Glyphosate 62 IPA Salt.
2. low concentration formaldehyde waste water reclaiming according to claim 1 reclaims technology, it is characterized in that: contain formaldehyde content < 300PPM in other impurity waste water.
3. low concentration formaldehyde waste water reclaiming according to claim 1 and 2 reclaims technology; It is characterized in that: during distillation operation; Get into rectifying tower behind the condensed heat transfer fluid of the cat head compressed vapour that the formaldehyde waste water of 1-5% concentration and falling-film evaporator come out; The formalin steam of rectifying tower cat head 5-9% gets into vapour compressor compression back and improves temperature, as the tower bottom heating thermal source.
4. low concentration formaldehyde waste water reclaiming according to claim 3 reclaims technology, it is characterized in that: concrete rectification step is: with low concentration formaldehyde waste water warp first interchanger, after the heat exchange of bottoms material; Again through second interchanger, the overhead condensation liquid heat exchange of coming out with falling-film evaporator; After vapor preheater gets into rectifying tower after being preheated to certain temperature; The steam that rectifying tower top rises is behind the vapour liquid separator separatory; The compressor that formalin steam the gets into matching Design intensification of boosting, the amplitude of boosting after compression 150-300KP, 15-30 ℃ of intensification amplitude; The shell side that the steam of compressor outlet gets into above-mentioned falling-film evaporator adds thermal material; The material of condensation is collected in after preheated feed in the water-soluble flow container of rich aldehyde; Obtain high purity 5-9% formalin, part is seen off out-of-bounds, part is delivered to above-mentioned recovery cat head reflux by reflux pump; Part is sent into the above-mentioned compressor cooling and is used; At the bottom of tower still waste water part was delivered to above-mentioned falling-film evaporator top and produced vapour phase and return tower by recycle pump, part was seen off out-of-bounds by waste water pump after first interchanger and charging heat exchange are lowered the temperature.
5. low concentration formaldehyde waste water reclaiming according to claim 1 and 2 reclaims technology; It is characterized in that: the by-product 5-18% ammoniacal liquor of seeing part off out-of-bounds high purity 5-9% formalin and glyphosate production process system iminodiethanoic acid generation by reflux pump reacts; Temperature of reaction 40-70 ℃, PH8-10 gets rare urotropine solution; Get the dense urotropine solution of 12-20% with multistage membrane-concentrated method, use raw material as chemical industry; Or carrying operating units such as dense, crystallization, centrifugal, drying through dehydration by evaporation again gets 99% urotropine product; Or adopt the energy-conservation evaporation of MVR, crystallization method directly to make liquid concentrator or 99% urotropine the above-mentioned rare urotropine solution; Membrane sepn water outlet in the above process or steam and absorb ammonia system ammoniacal liquor when water all can be used in the glyphosate production system iminodiethanoic acid.
6. low concentration formaldehyde waste water reclaiming according to claim 1 and 2 reclaims technology; It is characterized in that: directly high purity 5-9% formalin is carried through the compression rectification secondary dense to being used for the pmida98 building-up process more than 30%, or with high density 50% formaldehyde or Paraformaldehyde 96 allotment to being suitable for 30% formaldehyde is used for synthetic pmida98.
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|---|---|---|---|
| CN201210084374.7A CN102633314B (en) | 2012-03-27 | 2012-03-27 | Low-concentration formaldehyde wastewater resource recycling process |
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|---|---|---|---|
| CN201210084374.7A CN102633314B (en) | 2012-03-27 | 2012-03-27 | Low-concentration formaldehyde wastewater resource recycling process |
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| CN102633314B CN102633314B (en) | 2014-07-09 |
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Cited By (5)
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|---|---|---|---|---|
| CN102925220A (en) * | 2012-11-27 | 2013-02-13 | 淄博义丰机械工程有限公司 | Normal pressure phenol water evaporator used for coal gas generator |
| CN103524553A (en) * | 2013-10-21 | 2014-01-22 | 沙隆达集团公司 | Pmida mother liquor comprehensive treatment method |
| CN103663585A (en) * | 2012-09-14 | 2014-03-26 | 苏州工业园区七星电子有限公司 | Method and device for treating organic wastewater |
| CN104176868A (en) * | 2013-05-28 | 2014-12-03 | 涂远晖 | Formalin harmless processing method |
| CN105645654A (en) * | 2016-01-12 | 2016-06-08 | 浙江新华新材料科技有限责任公司 | Methoxylated amino resin formaldehyde wastewater recovery method and device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663585A (en) * | 2012-09-14 | 2014-03-26 | 苏州工业园区七星电子有限公司 | Method and device for treating organic wastewater |
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| CN104176868A (en) * | 2013-05-28 | 2014-12-03 | 涂远晖 | Formalin harmless processing method |
| CN103524553A (en) * | 2013-10-21 | 2014-01-22 | 沙隆达集团公司 | Pmida mother liquor comprehensive treatment method |
| CN105645654A (en) * | 2016-01-12 | 2016-06-08 | 浙江新华新材料科技有限责任公司 | Methoxylated amino resin formaldehyde wastewater recovery method and device |
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|---|---|
| CN102633314B (en) | 2014-07-09 |
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