CN1792857A - Process for removing formol and recovering methyl alcohol and butyl alcohol in amino resin waste water - Google Patents
Process for removing formol and recovering methyl alcohol and butyl alcohol in amino resin waste water Download PDFInfo
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- CN1792857A CN1792857A CN 200510122826 CN200510122826A CN1792857A CN 1792857 A CN1792857 A CN 1792857A CN 200510122826 CN200510122826 CN 200510122826 CN 200510122826 A CN200510122826 A CN 200510122826A CN 1792857 A CN1792857 A CN 1792857A
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- butanols
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Abstract
A process for removing formaldehyde from the sewage generated by preparing aminoresin and recovering methanol and butanol includes such steps as adding OH ions to said sewage proportionally, disproportionation reaction and fractional separation to recover methanol and butanol. Its advantages are high effect and low cost.
Description
Technical field
The present invention relates to a kind of method of from the waste water of producing the aminoresin generation, removing aldehydes and reclaiming methyl alcohol and butanols.
Background technology
Amino (NH
2) compound and formaldehyde is through polycondensation, produces aminoresin, for example alcohols etherify melamine resin, urea-formaldehyde resin, benzoguanamine formaldehyde resin with alcohols (for example methyl alcohol, butanols) modification again.In the waste water that produces deleterious formaldehyde is arranged not only, but also contain relatively large available methyl alcohol, butanols, and a spot of aminoresin and the useless polymers of other small molecules, waste water COD is very high, generally at 30-40 about ten thousand, but wherein some component considerably beyond the ability (the biochemical safe level as butanols is 0.042%, is about about 6% and waste water is actual) of biochemical treatment, thereby be difficult to handle by direct biochemical mode, the formaldehyde treated difficulty that especially toxicity is big is very big.
A large amount of patent report has the ammoniacal liquor of employing or contains amino (NH both at home and abroad
2) compound and formaldehyde formation polycondensate, to remove the method for formaldehyde, as Chinese patent CN86107846, the clear 49-132006 of Japanese Patent, 49-94626,50-038957,57-075187,56-010391 United States Patent (USP) 4088871,4338196 etc.These methods not only need add relatively large organic Ammonia, cause processing cost higher, form new organism, need increase subsequent disposal again, and relatively large COD (being mainly methyl alcohol and butanols) changes in the solid substance of reaction generation in the waste water, really do not removed, and wasted.
The disclosed employing through the cupric oxide of special activation treatment of the clear 54-3002 of Japanese Patent made catalyzer, makes formaldehyde carry out disproportionation under alkaline condition.The clear 49-087613 of Japanese Patent openly adds alkaline purification formaldehyde.These are only reported and are used to handle formaldehyde-containing wastewater, do not relate to the processing of the amino resin waste water that contains different components, and reclaim useful raw material.
In Chemical Industry Press (1998) " chemical environment protection design manual " and 2000 " process water and the waste water " " pre-treatment of amino waste water " of report; Xie Shao adopts and uses urea to remove formaldehyde under acidity or alkaline condition, reclaims methyl alcohol, butanols through distillation or rectifying again.Its deficiency is: amount of urea is big, and processing cost is higher; Secondly, product methyne urea purposes is uncertain, and post-processing difficulty is big, causes secondary pollution, and the water-intake rate height, and the solid-liquid separation difficulty is big, uses spin-on filter device, can take away this callable methyl alcohol and butanols again; Besides, adopt the plain metal random packing, liquid holdup is big, separation efficiency is low relatively, causes the reflux ratio height, and separating difficulty is big, poor operability, thereby distillation operation technology is too loaded down with trivial details, and need to put forward mode by gas and just can reach to make and contain lower methyl alcohol and butanols in the discharge water.
Domestic comparatively ripe employing burning disposal, but because of containing about water more than 90%, the burning disposal processing cost is high, and can cause the waste of useful raw material such as methyl alcohol and butanols.
Summary of the invention
The objective of the invention is to overcome the foot of above-mentioned prior art, provide a kind of processing cost low, economical, easy, workable, and remove the method for formaldehyde and recovery methyl alcohol and butanols in the amino resin waste water of recyclable methyl alcohol and butanols.
The object of the invention realizes, mainly is by adding mineral alkali, carry out disproportionation with formaldehyde, makes formaldehyde be transformed into methyl alcohol and dissolves in the inorganic formate of waste water, and then reclaim methyl alcohol, butanols again.Specifically, remove the method for formaldehyde and recovery methyl alcohol and butanols in the amino resin waste water of the present invention, it is characterized in that in waste water, adding 2 times to the OH of formaldehyde volumetric molar concentration
-Disproportionation reclaims methyl alcohol and butanols by the fraction separation method then.
The present invention said 2 times to the OH of formaldehyde volumetric molar concentration
-, mainly is to consider, and increases the recovery quantity of methyl alcohol, but actual process allows suitable deviation from removing the formaldehyde angle fully.
In the disproportionation of the present invention, better be for example suitably to heat to carry out under 50-90 ℃, help fast reaction speed.For helping fully removing formaldehyde, OH
-Add and better be excessive, the reaction later stage makes pH value at 9-11.
The said fraction of the present invention separates, a kind of better is to adopt distillation and rectifying and usefulness, go out the mixture of the higher methyl alcohol of content, fourth alcohol and water by fractionation by distillation, reclaim methyl alcohol, butanols by rectifying again, thereby simplify follow-up rectification process, and distillation and rectifying and with helping reducing recovery difficult, and can reduce cost recovery.
The said rectifying of the present invention, a kind of better is the packing tower that adopts metal structured packing, and higher separation efficiency is arranged under equal height.In the rectifying, a kind of better is to adopt secondary rectifying, removes big portion moisture in the distillation distillate by the first step rectifying earlier, and to improve methyl alcohol, butanol content, methyl alcohol, butanols are reclaimed in the second step rectifying.The first step rectifying: isolate high-load methyl alcohol-butanols-aqueous solution from cat head, as the second rectifying raw material, moisture is then by discharging at the bottom of the tower, the control tower top temperature is at 65-99 ℃, control reflux ratio 1-4, can make that methyl alcohol is no more than 0.5% in the drainage water, butanols is no more than 0.3%, can fully reclaim methyl alcohol, butanols; The second step rectifying: control reflux ratio 1-4, tower top temperature is in the time of 63-67 ℃, extraction methyl alcohol (content is greater than 98%) uses as finished product, in the time of tower top temperature 67-95 ℃, extraction methyl alcohol-butanols-the aqueous solution, mix as second go on foot the rectifying raw material next time with the first step overhead distillate, the mixture of bottom extraction butanols and water, cooling back layering, can obtain upper strata content and be about 75% butanols, as the aminoresin synthesis material, lower floor then is the butanols aqueous solution of content about 7%, returns and incorporates the first step rectifying into.
The mineral alkali of the abundant reacting weight of formaldehyde and formaldehyde carry out disproportionation conversion formaldehyde because employing is filled up earlier in the present invention, and then by fraction separation method recovery methyl alcohol and butanols, have than prior art: not only can effectively remove formaldehyde, and can increase the recovery quantity of methyl alcohol, thereby increased processing, reclaimed the economy of methyl alcohol, add the mineral alkali cost to remedy, thereby reduced processing cost.And the formate that mineral alkali and formaldehyde produce is water-soluble, and no solids generates, thereby need not secondary treatment; Adopt distillation and rectifying and usefulness, and rectifying tower employing metal structured packing, sepn process is easy, the operability epistasis, the separation efficiency height, steam consumption is few, can reduce 30-50%, separation costs is low, and the circulation rectifying of distillate, can be with wherein methyl alcohol, butanols reclaim substantially.Total cost can reduce more than 50%, greatly reduces processing costs.The inventive method, not only effectively handled amino resin waste water, but also recyclable useful methyl alcohol, butanols, it is lucrative that wastewater treatment is really become, and for enterprise increases economic benefit, and reduced waste water COD concentration, making originally can not biochemical pollutent, becoming can be biochemical, thereby can effectively remove COD, and subsequent treatment cost is low.
Produce 20000 tons in butyl ether aminoresin per year by designed capacity, 330 days meters of year operation, wastewater flow rate is about 13000 tons, and processing cost and income are seen attached list.
The present invention handles, reclaims income statement
| Total amount | Unit price | Total price | |
| Cost of investment depreciation (by 10 years) | 85030 yuan/year | 85030 yuan/year | 8.503 ten thousand yuan/year |
| Power cost | 200000 degree electricity/years | 0.5 unit/degree | 100,000 yuan/year |
| Steam cost | 1.5 ton steam/ton waste water | 80 yuan/ton | 1,560,000 yuan/year |
| Human cost | 7 people | 15000 yuan/people | 10.5 ten thousand yuan/year |
| Liquid caustic soda (30%) | 60KG/ ton waste water | 450 yuan/ton | 35.1 ten thousand yuan/year |
| Cost amounts to | 220.1 ten thousand yuan/year | ||
| Reclaim methyl alcohol | 390 tons/year | 2600 yuan/ton | 101.4 ten thousand yuan/year |
| Reclaim butanols | 650 tons/year | 7000 yuan/ton | 4,550,000 yuan/year |
| Income amounts to | 556.1 ten thousand yuan/year | ||
| Comprehensive benefit | Benefit=income-running cost=336.3 ten thousand yuan/year | ||
Below in conjunction with a preferred implementation, further specify the present invention.
Embodiment
Embodiment: get wastewater sample 1000g (measure COD about 310,000), add solid sodium hydroxide 25g (also can adopt its aqueous solution), be warming up to 60-70 ℃ keep 30min after, measure PH and equal 10.Be distilled to 96 ℃, bottoms discharging COD is about 40,000, gets distillate 307g and goes into rectifying tower, rectifying is carried out in the metal structured packing packing tower, rectifying for the first time: temperature rising reflux keeps reflux ratio 4, collect 68-97 ℃ of fraction 77g of cat head fluid, as rectifying second time raw material.Waste water discharges biochemical treatment at the bottom of the tower, and methanol content 0.4% in the drainage water, butanol content 0.2%.
Rectifying for the second time: get rectifying tower top distillate 77g for the first time, temperature rising reflux keeps reflux ratio 4, collects 64-67 ℃ of fraction 23g of cat head fluid, takes out as the methyl alcohol finished product.Collect 67-95 ℃ of fraction 27g of tower top temperature, mix the raw material of conduct rectifying for the second time as intermediate product with the overhead product after the rectifying for the first time.Bottom product, the cooling layering, obtaining upper strata content is 75% butanols 19.2g, as the finished product output; Lower floor's content is the aqueous solution 11.5g of 6.5% butanols, mixes with the distillation distillate, as the raw material of the rectifying first time.
Claims (9)
1, removes the method for formaldehyde and recovery methyl alcohol and butanols in the amino resin waste water, it is characterized in that in waste water, adding 2 times to the OH of formaldehyde volumetric molar concentration
-Disproportionation reclaims methyl alcohol and butanols by the fraction separation method then.
2, according to the method for removing formaldehyde and recovery methyl alcohol and butanols in the described amino resin waste water of claim 1, it is characterized in that said OH
-Be sodium hydroxide or its aqueous solution.
3 according to the method for removing formaldehyde and recovery methyl alcohol and butanols in claim 1 or the 2 described amino resin waste waters, it is characterized in that said disproportionation carries out in 50-90 ℃.
4, according to the method for removing formaldehyde and recovery methyl alcohol and butanols in claim 1 or the 2 described amino resin waste waters, it is characterized in that said adding OH
-The excessive pH value that makes is at 9-11.
5,, it is characterized in that said distillating is distillation and rectifying and usefulness according to the method for removing formaldehyde and recovery methyl alcohol and butanols in the described amino resin waste water of claim 1.
6,, it is characterized in that the packing tower of rectifying employing metal structured packing according to the method for removing formaldehyde and recovery methyl alcohol and butanols in the described amino resin waste water of claim 5.
7, according to the method for removing formaldehyde and recovery methyl alcohol and butanols in claim 5 or the 6 described amino resin waste waters, it is characterized in that rectifying is two step rectifying, big portion moisture in the distillation distillate is removed in the first step rectifying, and second goes on foot rectifying reclaims methyl alcohol, butanols.
8, according to the method for removing formaldehyde and recovery methyl alcohol and butanols in the described amino resin waste water of claim 7, it is characterized in that 65-99 ℃ of the first step rectifying tower top temperature, reflux ratio 1-4.
9, according to the method for removing formaldehyde and recovery methyl alcohol and butanols in the described amino resin waste water of claim 7, it is characterized in that the second step rectifying reflux ratio 1-4, tower top temperature is in the time of 63-67 ℃, extraction methyl alcohol, tower top temperature is extraction methyl alcohol-butanols-aqueous solution in the time of 67-95 ℃, the mixture of bottom extraction butanols and water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101228266A CN100347105C (en) | 2005-12-05 | 2005-12-05 | Process for removing formol and recovering methyl alcohol and butyl alcohol in amino resin waste water |
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| CNB2005101228266A CN100347105C (en) | 2005-12-05 | 2005-12-05 | Process for removing formol and recovering methyl alcohol and butyl alcohol in amino resin waste water |
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| CN1792857A true CN1792857A (en) | 2006-06-28 |
| CN100347105C CN100347105C (en) | 2007-11-07 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992423A (en) * | 2012-11-19 | 2013-03-27 | 江苏三木集团有限公司 | Technology for treating methylated amino resin wastewater |
| CN103435214A (en) * | 2013-09-09 | 2013-12-11 | 山东省泰和水处理有限公司 | Comprehensive treatment method for formaldehyde-containing acid wastewater |
| CN104710068A (en) * | 2015-03-16 | 2015-06-17 | 南京环保产业创新中心有限公司 | Treatment and recycling method for chloromethylated bead production wastewater |
| CN104909523A (en) * | 2015-07-01 | 2015-09-16 | 百川化工(如皋)有限公司 | High-concentration formaldehyde sewage treatment system and treatment method |
| CN106946651A (en) * | 2017-04-28 | 2017-07-14 | 南京科技职业学院 | A kind of method of extracting rectifying and reaction side line rectification process ethanol, isopropanol and formaldehyde composite waste |
| CN107117674A (en) * | 2017-04-28 | 2017-09-01 | 南京科技职业学院 | A kind of method of extracting rectifying and reaction side line rectification process amino resin waste water |
| CN108328847A (en) * | 2017-01-20 | 2018-07-27 | 彤程化学（中国）有限公司 | A kind of integrated conduct method of tire functional resin sewage |
| CN111252977A (en) * | 2019-11-28 | 2020-06-09 | 国合恒新环保江苏有限公司 | Process for neutralizing and rectifying high-hydrochloric-acid n-butanol wastewater |
| CN113354154A (en) * | 2021-06-30 | 2021-09-07 | 兖矿鲁南化工有限公司 | Formaldehyde wastewater comprehensive treatment method and device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2619369C2 (en) * | 1976-04-30 | 1982-06-16 | Siemens AG, 1000 Berlin und 8000 München | Liquid jet recorder |
| CN1019476B (en) * | 1988-06-17 | 1992-12-16 | 武汉市化工技术开发中心 | A kind of urea-formaldehyde resin wastewater treatment method |
| SU1699950A1 (en) * | 1990-01-26 | 1991-12-23 | Всесоюзный Комплексный Научно-Исследовательский И Конструкторско-Технологический Институт Водоснабжения, Канализации, Гидротехнических Сооружений И Инженерной Гидрогеологии "Водгео" | Method for purification of sewage, containing formaldehyde and methanol |
| HU210520B (en) * | 1992-11-11 | 1995-07-28 | Szerves Vegyipari Kutato Int | Method for treating and recirculating of phenol and other organic compound contain wastes |
-
2005
- 2005-12-05 CN CNB2005101228266A patent/CN100347105C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992423A (en) * | 2012-11-19 | 2013-03-27 | 江苏三木集团有限公司 | Technology for treating methylated amino resin wastewater |
| CN103435214A (en) * | 2013-09-09 | 2013-12-11 | 山东省泰和水处理有限公司 | Comprehensive treatment method for formaldehyde-containing acid wastewater |
| CN103435214B (en) * | 2013-09-09 | 2014-09-03 | 山东省泰和水处理有限公司 | Comprehensive treatment method for formaldehyde-containing acid wastewater |
| CN104710068A (en) * | 2015-03-16 | 2015-06-17 | 南京环保产业创新中心有限公司 | Treatment and recycling method for chloromethylated bead production wastewater |
| CN104909523A (en) * | 2015-07-01 | 2015-09-16 | 百川化工(如皋)有限公司 | High-concentration formaldehyde sewage treatment system and treatment method |
| CN108328847A (en) * | 2017-01-20 | 2018-07-27 | 彤程化学（中国）有限公司 | A kind of integrated conduct method of tire functional resin sewage |
| CN106946651A (en) * | 2017-04-28 | 2017-07-14 | 南京科技职业学院 | A kind of method of extracting rectifying and reaction side line rectification process ethanol, isopropanol and formaldehyde composite waste |
| CN107117674A (en) * | 2017-04-28 | 2017-09-01 | 南京科技职业学院 | A kind of method of extracting rectifying and reaction side line rectification process amino resin waste water |
| CN107117674B (en) * | 2017-04-28 | 2020-09-29 | 南京科技职业学院 | Method for treating amino resin wastewater by extractive distillation and reaction side-stream distillation |
| CN111252977A (en) * | 2019-11-28 | 2020-06-09 | 国合恒新环保江苏有限公司 | Process for neutralizing and rectifying high-hydrochloric-acid n-butanol wastewater |
| CN113354154A (en) * | 2021-06-30 | 2021-09-07 | 兖矿鲁南化工有限公司 | Formaldehyde wastewater comprehensive treatment method and device |
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| CN100347105C (en) | 2007-11-07 |
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