CN101381179A - Formaldehyde comprehensive utilization method in acidic industrial effluent - Google Patents
Formaldehyde comprehensive utilization method in acidic industrial effluent Download PDFInfo
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- CN101381179A CN101381179A CNA2008101581660A CN200810158166A CN101381179A CN 101381179 A CN101381179 A CN 101381179A CN A2008101581660 A CNA2008101581660 A CN A2008101581660A CN 200810158166 A CN200810158166 A CN 200810158166A CN 101381179 A CN101381179 A CN 101381179A
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Abstract
The invention relates to a method for comprehensively utilizing formaldehyde in acid industrial wastewater and manufacturing a scale inhibitor for water treatment. The method transforms the formaldehyde in the acid industrial wastewater into a methylene thiourea precipitate so as to be separated from the wastewater, thereby eliminating the pollution of the formaldehyde in the wastewater on environment and saving wastewater treatment cost. In addition, the precipitate is taken as a raw material of reaction so as to prepare the scale inhibitor for water treatment by adding in a certain amount of other chemical raw materials, which realizes the comprehensive utilization of resources. The method is applicable to the treatment and comprehensive utilization of formaldehyde-containing wastewater produced in organic phosphine industry and other acid industries.
Description
Technical field
The present invention relates to a kind of wastewater treatment and comprehensive utilization technique, particularly remove the trade effluent of organic phosphine production process generation and the formaldehyde in other acidic industrial effluent, formaldehyde in the acidic industrial effluent is separated from waste water with the form of methyne urea solid precipitation, and with the solid precipitation that generates as basic material, add a certain amount of other industrial chemicals, prepare phosphorous water treatment Scale inhibitors through chemical reaction.
Background technology
Formaldehyde is defined as carcinogenic and teratogen by the World Health Organization, also is the allergen of generally acknowledging.Easy central nervous system and retina to the people caused damage after formaldehyde entered water body.Derive from organic synthesis, synthon, dyestuff, plastics, process hides, wood working and the system of formaldehyde coated with lacquer the waste water that industry enters in the water.Because formaldehyde can suppress the microbial growth breeding, formaldehyde waste water also is difficult to biochemical degradation.Therefore, country has proposed more strict limitation standard to the formaldehyde content in heavy chemicals, house decoration, the industrial wastewater discharge, requires the formaldehyde mass concentration in the waste water to be controlled at below the 0.5mg/L.
The treatment process of at present a large amount of formaldehyde-containing wastewaters mainly adopts biochemical process (anaerobism, oxygen consumption method), catalytic oxidation, blow-off method.But aforesaid method respectively has shortcoming, all can not reach the purpose of comprehensive utilization in the pollution problem that thoroughly solves formaldehyde waste water.Biochemical process can only be handled low concentration formaldehyde waste water (content≤0.1%), catalytic oxidation equipment and processing cost costliness, and blow-off method only is applicable to high-concentration formaldehyde wastewater and can not thoroughly solves the formaldehyde pollution problem.
In the production process of water conditioner organic phosphine, the hydrochloric acid of unnecessary formaldehyde and reaction generation can be removed by the distillatory mode, and formaldehyde content 2-8% in the product that steams, content of hydrochloric acid 0.5-18%.Comprehensive utilization to this part trade effluent is the anxious pending difficult problem of organic phosphine manufacturing enterprise all the time.
Chinese invention patent application 97110414.X, name is called " production method of quick-acting urea-formaldehyde nitrogen fertilizer " and discloses the method for producing urea-formaldehyde fertilizer with formaldehyde waste water, but this method can only be applicable to concentration higher (content 〉=9%) waste water, and produce the waste water that finishes and still have a large amount of formaldehyde, thereby can not thoroughly solve environmental issue.
Chinese invention patent 01128031.X has proposed a kind of improvement of formaldehyde-containing wastewater treatment process.This technology be with formaldehyde waste water after spraying gun atomizing, be sprayed at just on the slag that comes out from boiler, after formaldehyde waste water is met high temperature and oxygen, be cracked into carbonic acid gas and water vapor immediately,, enter atmosphere by gas skirt, aiutage, last trace formaldehyde adsorbs through the porous slag again.This patent is fit to the processing of a small amount of formaldehyde-containing wastewater, and this technology is not fully utilized wherein formaldehyde.
Chinese invention patent 86107846, name is called " the methyne urea precipitator method are removed the formaldehyde in the trade effluent ", the method of formaldehyde is removed in this invention from trade effluent with the sedimentary form of methyne urea, make catalyzer with acids, under normal temperature or waste water boiling temperature, utilize the formaldehyde in urea and the waste water to react, generate insoluble methyne urea white precipitate, separating reaction throw out then, to remove the formaldehyde in the trade effluent, for containing the waste water of formaldehyde 3%, the formaldehyde clearance is 97-99%, it is strong that this invention removes formaldehyde method selectivity, is not subjected to the interference of other coexistence component in the waste water.This patent is not with the throw out comprehensive utilization that produces.
Summary of the invention
The invention provides formaldehyde comprehensive utilization method in a kind of acidic industrial effluent, it is to utilize formaldehyde waste water to prepare urea groups methylenephosphonic acid scale inhibition water conditioner, in removing waste water, in the formaldehyde, obtain useful Chemicals, reached the purpose of comprehensive utilization of resources.The present invention is applicable to the processing and the comprehensive utilization of the trade effluent and the acidic industrial effluent that other industry contains formaldehyde of organic phosphine industry generation.
Treatment process of the present invention may further comprise the steps:
(1) in containing the acidic industrial effluent of formaldehyde, add certain amount of urea, control reaction temperature and reaction times, generate white depositions, filter;
(2) get a certain amount of filter cake, add phosphorus trichloride and formaldehyde, control reaction temperature and time,, obtain urea groups methylenephosphonic acid scale inhibition water conditioner purification of products;
(3) get a certain amount of filtrate, de-chlorine hydride resorber absorbing hydrogen chloride makes technical hydrochloric acid.
Described preparation technology, it is characterized in that: in the step (1), add a certain amount of urea, the add-on that is meant urea satisfies following ratio: the mol ratio of formaldehyde and urea is 0.5:1～5:1, adding can be disposable adding or add in batches, add in batches and refer to be divided into secondary, the feed way more than three times or four times.
Described preparation technology is characterized in that: in the step (1), control reaction temperature refers to temperature of reaction is controlled at 25-100 ℃.
Described preparation technology is characterized in that: in the step (1), the reaction times refers to the reaction times was controlled at 0.5-5 hour.
Described preparation technology is characterized in that: in the step (2), the amount that adds phosphorus trichloride is 1-10 a times of filter cake quality, and the add-on of formaldehyde is 1-10 a times of filter cake quality.
Described preparation technology is characterized in that: in the step (2), control reaction temperature refers to temperature of reaction is controlled at 30-120 ℃.
Described preparation technology is characterized in that: in the step (2), the reaction certain hour refers to the reaction times was controlled at 1-5 hour.
The method of comprehensive utilization of formaldehyde in the above-mentioned acidic industrial effluent, the formaldehyde decreasing ratio can reach more than 98% in the trade effluent, prepare urea groups methylenephosphonic acid water conditioner, under the identical situation of dosage, its static-state scale inhibition rate can reach and Amino Trimethylene Phosphonic Acid (ATMP) and the suitable degree of hydroxy ethylene phosphonic acids (HEDP).
The present invention has very significant advantage: (1) the present invention can remove the formaldehyde in the acidic industrial effluent, the particularly removal of the formaldehyde-containing wastewater that the organic phosphine production process is produced, with interior trade effluent, the clearance of formaldehyde reaches more than 98% PARA FORMALDEHYDE PRILLS(91,95) content at 1-8%; (2) the present invention in the formaldehyde, is used to the white precipitate that produces in removing trade effluent, as producing the raw material of scale inhibition with water conditioner, adds a certain amount of phosphorus trichloride and formaldehyde, prepares urea groups methylenephosphonic acid scale inhibition water conditioner; (3) the urea groups methylenephosphonic acid scale inhibition water conditioner for preparing, under the identical situation of dosage, its static-state scale inhibition rate can reach and Amino Trimethylene Phosphonic Acid (ATMP) and the suitable degree of hydroxy ethylene phosphonic acids (HEDP), has reached the purpose of comprehensive utilization of resources; (4) filtrate continuation absorbing hydrogen chloride makes technical hydrochloric acid, and reaching turns waste into wealth, and has high economic and social benefit; (5) operational condition gentleness of the present invention, easy handling.
Description of drawings
Figure is a process flow sheet of the present invention.
Embodiment
The present invention as shown in the figure, its production technique may further comprise the steps:
(1) in containing the acidic industrial effluent of formaldehyde, add certain amount of urea, control reaction temperature and reaction times, generate white depositions, filter;
(2) get a certain amount of filter cake, add phosphorus trichloride and formaldehyde, control reaction temperature and time,, obtain urea groups methylenephosphonic acid scale inhibition water conditioner purification of products;
(3) get a certain amount of filtrate, de-chlorine hydride resorber absorbing hydrogen chloride makes technical hydrochloric acid.
Indication production technique embodiment of the present invention is as follows:
Embodiment 1:
Contain in the organophosphorus industrial production waste water of formaldehyde at 400kg, the amount that contains formaldehyde is 2.5%, hydrochloric amount is 4%, add urea 15kg in two batches, 80 ℃ of control reaction temperature, the reaction times is 2 hours, generates methyne urea white precipitate, filter, filtrate is used for membrance-type absorber and continues absorbing hydrogen chloride gas to prepare industrial concentrated hydrochloric acid.Obtain white precipitate 13kg after the filtration, collect the resulting white precipitate of merging.The deposition rate of formaldehyde is more than 98% in the trade effluent.
In reactor, add white precipitate 100kg, add phosphorus trichloride 120kg, stir, when being warmed up to 60 ℃, drip formaldehyde 130kg, dripped in 30 minutes, continue reaction 3 hours afterwards, unreacted monomer is steamed, obtain urea groups methylenephosphonic acid water treatment Scale inhibitors in the reactor.
Embodiment 2:
Contain in the organophosphorus industrial production waste water of formaldehyde at 400kg, the amount that contains formaldehyde is 5%, hydrochloric amount is 4%, add urea 25kg in two batches, 90 ℃ of control reaction temperature, the reaction times is 3 hours, generates methyne urea white precipitate, filter, filtrate is used for membrance-type absorber and continues absorbing hydrogen chloride gas to prepare industrial concentrated hydrochloric acid.Obtain white precipitate 22kg after the filtration, collect the resulting white precipitate of merging.The deposition rate of formaldehyde is more than 98% in the trade effluent.
In reactor, add white precipitate 100kg, add phosphorus trichloride 308kg, stir, when being warmed up to 80 ℃, drip formaldehyde 128kg, dripped in 1 hour, continue reaction 2 hours afterwards, unreacted monomer is steamed, obtain urea groups methylenephosphonic acid water treatment Scale inhibitors in the reactor.
Embodiment 3:
Contain in the organophosphorus industrial production waste water of formaldehyde at 400kg, the amount that contains formaldehyde is 8%, hydrochloric amount is 6%, add urea 35kg in two batches, 60 ℃ of control reaction temperature, the reaction times is 1 hour, generates methyne urea white precipitate, filter, filtrate is used for membrance-type absorber and continues absorbing hydrogen chloride gas to prepare industrial concentrated hydrochloric acid.Obtain white precipitate 38kg after the filtration, collect the resulting white precipitate of merging.The deposition rate of formaldehyde is more than 98% in the trade effluent.
In reactor, add white precipitate 100kg, add phosphorus trichloride 540kg, stir, when being warmed up to 60 ℃, drip formaldehyde 325kg, dripped in 1 hour, continue reaction 3 hours afterwards, unreacted monomer is steamed, obtain urea groups methylenephosphonic acid water treatment Scale inhibitors in the reactor.
The water treatment of the resulting urea groups methylenephosphonic acid of the present invention is as follows with the scale-inhibiting properties test of Scale inhibitors:
By static-state scale inhibition rate and Bubbling method this product and existing ATM P, HEDP, PBTCA etc. are compared.The mensuration of method reference≤water treatment scale performance--tosca method, Bubbling method 〉=(GB16632--1996), the results are shown in following table:
Table 1 static-state scale inhibition rate
Utilize the urea groups methylenephosphonic acid water treatment Scale inhibitors of the prepared formaldehyde in the trade effluent, compare with the organophosphorus Scale inhibitors of routine, have similar chemical property, also have certain advantage to a certain extent, therefore can use as a kind of novel anti-incrustation corrosion inhibitor.
Calcium ion steady concentration (adding the dose homogeneous phase together) with dynamic Bubbling method is surveyed sees Table 2.
Table 2 calcium ion steady concentration
Aspect the calcium ion steady concentration, compare slightly gap with the organophosphor of routine, after still disposing waste liquid as formalin Residue, can make the product with certain use value, realized the purpose of its comprehensive utilization of resources.
Claims (7)
1, formaldehyde comprehensive utilization method in a kind of acidic industrial effluent, it is characterized in that: treatment process may further comprise the steps:
(1) in containing the acidic industrial effluent of formaldehyde, add certain amount of urea, control reaction temperature and reaction times, generate white depositions, filter;
(2) get a certain amount of filter cake, add phosphorus trichloride and formaldehyde, control reaction temperature and time,, obtain urea groups methylenephosphonic acid scale inhibition water conditioner purification of products;
(3) get a certain amount of filtrate, de-chlorine hydride resorber absorbing hydrogen chloride makes technical hydrochloric acid.
2, preparation technology as claimed in claim 1, it is characterized in that: in the step (1), add urea, the add-on that is meant urea satisfies following ratio: the mol ratio of formaldehyde and urea is 0.5:1～5:1, adding can be disposable adding or add in batches, add in batches and refer to be divided into secondary, the feed way more than three times or four times.
3, preparation technology as claimed in claim 1 is characterized in that: in the step (1), control reaction temperature refers to temperature of reaction is controlled at 25-100 ℃.
4, preparation technology as claimed in claim 3 is characterized in that: in the step (1), controlling reaction time refers to the reaction times was controlled at 0.5 hour to 5 hours.
5, preparation technology as claimed in claim 4 is characterized in that: in the step (2), the phosphorus trichloride of adding is 1-10 a times of solid precipitation weight, and the formaldehyde of adding is 1-10 times of solid precipitation weight.
6, preparation technology as claimed in claim 1 is characterized in that: in the step (2), control reaction temperature refers to temperature of reaction is controlled at 30-120 ℃.
7, preparation technology as claimed in claim 1 is characterized in that: in the step (2), controlling reaction time refers to the reaction times was controlled at 1-3 hour.
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| CN2008101581660A CN101381179B (en) | 2008-10-23 | 2008-10-23 | Formaldehyde comprehensive utilization method in acidic industrial effluent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060392A (en) * | 2010-11-22 | 2011-05-18 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
| CN103408176A (en) * | 2013-07-22 | 2013-11-27 | 沈阳理工大学 | Method for treatment of (methyl) acrylic acid production wastewater and recovery of sodium acetate |
| CN103408175A (en) * | 2013-07-22 | 2013-11-27 | 沈阳理工大学 | Treatment and reclamation method of (methyl) acrylic acid production 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 |
| CN109180724A (en) * | 2018-10-22 | 2019-01-11 | 长江大学 | A kind of environment-friendly type calcium scale is drawn up agent and preparation method thereof |
-
2008
- 2008-10-23 CN CN2008101581660A patent/CN101381179B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060392A (en) * | 2010-11-22 | 2011-05-18 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
| CN102060392B (en) * | 2010-11-22 | 2012-02-08 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
| CN103408176A (en) * | 2013-07-22 | 2013-11-27 | 沈阳理工大学 | Method for treatment of (methyl) acrylic acid production wastewater and recovery of sodium acetate |
| CN103408175A (en) * | 2013-07-22 | 2013-11-27 | 沈阳理工大学 | Treatment and reclamation method of (methyl) acrylic acid production 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 |
| CN109180724A (en) * | 2018-10-22 | 2019-01-11 | 长江大学 | A kind of environment-friendly type calcium scale is drawn up agent and preparation method thereof |
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| CN101381179B (en) | 2010-08-11 |
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Owner name: SHANGDONG TAIHE WATER TREATMENT TECHNOLOGIES CO., Free format text: FORMER NAME: SHANDONG TAIHE WATER TREATMENT CO., LTD. |
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Address after: Shandong Hong Village 277000 Zaozhuang City District Xi Wang Zhuang Xiang Patentee after: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES CO., LTD. Address before: Shandong Hong Village 277000 Zaozhuang City District Xi Wang Zhuang Xiang Patentee before: Shandong Taihe Water Treatment Co., Ltd. |