CN102173493A - Process for removing polyvinyl alcohol in waste water - Google Patents
Process for removing polyvinyl alcohol in waste water Download PDFInfo
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- CN102173493A CN102173493A CN 201110055613 CN201110055613A CN102173493A CN 102173493 A CN102173493 A CN 102173493A CN 201110055613 CN201110055613 CN 201110055613 CN 201110055613 A CN201110055613 A CN 201110055613A CN 102173493 A CN102173493 A CN 102173493A
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- waste water
- formaldehyde
- hydrochloric acid
- polyvinyl alcohol
- pva
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Abstract
The invention discloses a process for removing polyvinyl alcohol in waste water, which comprises the following steps of: 1) adding formaldehyde and hydrochloric acid into the waste water containing polyvinyl alcohol (PVA), and controlling the temperature of the waste water to be 70 to 90 DEG C; 2) reacting the added formaldehyde with the PVA in the waste water, wherein the specific reaction process is described in the specification; and 3) separating the generated polyvinyl formal glue as colloidal solid by adopting a separation device and recovering the colloidal solid.
Description
Technical field
The present invention relates to a kind of treatment process of waste water, a kind of technology of removing polyvinyl alcohol in the waste water of saying so more specifically.
Background technology
Polyvinyl alcohol (Polyvinyl A lcohol) is called for short PVA, it is the macromolecular compound that generates through saponification by Vinyl Acetate Copolymer vinegar, the performance of PVA is between rubber and plastics, be that purposes is quite extensive, the high molecular weight water soluble polymer that performance is very good, contain PVA every gram appointment formation 0.10 gram BOD and 1.84 gram COD in every liter of waste water, be that the BOD/COD value is about 0.055, and because the PVA content height in the waste water, the concentration that causes COD in the waste water is up to 47000mg/L, again because PVA belongs to high molecular weight water soluble polymer, be typical hardly degraded organic substance, and biodegradability is very poor.That is to say that employed microorganism is difficult to its degraded in the conventional sewage treatment process, and be subjected in the waste water inhibition as destarch auxiliary agents such as tensio-active agent, SYNTHETIC OPTICAL WHITNER through its activity of microorganism of the degraded PVA of domestication.Therefore how effectively handling the PVA in the waste water, is the current problem that presses for solution.
The materialization treatment technology of PVA mainly contains evaporation concentration method, chemical coagulation method and ultrafiltration process in the waste water at present, advantages such as equipment is simple, easy and simple to handle though the materialization treatment technology has, technical maturity, but organic pollutant is just transferred to solid phase or gas phase from liquid phase, not degraded fully, and, because on some Technological Economies, organic pollutant is not recycled well, has caused the accumulation and the secondary pollution of refuse.
In addition, also occur high-level oxidation technology at present and handle PVA in the waste water, mainly comprise photocatalytic oxidation, Fenton class oxidation style, ozone class oxidation style, supercritical water oxidation method and radiation method.But the ubiquity processing costs is higher, and is to low concentration wastewater treatment effect characteristics preferably, bad for the water treatment effect of high density.
Summary of the invention
The object of the present invention is to provide the treatment process of PVA in a kind of waste water, utilize this technology to handle, and can prevent the generation of secondary pollution after handling the waste water of high density.
The technology of removing polyvinyl alcohol in the waste water among the present invention includes following steps:
1) in containing the waste water of PVA, add formaldehyde, add hydrochloric acid simultaneously, and the temperature of control waste water is between 70-90 ℃;
2) PVA that adds in formaldehyde and the waste water reacts, and concrete reaction process is as follows:
3) formaldehyde polyvinyl acetal of reaction generation is a colloidal solid, adopts tripping device to separate again, reclaims colloidal solid.
In the described step 1), be that to add volume be 1 to 4 times hydrochloric acid of formaldehyde for 1: 100 waste water in the volume ratio of formaldehyde and waste water.
In the described step 1), the volume ratio of described formaldehyde, hydrochloric acid and waste water is 1: 4: 100.
Described formaldehyde and the hydrochloric acid residence time in waste water is 2-4 hour.
Described formaldehyde and the hydrochloric acid residence time in waste water is 2 hours.
Utilization of the present invention adds formaldehyde in waste water, PVA and formaldehyde are reacted under the katalysis of hydrochloric acid generate formaldehyde polyvinyl acetal,, be solid state because formaldehyde polyvinyl acetal is water insoluble, can utilize tripping device from waste water, to separate, and then reduce the concentration of COD.That is to say that according to certain proportioning, add formaldehyde, and use the salt acid for adjusting pH value, the temperature that control is suitable can make COD concentration reach more than 50% up to the COD removal of 47000mg/L in containing the waste water of PVA.
Be formaldehyde and hydrochloric acid owing to what introduce in the treating processes in addition,, can remove in follow-up biochemical treatment unit because the biochemical of formaldehyde and hydrochloric acid is good.And isolated formaldehyde polyvinyl acetal can reuse, and can prevent the generation of secondary pollution.
Embodiment
To the specific embodiment among the present invention be elaborated below.
The present invention removes that the technology of PVA may further comprise the steps in the waste water:
1) in containing the waste water of PVA, add formaldehyde, add hydrochloric acid simultaneously, wherein in the waste water concentration of COD up to more than the 47000mg/L.
2) amount of adding formaldehyde is big more, and speed of response is fast more, and the gelatinoid density of generation is bigger.HCl makes catalyzer, and the volume ratio of formaldehyde, HCl, waste water is 1: 4: 100, and temperature is controlled between 70～90 ℃, reacts more abundant.
PVA reacts with formaldehyde in waste water, and concrete reaction process is as follows:
3) formaldehyde polyvinyl acetal of reaction generation is a colloidal solid, adopts tripping device to separate, and reclaims colloidal solid.
Respectively a plurality of embodiment are specified below:
Embodiment one
Get 4 groups respectively and contain each 150 milliliters of the waste water that PVA, concentration are 47000mg/L, and be numbered, in every group of waste water, add formaldehyde, hydrochloric acid simultaneously, specifically see the following form 1.
Table 1
| 1# | 2# | 3# | 4# | |
| PVA waste water (mL) | 150 | 150 | 150 | 150 |
| Formaldehyde (mL) | 1.5 | 1.5 | 1.5 | 1.5 |
| HCl(mL) | 1.5 | 3.0 | 4.5 | 6.0 |
The temperature of each group all is controlled between 70～90 ℃, and it is inconsistent that each group is tested the time that flco occurs, and one group that the adding hydrochloric acid content is maximum is that 4# produces big flco at first, and reaches reaction end the earliest.Add minimum one group of hydrochloric acid content, reaction has been carried out 4 hours, has produced bigger flco, but has failed to form gelatinous precipitate.The clearance of COD is respectively as following table 2 in concrete reaction times and the waste water:
Table 2
| Experiment content | COD(mg/L) | COD clearance (%) | Reaction times |
| The former water of PVA | 47300 | ||
| 1# | - | - | 4 hours |
| 2# | 38700 | 18.18 | 3 hours |
| 3# | 23000 | 51.37 | 2.5 hour |
| 4# | 22800 | 51.80 | 2 hours |
By above-mentioned experiment as can be known:
(1) hydrochloric acid of adding 3 times (volume ratios) can be removed the COD about 50%;
(2) add 3 times hydrochloric acid and 4 times hydrochloric acid, the clearance of COD is more or less the same, but required time phase difference half hour;
Embodiment two
Get the two group waste water of 200 milliliters of COD concentration respectively, and to add clear water respectively be original 5 times with wastewater dilution, add formaldehyde and hydrochloric acid again, specifically see as following table 3 up to 47000mg/L:
Table 3
| 1# | 2# | |
| PVA waste water (mL) | 200 | 200 |
| Tap water (mL) | 800 | 800 |
| Formaldehyde (mL) | 2 | 2 |
| ?HCl(mL) | 6 | 8 |
Two groups of waste water after will diluting again are divided into 4 parts, analyze the response situation of different time, and temperature is controlled at 70～90 ℃.Operation different time (being respectively 3 and 4 hours), the after-filtration of taking a sample is surveyed COD.Result such as following table 4:
Table 4
| Experiment content | COD(mg/L) | COD clearance (%) |
| 5 times of former water dilutions | 10000 | - |
| 1#-1 (3 hours) | 8830 | 27.80 |
| 2#-1 (3 hours) | 4730 | 50.00 |
| 1#-2 (4 hours) | 6310 | 33.30 |
| 2#-2 (4 hours) | 4740 | 49.89 |
By The above results as can be seen, when the volume ratio of adding hydrochloric acid is 4 times, the clearance height of COD.When the hydrochloric acid volume ratio that adds was 3 times, the clearance of COD was low relatively, but along with the increase in reaction times, the clearance of COD also further improves; But to adding the hydrochloric acid ratio is 4 times water sample, even prolong the reaction times, little to the clearance influence of COD.
Claims (5)
1. remove that the technology of polyvinyl alcohol includes following steps in the waste water for one kind:
1) in containing the waste water of PVA, add formaldehyde, add hydrochloric acid simultaneously, and the temperature of control waste water is between 70-90 ℃;
2) PVA that adds in formaldehyde and the waste water reacts, and concrete reaction process is as follows:
3) formaldehyde polyvinyl acetal of reaction generation is a colloidal solid, adopts tripping device to separate again, reclaims colloidal solid.
2. the technology of polyvinyl alcohol is characterized in that in the removal waste water according to claim 1, in the described step 1), is that to add volume be 1 to 4 times hydrochloric acid of formaldehyde for 1: 100 waste water in the volume ratio of formaldehyde and waste water.
3. the technology of polyvinyl alcohol is characterized in that in the removal waste water according to claim 2, and in the described step 1), the volume ratio of described formaldehyde, hydrochloric acid and waste water is 1: 4: 100.
4. the technology of polyvinyl alcohol is characterized in that in the removal waste water according to claim 1, and described formaldehyde and the hydrochloric acid residence time in waste water is 2-4 hour.
5. the technology of polyvinyl alcohol is characterized in that in the removal waste water according to claim 3, and described formaldehyde and the hydrochloric acid residence time in waste water is 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201110055613 CN102173493A (en) | 2011-03-08 | 2011-03-08 | Process for removing polyvinyl alcohol in waste water |
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| CN 201110055613 CN102173493A (en) | 2011-03-08 | 2011-03-08 | Process for removing polyvinyl alcohol in waste water |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874948A (en) * | 2012-09-26 | 2013-01-16 | 沈阳化工大学 | Method for recycling formaldehyde wastewater generated during production of A-stage phenolic resin |
| CN103468175A (en) * | 2013-08-15 | 2013-12-25 | 浙江工业大学 | Method for preparing paper tube adhesive through utilizing high-concentration printing, dyeing and desizing wastewater |
| CN108840479A (en) * | 2018-07-15 | 2018-11-20 | 杭州火蓝刀锋科技咨询有限公司 | A kind of printing and dyeing PVA pretreatment method for wastewater |
| CN109535285A (en) * | 2018-12-20 | 2019-03-29 | 深圳市星河环境技术有限公司 | A kind of PVA discards the resource utilization method and system of adhesive |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054093A (en) * | 1990-02-13 | 1991-08-28 | 泰州市实验化工厂 | Use technology for producing polyvinyl formal glue from waste vinylon |
| US20040198849A1 (en) * | 2001-12-05 | 2004-10-07 | Tejraj Aminabhavi | Ion exchange membranes, methods and processes for production thereof and uses in specific applications |
| CN1613798A (en) * | 2003-11-03 | 2005-05-11 | 中国科学院成都生物研究所 | Carrier for waste water biological treatment and its preparation |
| CN1765779A (en) * | 2005-09-02 | 2006-05-03 | 浙江大学 | Printing and dyeing wastewater recovery and disposal method |
| CN101337725A (en) * | 2008-06-12 | 2009-01-07 | 林啟贤 | PVA precipitant and processing method for desizing waste water |
-
2011
- 2011-03-08 CN CN 201110055613 patent/CN102173493A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054093A (en) * | 1990-02-13 | 1991-08-28 | 泰州市实验化工厂 | Use technology for producing polyvinyl formal glue from waste vinylon |
| US20040198849A1 (en) * | 2001-12-05 | 2004-10-07 | Tejraj Aminabhavi | Ion exchange membranes, methods and processes for production thereof and uses in specific applications |
| CN1613798A (en) * | 2003-11-03 | 2005-05-11 | 中国科学院成都生物研究所 | Carrier for waste water biological treatment and its preparation |
| CN1765779A (en) * | 2005-09-02 | 2006-05-03 | 浙江大学 | Printing and dyeing wastewater recovery and disposal method |
| CN101337725A (en) * | 2008-06-12 | 2009-01-07 | 林啟贤 | PVA precipitant and processing method for desizing waste water |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874948A (en) * | 2012-09-26 | 2013-01-16 | 沈阳化工大学 | Method for recycling formaldehyde wastewater generated during production of A-stage phenolic resin |
| CN103468175A (en) * | 2013-08-15 | 2013-12-25 | 浙江工业大学 | Method for preparing paper tube adhesive through utilizing high-concentration printing, dyeing and desizing wastewater |
| CN103468175B (en) * | 2013-08-15 | 2015-03-04 | 浙江工业大学 | Method for preparing paper tube adhesive through utilizing high-concentration printing, dyeing and desizing wastewater |
| CN108840479A (en) * | 2018-07-15 | 2018-11-20 | 杭州火蓝刀锋科技咨询有限公司 | A kind of printing and dyeing PVA pretreatment method for wastewater |
| CN109535285A (en) * | 2018-12-20 | 2019-03-29 | 深圳市星河环境技术有限公司 | A kind of PVA discards the resource utilization method and system of adhesive |
| CN109535285B (en) * | 2018-12-20 | 2021-06-01 | 深圳市星河环境技术有限公司 | Resource utilization method and system for PVA waste adhesive |
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Application publication date: 20110907 |