CN105399620A - Acrylic acid extraction recovery technology - Google Patents
Acrylic acid extraction recovery technology Download PDFInfo
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- CN105399620A CN105399620A CN201510774339.1A CN201510774339A CN105399620A CN 105399620 A CN105399620 A CN 105399620A CN 201510774339 A CN201510774339 A CN 201510774339A CN 105399620 A CN105399620 A CN 105399620A
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- acrylic acid
- extraction
- waste water
- acid content
- extraction agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an acrylic acid extraction recovery technology which is characterized by comprising the following steps: S1, taking 1000g of primary wastewater (esterification generated water or water washing wastewater of the first two times of washing) with the acrylic acid content of 12.8wt%, adding 500g of an extracting agent, stirring at 40-45 DEG C for 15min, then pouring into a separating funnel, and sealing for standing; S2, after standing, separately containing the wastewater of the lower layer and the extracting agent of the upper layer, and adding 500g of the extracting agent to perform extraction for the second time according to the step 1, wherein the acrylic acid content in the wastewater of the lower layer after extraction once is lowered to 4-5wt%; and the like.
Description
Technical field
The present invention designs recovery field, more specifically, designs a kind of acrylic acid extraction recovery technology.
Background technology
Acrylic ester monomer (such as DPGDA, TPGDA, NPGDA, HDDA, TMPTA etc.), it is maximum, the widest acrylate monomer of current UV paint field consumption, there is superior over-all properties, cured paint film performance is good, there is very strong dilution capacity simultaneously, be employed at numerous areas, as photo-cured coating, printing-ink, tackiness agent and matrix material etc.The method of current this type of acrylate monomer of production is generally by direct esterification, after esterification, through alkali lye neutralization, extraction, washing and solvent removed by vacuum, finally obtains product.Specifically alcohols (dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, the alcohols such as 6-hexylene glycol, TriMethylolPropane(TMP)) and vinylformic acid, catalyzer (as methylsulphonic acid, p-methyl benzenesulfonic acid, inorganic heteropolyacid) and stopper (as Resorcinol, MEHQ, phenol, copper sulfate, cupric chloride, cuprous chloride etc. one or more) effect under, by use band water solvent (as toluene, normal heptane, normal hexane, hexanaphthene etc. one or more) constantly carry out esterification dehydration.Due in actual production formula, in order to reach higher esterification degree, acrylic acid amount is generally excessive 8 ~ 15%, that is, after esterification terminates, remained in esterifying liquid in a large amount of vinylformic acid (accounting for 6 ~ 8%) and esterification generation water also containing a large amount of vinylformic acid (accounting for 10 ~ 15%).In order to obtain qualified product further, must to use in low-concentration alkali liquor and excessive acid, an acidic catalyst and extract stopper in esterifying liquid, finally vacuumizing and remove band water solvent.Therefore, at home in the actual production of numerous monomer manufacturing enterprise, substantially be the technique adopting above-mentioned neutralization, extraction, washing, produce the waste water that the monomer product of 1 ton about produces 1 ~ 2 ton as calculated, a large amount of waste water also because in and vinylformic acid and producing, create a large amount of waste residues (sodium acrylate) simultaneously, not only a large amount of vinylformic acid of loss, too increases cost for wastewater treatment, brings negative impact to environment, economic benefit is also low, is a kind of pole production technique not environmentally.How existing technique is improved, reduce acrylic acid wastage rate, reduce the generation of waste water and dregs simultaneously.
Summary of the invention
In order to solve above problem, the invention provides a kind of acrylic acid extraction recovery technology, comprising the following steps:
S1. get 1000g primary wastewater (esterification generates water or twice washing waste water), the acrylic acid content of waste water is 12.8wt%, adds 500g extraction agent, and after stirring 15min at 40 ~ 45 DEG C, pours sealing and standing in separating funnel into;
S2. after leaving standstill, lower floor's waste water and upper strata extraction agent are separately held, lead to acrylic acid content in the lower floor's waste water after going over extraction and be reduced to 4 ~ 5wt%, add 500g extraction agent and carry out second time extraction by step 1);
S3. after second time extraction terminates, in lower floor's waste water, acrylic acid content has been reduced to below 2wt%, and so repeatedly extract four to five times, in lower floor's waste water, acrylic acid content is down to below 0.5wt%, collect the upper strata extraction agent after extraction, the acrylic acid content of upper strata extraction agent is at 10 ~ 12wt%;
S4. the mixed solution containing vinylformic acid, extraction agent is poured in the four-hole boiling flask of band stirring and heating jacket, add a small amount of stopper (phenols, mantoquita etc.), build is highly that (every root rectifying column is about 25cm to 1 ~ 1.5 meter of Webster rectifying column, need 4 ~ 6) and prolong, pumped vacuum systems, a small amount of zeolite is filled at every root interface place, is warming up to 90 ~ 100 DEG C, and progressively gas clean-up is to-0.085 ~-0.095kpa, after rectifying 2 ~ 3h, both.
Vinylformic acid purity after recovery is higher than 98%, and the rate of recovery, more than 85%, can be directly used in the production synthesis of acrylate monomer.
The present invention has the following advantages:
1) vinylformic acid wastage rate are reduced;
2) the waste water and dregs generation in actual production process is reduced;
3) waste water and dregs processing cost is reduced;
4) after the acrylic acid extraction in waste water, washing monomer can be used for, reduce the water consumption of monomer.
Embodiment
The present invention is further described below in conjunction with specific embodiment.Unless stated otherwise, the present invention adopts reagent, equipment and method are conventional commercial reagent, equipment and the conventional method used of the art.
Embodiment 1
1) get 1000g primary wastewater (esterification generates water or twice washing waste water), the acrylic acid content of waste water is 12.8wt%, adds 500g extraction agent, and after stirring 15min at 40 ~ 45 DEG C, pours sealing and standing in separating funnel into;
2) after leaving standstill, lower floor's waste water and upper strata extraction agent are separately held, lead to acrylic acid content in the lower floor's waste water after going over extraction and be reduced to 4 ~ 5wt%, add 500g extraction agent and carry out second time extraction by step 1);
3) after second time extraction terminates, in lower floor's waste water, acrylic acid content has been reduced to below 2wt%, and so repeatedly extract four to five times, in lower floor's waste water, acrylic acid content is down to below 0.5wt%, collect the upper strata extraction agent after extraction, the acrylic acid content of upper strata extraction agent is at 10 ~ 12wt%;
4) mixed solution containing vinylformic acid, extraction agent is poured in the four-hole boiling flask of band stirring and heating jacket, add a small amount of stopper (phenols, mantoquita etc.), build is highly that (every root rectifying column is about 25cm to 1 ~ 1.5 meter of Webster rectifying column, need 4 ~ 6) and prolong, pumped vacuum systems, a small amount of zeolite is filled at every root interface place, is warming up to 90 ~ 100 DEG C, progressively gas clean-up is to-0.085 ~-0.095kpa, after rectifying 2 ~ 3h, obtain the vinylformic acid 115g after purifying, purity is 98.2%;
5) known by above-mentioned case, the vinylformic acid rate of recovery is more than 85%, and after reclaiming, vinylformic acid purity reaches more than 98%, and it is produce synthesis that the vinylformic acid after this recovery can be directly used in acrylate monomer;
6) by the vinylformic acid after above-mentioned recovery in 50% sour ratio drop into synthesis lab scale, pilot run shows that product yield is more than 95%, and finished product look number reaches 40(APHA) below.
The present invention is on the basis of existing acrylic ester monomer production technique, the elementary waste liquid produced in monomer production process (esterification generates the waste water of water and twice washing) is extracted, vinylformic acid in extraction and recovery waste liquid, and by the vinylformic acid after reclaiming for the production of, reach the object reducing acrylic acid wastage rate, reduce waste water and dregs generation.
The object of the invention realizes, main improvement is the use of a kind of acrylic acid extraction agent and carries out degree of depth extraction to the primary wastewater produced in production process, acrylic acid extraction in waste water is separated, then by vinylformic acid and extraction agent fractionation by distillation, obtains the vinylformic acid of purity more than 98%.By the waste water after process of the present invention, namely achieve acrylic acid recovery cycling and reutilization, also make esterifying liquid post-processed no longer need the alkali lye of multistep to neutralize, greatly reduce the generation of waste water.Meanwhile, because in waste liquid, vinylformic acid decreases, waste residue sodium acrylate also reduces thereupon, and total waste residue amount have also been obtained good control, not only reduces the processing cost of waste water and dregs, also mitigates the pollution that process waste water and dregs brings to environment.
Claims (3)
1. an acrylic acid extraction recovery technology, is characterized in that, comprises the following steps
S1. get 1000g primary wastewater (esterification generates water or twice washing waste water), the acrylic acid content of waste water is 12.8wt%, adds 500g extraction agent, and after stirring 15min at 40 ~ 45 DEG C, pours sealing and standing in separating funnel into;
S2. after leaving standstill, lower floor's waste water and upper strata extraction agent are separately held, lead to acrylic acid content in the lower floor's waste water after going over extraction and be reduced to 4 ~ 5wt%, add 500g extraction agent and carry out second time extraction by step 1);
S3. after second time extraction terminates, in lower floor's waste water, acrylic acid content has been reduced to below 2wt%, and so repeatedly extract four to five times, in lower floor's waste water, acrylic acid content is down to below 0.5wt%, collect the upper strata extraction agent after extraction, the acrylic acid content of upper strata extraction agent is at 10 ~ 12wt%;
S4. the mixed solution containing vinylformic acid, extraction agent is poured in the four-hole boiling flask of band stirring and heating jacket, add a small amount of stopper (phenols, mantoquita etc.), build is highly that (every root rectifying column is about 25cm to 1 ~ 1.5 meter of Webster rectifying column, need 4 ~ 6) and prolong, pumped vacuum systems, a small amount of zeolite is filled at every root interface place, is warming up to 90 ~ 100 DEG C, and progressively gas clean-up is to-0.085 ~-0.095kpa, after rectifying 2 ~ 3h, both.
2. acrylic acid extraction recovery technology according to claim 1, is characterized in that, the vinylformic acid purity after recovery is higher than 98%, and the rate of recovery is more than 85%.
3. the vinylformic acid of an acrylic acid extraction recovery technology gained according to claim 1 is directly used in the production synthesis of acrylate monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510774339.1A CN105399620A (en) | 2015-11-13 | 2015-11-13 | Acrylic acid extraction recovery technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510774339.1A CN105399620A (en) | 2015-11-13 | 2015-11-13 | Acrylic acid extraction recovery technology |
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| CN105399620A true CN105399620A (en) | 2016-03-16 |
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| CN201510774339.1A Pending CN105399620A (en) | 2015-11-13 | 2015-11-13 | Acrylic acid extraction recovery technology |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684470A (en) * | 2019-10-21 | 2020-01-14 | 江苏利田科技股份有限公司 | Method for preparing acrylate adhesive by using UV monomer wastewater and acrylate adhesive |
| CN111807960A (en) * | 2020-08-01 | 2020-10-23 | 浙江亦龙新材料有限公司 | Preparation process of isooctyl acrylate |
| CN111848396A (en) * | 2020-08-01 | 2020-10-30 | 浙江亦龙新材料有限公司 | Synthetic system of isooctyl acrylate |
| CN113233637A (en) * | 2021-04-19 | 2021-08-10 | 珠海展辰新材料股份有限公司 | Waste water treatment method |
| CN113387493A (en) * | 2021-04-15 | 2021-09-14 | 佳化化学科技发展（上海）有限公司 | Wastewater treatment process in production of active diluent |
Citations (4)
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|---|---|---|---|---|
| CN1249739A (en) * | 1997-03-07 | 2000-04-05 | 巴斯福股份公司 | Method for extracting (meth) acrylic acid |
| CN1683309A (en) * | 2005-02-06 | 2005-10-19 | 蓝仁水 | Process for purifying (methyl) propenoic acid by combined extracting and azeotropic rectification |
| CN102267890A (en) * | 2010-11-16 | 2011-12-07 | 中国环境科学研究院 | Method for extracting and recovering acrylic acid from acrylic ester production wastewater |
| CN104557511A (en) * | 2015-01-24 | 2015-04-29 | 淄博市兴鲁化工有限公司 | Method for recovering acrylic acid from acrylic acid water |
-
2015
- 2015-11-13 CN CN201510774339.1A patent/CN105399620A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249739A (en) * | 1997-03-07 | 2000-04-05 | 巴斯福股份公司 | Method for extracting (meth) acrylic acid |
| CN1683309A (en) * | 2005-02-06 | 2005-10-19 | 蓝仁水 | Process for purifying (methyl) propenoic acid by combined extracting and azeotropic rectification |
| CN102267890A (en) * | 2010-11-16 | 2011-12-07 | 中国环境科学研究院 | Method for extracting and recovering acrylic acid from acrylic ester production wastewater |
| CN104557511A (en) * | 2015-01-24 | 2015-04-29 | 淄博市兴鲁化工有限公司 | Method for recovering acrylic acid from acrylic acid water |
Non-Patent Citations (1)
| Title |
|---|
| 侯有军: "特种丙烯酸酯单体的研究进展", 《涂料工业》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684470A (en) * | 2019-10-21 | 2020-01-14 | 江苏利田科技股份有限公司 | Method for preparing acrylate adhesive by using UV monomer wastewater and acrylate adhesive |
| CN110684470B (en) * | 2019-10-21 | 2022-03-01 | 江苏利田科技股份有限公司 | Method for preparing acrylate adhesive by using UV monomer wastewater and acrylate adhesive |
| CN111807960A (en) * | 2020-08-01 | 2020-10-23 | 浙江亦龙新材料有限公司 | Preparation process of isooctyl acrylate |
| CN111848396A (en) * | 2020-08-01 | 2020-10-30 | 浙江亦龙新材料有限公司 | Synthetic system of isooctyl acrylate |
| CN111807960B (en) * | 2020-08-01 | 2022-04-22 | 浙江亦龙新材料有限公司 | Preparation process of isooctyl acrylate |
| CN113387493A (en) * | 2021-04-15 | 2021-09-14 | 佳化化学科技发展（上海）有限公司 | Wastewater treatment process in production of active diluent |
| CN113387493B (en) * | 2021-04-15 | 2023-12-05 | 佳化化学科技发展（上海）有限公司 | Wastewater treatment process in reactive diluent production |
| CN113233637A (en) * | 2021-04-19 | 2021-08-10 | 珠海展辰新材料股份有限公司 | Waste water treatment method |
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