CN104557540A - Clean technique for producing acrylate-hydroxy ester by adopting continuous process - Google Patents
Clean technique for producing acrylate-hydroxy ester by adopting continuous process Download PDFInfo
- Publication number
- CN104557540A CN104557540A CN201510035372.2A CN201510035372A CN104557540A CN 104557540 A CN104557540 A CN 104557540A CN 201510035372 A CN201510035372 A CN 201510035372A CN 104557540 A CN104557540 A CN 104557540A
- Authority
- CN
- China
- Prior art keywords
- reaction
- stopper
- ethylene oxide
- hydroxy ester
- oxyethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a clean technique for producing acrylate-hydroxy ester by adopting a continuous process. The clean technique for producing acrylate-hydroxy ester by adopting the continuous process comprises the following steps: 1) dissolving a catalyst and a polymerization inhibitor in acrylic acid, mixing and measuring, and then continuously pumping the obtained mixture into a tubular reactor with ethylene oxide at a certain ratio, wherein the mole ratio of acrylic acid to ethylene oxide is 1:(1.1-1.5); and 2) after reaction is finished, recycling ethylene oxide through low boiling fraction removal, and causing the rest reaction product to continuously enter an evaporator, so that the finished product is obtained. The clean technique for producing the acrylate-hydroxy ester by adopting the continuous process has the beneficial effects that ethylene oxide is excessive, so that the reaction time is short, and less byproducts are produced; reaction polymerization and reaction exotherm controllability is improved, and the production safety is greatly improved; the reaction time is short, the usage amount of the polymerization inhibitor is reduced, colour number can be effectively reduced, and the production cost is reduced; no steam is consumed in a continuous reaction process, and the production energy consumption is reduced; no replacement is required to be carried out after reaction is normally carried out, basically no nitrogen is consumed during production, and the amount of waste gas discharged out is reduced; and ethylene oxide in a degassing process during normal production can be recycled and is not discharged out, so that no pollution is produced to the air and water.
Description
Technical field
The present invention relates to a kind of crylic acid hydroxy ester continuous processing process for cleanly preparing.
Background technology
Crylic acid hydroxy ester has as the extraordinary ester of vinylformic acid: Hydroxyethyl Acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410 four products, because product reaction type is identical, reaction conditions is close, available a set of production unit switches to be produced.All adopt (methyl) vinylformic acid, epoxy second (third) alkane additive process at present, for Hydroxyethyl acrylate, first vinylformic acid is added in reactor, then drip oxyethane, control temperature of reaction 70 ~ 90 DEG C, get product after degassed, thin film evaporation after insulation.
Due to reaction and soaking time longer, byproduct of reaction vinylformic acid binaryglycol ester and ethylene glycol diacrylate more, unstable product quality, average product content only has about 93%; In degassed link in production process, oxyethane is water-soluble after extracting out, can cause certain pollution to water body; Esterification is batch technology, needs constantly to replace, feeds intake, heats up, reacts cooling, blowing, and quality fluctuation is large, and energy consumption is large, labor intensity of operating staff is large.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of crylic acid hydroxy ester continuous processing process for cleanly preparing.
To achieve these goals, the present invention adopts following technical scheme:
A kind of crylic acid hydroxy ester continuous processing process for cleanly preparing, comprises the following steps:
1). catalyzer, stopper are dissolved in vinylformic acid, squeeze into continuously in tubular reactor with oxyethane by a certain percentage after mixing weighing; Vinylformic acid and molar are than being 1:1.1 ~ 1:1.5; In the excessive situation of oxyethane, react fast.
2). after completion of the reaction after de-light recovery oxyethane, enter vaporizer continuously and namely obtain the finished product, reclaim gained oxyethane reusable edible.
Described step 1) in, temperature of reaction 70 ~ 90 DEG C, pressure 0.4 ~ 0.8Mpa, the residence time 50 ~ 90min;
Described step 2) in, de-light recovered temperature 60 ~ 70 DEG C, pressure-0.095Mpa, the residence time is about 20min; Evaporator temperature 85 ~ 95 DEG C, working pressure≤200torr (absolute pressure), material is residence time <5min in a device.
Further, in technique scheme, described stopper 705 (tetramethyl piperidine nitrogen oxygen free radical tris phosphite) and stopper MEHQ (MEHQ).
Further, in technique scheme, described catalyzer is chromium acetate.
Further, in technique scheme, described vaporizer is thin-film evaporator.
Further, in technique scheme, stopper MEHQ: stopper 705: oxyethane weight ratio is 1:3:10:140 ~ 190.
The beneficial effect of the invention
1) because oxyethane is excessive, the reaction times is short, and by product is few, and thick ester content significantly improves.
2) in reaction process, system liquid holdup is little, and the controllability for reactive polymeric, exothermic heat of reaction improves, and occur that the uncontrollable factor of sharply heat release reduces, production security improves greatly.
3) reaction times is short, and stopper consumption reduces, and effectively can reduce look number, reduces production cost.
4) in tandem reaction sequence without the need to start, do not consume steam, production energy consumption reduce.Do not need displacement after the normal operation of reaction, substantially without nitrogen consumption in production process, the outer discharge capacity of waste gas reduces.
5) in normal production run, the oxyethane of degassing process is recyclable, without outer row, does not cause air and water pollution.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
Further illustrate with reference to the accompanying drawings.
Embodiment 1
As shown in Figure 1, a kind of crylic acid hydroxy ester continuous processing process for cleanly preparing, comprises the following steps:
1). 3 grams of catalyzer, 3 grams of stoppers are dissolved in 500 grams of vinylformic acid, squeeze into continuously in tubular reactor than for 1:1.3 by vinylformic acid and molar after mixing weighing; In the excessive situation of oxyethane, react fast.
2). after completion of the reaction after de-light recovery oxyethane, enter vaporizer continuously and namely obtain the finished product, reclaim gained oxyethane reusable edible.
Step 1) in, temperature of reaction 80 DEG C, pressure 0.6Mpa, residence time 60min;
Step 2) in, de-light recovered temperature 65 DEG C, pressure-0.095Mpa, the residence time is about 20min; Evaporator temperature 90 DEG C, working pressure 200torr (absolute pressure), material is residence time <5min in a device.
Stopper is stopper 705 (tetramethyl piperidine nitrogen oxygen free radical tris phosphite) and stopper MEHQ (MEHQ).Stopper MEHQ: stopper 705 mass ratio is 1:3.
Above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (6)
1. a crylic acid hydroxy ester continuous processing process for cleanly preparing, is characterized in that comprising the following steps:
1). catalyzer, stopper are dissolved in vinylformic acid, squeeze into continuously in tubular reactor with oxyethane by a certain percentage after mixing weighing; Vinylformic acid and molar are than being 1:1.1 ~ 1.5;
2). after completion of the reaction after de-light recovery oxyethane, enter vaporizer continuously and namely obtain the finished product;
Described step 1) in, temperature of reaction 70 ~ 90 DEG C, pressure 0.4 ~ 0.8Mpa, the residence time 50 ~ 90min;
Described step 2) in, de-light recovered temperature 60 ~ 70 DEG C, pressure-0.095Mpa, the residence time is about 20min; Evaporator temperature 85 ~ 95 DEG C, working pressure≤200torr, material is residence time <5min in a device.
2. technique according to claim 1, is characterized in that: described stopper is stopper 705 and stopper MEHQ.
3. technique according to claim 1, is characterized in that: described catalyzer is chromium acetate.
4. technique according to claim 2, is characterized in that: stopper MEHQ: stopper 705: oxyethane weight ratio is 1:3:10:140 ~ 190.
5. technique according to claim 2, is characterized in that: described vaporizer is thin-film evaporator.
6. the technique according to claim 1-5 any one, is characterized in that: reclaim gained oxyethane reusable edible.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510035372.2A CN104557540A (en) | 2015-01-24 | 2015-01-24 | Clean technique for producing acrylate-hydroxy ester by adopting continuous process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510035372.2A CN104557540A (en) | 2015-01-24 | 2015-01-24 | Clean technique for producing acrylate-hydroxy ester by adopting continuous process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104557540A true CN104557540A (en) | 2015-04-29 |
Family
ID=53074722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510035372.2A Pending CN104557540A (en) | 2015-01-24 | 2015-01-24 | Clean technique for producing acrylate-hydroxy ester by adopting continuous process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104557540A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602380A (en) * | 2017-09-06 | 2018-01-19 | 江苏安顺新材料科技有限公司 | The continuous producing method and device of a kind of hydroxy-ethyl acrylate |
| CN108409568A (en) * | 2018-04-03 | 2018-08-17 | 上海华谊新材料有限公司 | （Methyl）The preparation method of acrylic acid hydroxy alkyl ester |
| CN109467505A (en) * | 2018-11-16 | 2019-03-15 | 潍坊科麦化工有限公司 | A kind of preparation method of hydroxyethyl methacrylate |
| CN112939774A (en) * | 2021-03-05 | 2021-06-11 | 武汉海翎化学工业有限公司 | Production method of methacrylic acid hydroxy ester or acrylic acid hydroxy ester |
| CN116102421A (en) * | 2023-02-10 | 2023-05-12 | 山东兴鲁承宏新材料科技有限公司 | Continuous production process of high-yield acrylic acid alkyl ester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632854A (en) * | 1968-03-09 | 1972-01-04 | Bp Chem Int Ltd | Production of esters |
| US3875211A (en) * | 1973-01-22 | 1975-04-01 | Alcolac Inc | Process for preparing 2-hydroxyalkylacrylates and 2-hydroxyalkylmethacrylates |
| CN1483718A (en) * | 2002-08-12 | 2004-03-24 | 株式会社日本触媒 | Procdss for preparing hydroxyaldyl (meth) acrylate |
| CN102584582A (en) * | 2012-01-16 | 2012-07-18 | 常州海克莱化学有限公司 | Preparing technology of hydroxyethyl acrylate |
-
2015
- 2015-01-24 CN CN201510035372.2A patent/CN104557540A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632854A (en) * | 1968-03-09 | 1972-01-04 | Bp Chem Int Ltd | Production of esters |
| US3875211A (en) * | 1973-01-22 | 1975-04-01 | Alcolac Inc | Process for preparing 2-hydroxyalkylacrylates and 2-hydroxyalkylmethacrylates |
| CN1483718A (en) * | 2002-08-12 | 2004-03-24 | 株式会社日本触媒 | Procdss for preparing hydroxyaldyl (meth) acrylate |
| CN102584582A (en) * | 2012-01-16 | 2012-07-18 | 常州海克莱化学有限公司 | Preparing technology of hydroxyethyl acrylate |
Non-Patent Citations (1)
| Title |
|---|
| 翁羽飞等: "丙烯酸β-羟乙酯的合成研究", 《化学世界》, no. 11, 31 December 1999 (1999-12-31), pages 592 - 595 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602380A (en) * | 2017-09-06 | 2018-01-19 | 江苏安顺新材料科技有限公司 | The continuous producing method and device of a kind of hydroxy-ethyl acrylate |
| CN108409568A (en) * | 2018-04-03 | 2018-08-17 | 上海华谊新材料有限公司 | （Methyl）The preparation method of acrylic acid hydroxy alkyl ester |
| CN109467505A (en) * | 2018-11-16 | 2019-03-15 | 潍坊科麦化工有限公司 | A kind of preparation method of hydroxyethyl methacrylate |
| CN112939774A (en) * | 2021-03-05 | 2021-06-11 | 武汉海翎化学工业有限公司 | Production method of methacrylic acid hydroxy ester or acrylic acid hydroxy ester |
| CN116102421A (en) * | 2023-02-10 | 2023-05-12 | 山东兴鲁承宏新材料科技有限公司 | Continuous production process of high-yield acrylic acid alkyl ester |
| CN116102421B (en) * | 2023-02-10 | 2024-03-26 | 山东兴鲁承宏新材料科技有限公司 | Continuous production process of high-yield alkyl acrylate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104557540A (en) | Clean technique for producing acrylate-hydroxy ester by adopting continuous process | |
| CN105384639B (en) | Refined purifying plant for continuously producing LITHIUM BATTERY dimethyl carbonate | |
| JP7122764B2 (en) | Systems and processes for co-producing dimethyl carbonate and ethylene glycol | |
| CN103044257B (en) | Terylene waste material produces alcoholysis method and the apparatus system of dioctyl terephthalate | |
| CN102451573B (en) | Acetic acid dehydrating tower rectifying method | |
| CN102557932B (en) | Method for producing isobutyl acetate | |
| CN103113614B (en) | PVA (Polyvinyl Alcohol) Energy-Saving and Consumption-Reducing Production New Technology Method | |
| CN102795961B (en) | Device and method for synthesizing sec-butyl alcohol by continuous reaction-rectification | |
| CN104086363B (en) | The energy-saving reclaiming process of N-BUTYL ACETATE and butanols in waste acid water | |
| CN104151144A (en) | Method for preparing phenol/acetone by decomposing cumene hydroperoxide | |
| CN106220499B (en) | A kind of device and method for producing dimethyl adipate | |
| CN106242970B (en) | A kind of device and method producing dimethyl adipate | |
| CN108752192B (en) | Method for treating DMAc waste liquid containing acetic acid in spandex | |
| CN112047838B (en) | Relay type ethyl acetate industrial preparation process | |
| CN105669445B (en) | The production technology of ethyl acetate | |
| CN102895861B (en) | Method and device for recovering phosphorus trichloride tail gas and byproduct phosphorous acid | |
| CN107311864A (en) | A kind of chemical purification process | |
| CN106905269A (en) | The technique that a kind of autoclave continuously hydrogen adding produces 2 methyltetrahydrofurans | |
| CN109569488B (en) | Continuous rectification alcohol ester twelve-production system and method for producing alcohol ester twelve | |
| CN203007176U (en) | Alcoholysis device system for preparing dioctyl terephthalate from Dacron wastes | |
| CN105001999A (en) | Method for producing biodiesel through continuous esterification of waste oil | |
| CN216005722U (en) | Production system for preparing ethyl p-aminobenzoate through continuous reaction | |
| CN102812055B (en) | Production Method And Production Device For Polyvinyl Alcohol | |
| CN102452925B (en) | Method for separating acetic acid from water | |
| CN213853156U (en) | NMP solvent regeneration recovery system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150429 |