CN102775295B - Method for purifying acrylic acid - Google Patents
Method for purifying acrylic acid Download PDFInfo
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- CN102775295B CN102775295B CN201210283215.XA CN201210283215A CN102775295B CN 102775295 B CN102775295 B CN 102775295B CN 201210283215 A CN201210283215 A CN 201210283215A CN 102775295 B CN102775295 B CN 102775295B
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Abstract
The invention relates to a method for purifying acrylic acid. Particularly, the method comprises an absorption tower process flow and a purifying tower process flow. By coupling of the acrylic acid cooling, absorption and purification process, a system composed of two towers can be utilized to finish recycle refining of acrylic acid, water is recycled to serve as an absorbent and a cooling agent simultaneously, other solvents (an extracting agent and an entrainer) are not required, water does not need supplementing additionally, pollution to the environment caused by the solvents is avoided, and discharge free of waste water is also achieved. The method is simple in process, and the equipment investment cost and the operating cost are remarkably reduced. Simultaneously, the method has the advantages of being low in energy consumption and auxiliary raw material consumption and belongs to cleaning production processes.
Description
Technical field
The present invention relates to a kind of from containing isolation andpurification acrylic acid acrylic acid gas phase mixture, relate in particular to a kind of from vinylformic acid reactor obtain containing isolation andpurification acrylic acid acrylic acid mixed gas
Background technology
Vinylformic acid is important Organic Chemicals, is mainly used in the production of acrylate and polyacrylic acid (salt) class.Wherein, acrylate series products is widely used in the industries such as topcoating, textile auxiliary agent, tamanori, leather, papermaking; Polyacrylic acid (salt) class is then for fields such as super absorbent resin, washing composition and water conditioners.
Vinylformic acid production technology has ten several methods such as chloroethanol method, ketenes method, Reppe method, but at present, all vinylformic acid large production equipments all adopt PROPENE IN GAS PHASE OXIDATION method to produce in the world.Oxidation of propylene produces acrylic acid Technology has various feature to be thus widely used in actual production.
The method, is reacted by beds under water vapor and other rare gas element exist for raw material with propylene and air.Reaction is divided into two steps to carry out.
The first step, under MoBiFe composite oxide catalysts exists, propylene is oxidized by oxygen generation propenal:
CH
2=CHCH
3+ O
2→ CH
2=CHCHO+H
2o, reaction heat is: 3.4 × 105J/mol
Second step, under MoVWCu composite oxide catalysts exists, propenal is oxidized to vinylformic acid further:
2CH
2=CHCHO+O
2→ 2CH
2=CHCOOH, reaction heat is: 2.52 × 105J/mol
In acrylic acid process that purification and recover oxidation is obtained, mainly pass through certain step such as absorption, extraction, rectifying the N in reaction product
2, O
2, CO
x, H
2the components such as O, acetic acid, maleic anhydride are separated from vinylformic acid.Due to the characteristic that at high temperature vinylformic acid is easily polymerized, be reduce service temperature, directly can not carry out acrylic acid separation with traditional rectificating method.
At present conventionally mainly contain three kinds of different technological lines containing acrylic acid separating technology in acrylic acid mixed gas: solvent absorbing distillation technology, water absorb azeotropic distillation technology and water absorbs extraction and distillation technology.
Solvent absorbing distillation technology, advantage is that flow process is short, energy consumption is low; In order using, solvent absorbs vinylformic acid shortcoming, service temperature is high, and vinylformic acid is easily polymerized, and the cycle of operation is short.In patent CN1165808A, use the mixture of phenyl ether and biphenyl as absorption agent absorbing propenoic acid, then carry out rectifying separation and go out purer vinylformic acid, this method needs to use environmentally harmful solvent, and each step all needs to add expensive stopper and prevents acroleic acid polymerization.
Water absorbs azeotropic distillation technology, and advantage is that flow process is shorter, and investment cost is low; Shortcoming is for need use entrainer energy consumption higher, and working cost is high.Water absorbs extraction and distillation technology, and advantage is that energy consumption is low, working cost is low; Shortcoming is that the longer investment cost of flow process is high, use extraction agent, stopper consume high.
In general, adopt non-exhaust gas circulation process, use water as the Technology of absorption agent, after absorbing, the concentration of acrylic acid aqueous solution is 45-55wt%.Adopt the acroleic acid device of exhaust gas circulation process, acrylic acid aqueous solution concentration is about 63wt%.For the purification of acrylic acid aqueous solution, consider from Energy Angle, high density acrylic acid aqueous solution should adopt azeotropic distillation technique to remove water, and lower concentration acrylic acid aqueous solution adopts the technique of extraction+rectifying removal water more suitable.
Azeotropic distillation flow process is shorter, and investment cost is lower, but because Separation of Water is by being separated with vinylformic acid, so energy consumption is higher with entrainer formation azeotrope.In patent CN1865216A, propose the system be made up of four towers, use the compositional liquor of ethylcyclohexane and toluene, ethyl acetate and toluene as entrainer, be separated and obtain acrylic acid solution and acetic acid solution.In patent CN101555200A, in order to reduce the water-content in acrylic acid product, siccative is added in Distallation systm, such as acetals, keto acetals, halogenation anhydrides, isocyanates etc., these reactive drying agent and water react, finally obtain the acrylic acid product that water-content did not grasp 0.2wt%, adding of siccative adds production cost, has also manufactured trouble for follow-up process.
Extracting rectifying energy consumption is lower, but long flow path, investment cost is high, and each tower needs to add stopper and prevents acrylic acid polymerization simultaneously, and stopper add-on is more, and stopper is very expensive chemical thus increase vinylformic acid production cost.Proposing in patent CN1241892C by using extraction agent, as toluene, ethyl acetate, butylacetate, ethyl propionate etc., vinylformic acid being separated from the aqueous solution, then remove light constituent as water and acetic acid etc. by methods such as azeotropic distillations.In extraction process, the stop of vinylformic acid in equipment is longer, makes vinylformic acid more easily be polymerized and occluding device under heating status.On the other hand, no matter be azeotropic distillation and extracting rectifying process, all need to use solvent, both increase production cost and environmental protection cost.
Azeotropic distillation technique and extraction rectification technique have his own strong points, but are not desirable separation methods, and first equipment is complicated, and cost of investment is higher, simultaneously because the waste water using environmentally harmful extraction agent more with discharge, also create a lot of environmental problem.For acrylic acid separation, desirable method neither uses solvent, and simultaneously flow process is simple again, running cost and cost of investment low.
Summary of the invention
The invention provides and a kind ofly isolate the method for acrylic acid product from least one containing the gas phase mixture of acrylic precursor, by vinylformic acid cooling, absorb and the coupling of purification process, use the system of two tower compositions just can complete acrylic acid purification and recover, the water of recycle is simultaneously as absorption agent and refrigerant, do not use other solvents (extraction agent, entrainer), do not need extra make up water, avoid the pollution of solvent to environment, accomplished non-wastewater discharge yet yet.
The present invention realizes like this, a kind of process for purifying acrylic acid, the method comprises absorption tower and purification tower two tower process flow process, from vinylformic acid reactor obtain containing acrylic acid mixed gas in absorbing tower and from purification tower tower top the crude acrylic acid solution containing acetic acid and partially absorb tower the mixing of tower reactor circulation fluid after heated by interchanger after enter Ta Nei and containing acrylic acid mixed gas counter current contact, vinylformic acid in mixed gas, part acetic acid, water are cooled, and become liquid state.Not cooled vinylformic acid, acetic acid, the absorber portion of water on absorbing tower top are absorbed by the aqueous acetic acid of tower top; The acetic acid that absorption tower tower top is discharged with rare gas element and water, enter the gas cooling section at absorbing tower top, by controlling gas cooling section gas outlet temperature, the water of part and acetic acid are condensed, absorption agent as absorption tower returns in tower, the water be not condensed, acetic acid and other rare gas element, participate in except reaction ratio except a part returns vinylformic acid reactor, remaining gas is delivered to emission-control equipment and is processed; After absorption extraction, the acetic acid that reaction generates is discharged from absorption tower tower top, and tower reactor acrylic acid aqueous solution concentration reaches more than 80.0wt%; The high density acrylic acid solution containing part acetic acid and water of absorption tower tower reactor enters purification tower, and the acrylic acid solution of purification tower top gaseous phase containing acetic acid after condenser condenses returns to absorption tower as cooling fluid, as the gas coolant on absorption tower; Purification tower side line obtains vinylformic acid, and purity is greater than 99.0wt%, and tower reactor obtains the vinylformic acid heavy constituent that purity is 70.0wt%.
Being obtained through gaseous oxidation by least one acrylic precursor containing acrylic acid mixed gas described in the present invention.
Absorption tower described in the present invention is divided into absorber portion and the upper and lower two portions of cooling section.
The acrylic acid content entered in the liquid phase stream of purification tower described in the present invention is 80.0wt% ~ 87.50wt%.
Top gaseous phase logistics acrylic acid content <0.3wt% in the cooled phlegma of cooling section on the absorption tower described in the present invention.
Described in the present invention from purification tower tower side line flow out vinylformic acid be liquid form.
Described in the present invention from purification tower tower side line flow out propylene liquid acid concentration be 99.50wt% ~ 99.85wt%.
Described in the present invention from the isolated material of the tower top of purification tower be gas.
Described in the present invention from the isolated gas of the tower top of purification tower acrylic acid concentration 80.0wt% ~ 87.50wt% through cooled liquid.
Concentration 5.5wt% ~ the 10.0wt% from the isolated gas of the tower top of purification tower acetic acid through cooled liquid described in the present invention.
The present invention uses the cooling-absorption-separation system be simply made up of absorption tower and purification tower two towers, be oxidized under high-speed catalyst action in obtained acrylic precursor gas phase mixture from propylene and isolate acrylic acid product, by process of cooling, absorption process and purification process coupling, utilize the acrylic acid solution containing acetic acid as quenching medium, aqueous acetic acid carries out acrylic acid absorption as absorption agent, the acetic acid that reaction generates is separated from the tower top on absorption tower and discharges, highly purified liquid acrylic is isolated in purification tower, simultaneously the vinylformic acid that obtains after cooling of overhead gas and acetic acid mixing solutions return to absorption tower as cooling and absorption agent, in whole cooling-absorption-sepn process, water obtains recycle, do not produce waste water, do not need other solvents.Compared to current extraction rectification technique and azeotropic distillation technique, double tower cooling-absorption-separation system the equipment that the present invention relates to is few, flow process is simple, facility investment expense and working cost there is significant reduction, simultaneously the present invention also has that energy expenditure is low, auxiliary material consumes low advantage, belongs to process for cleanly preparing.
Accompanying drawing explanation
Fig. 1 is two tower process schematic flow sheets of absorption tower of the present invention and purification tower.
Fig. 2 is absorption tower of the present invention process flow diagram.
Fig. 3 is purification tower process flow diagram of the present invention.
Embodiment
The invention provides and a kind of reclaim process for purifying acrylic acid, the main ingredient in 170 DEG C of reactant gasess of vinylformic acid reactor and consisting of: N
2(70.3wt%), O
2(0.36wt%), COx(0.34wt%), vinylformic acid (13.7wt%), acetic acid (1.0wt%) and water (7.3wt%) and toxilic acid etc., wherein x equals 1 or 2; First vinylformic acid, acetic acid, part water and maleic anhydride must being cooled to liquid state by steam state during separation, then uncooled vinylformic acid, acetic acid, part water and maleic anhydride etc. being separated by absorbing from noncondensable gas.
This technique is by the coupling of absorption process and purification process, and utilize acrylic acid solution containing acetic acid as quenching medium, aqueous acetic acid carries out acrylic acid absorption as absorption agent, and the acetic acid that reaction generates discharges (see figure 1) from absorption tower tower top.Detailed process is as follows:
Main ingredient in 170 DEG C of reactant gasess of vinylformic acid reactor and consisting of: N
2(70.3wt%), O
2(0.36wt%), COx(0.34wt%), vinylformic acid (13.7wt%), acetic acid (1.0wt%) and water (7.3wt%) etc., wherein x equals 1 or 2.In absorbing tower and from purification tower tower top the crude acrylic acid solution containing acetic acid and partially absorb tower the mixing of tower reactor circulation fluid after heated by interchanger after to enter in absorption tower and containing acrylic acid mixed gas counter current contact, be cooled containing the vinylformic acid in acrylic acid mixed gas, part acetic acid, water, become liquid state.Not cooled vinylformic acid, acetic acid, the absorber portion of water on top, absorption tower are absorbed by the aqueous acetic acid of tower top,
The acetic acid that absorption tower tower top is discharged with rare gas element and water, enter the gas cooling section at top, absorption tower, by controlling gas cooling section gas outlet temperature, the water of part and acetic acid are condensed, absorption agent as absorption tower returns in tower, the water be not condensed, acetic acid and other rare gas element, participate in except reaction ratio except a part returns vinylformic acid reactor, remaining gas is delivered to emission-control equipment and is processed.After absorption extraction, the acetic acid that reaction generates is discharged from absorption tower tower top, and tower reactor acrylic acid aqueous solution concentration reaches more than 80.0wt%.
The high density acrylic acid solution containing part acetic acid and water of absorption tower tower reactor enters purification tower, and purification tower top gaseous phase returns to absorption tower as cooling fluid after condenser condenses, as the gas coolant on absorption tower.Purification tower tower side line obtains technical grade vinylformic acid, and purity is greater than 99.0wt%, and purification tower tower reactor obtains the vinylformic acid heavy constituent that purity is about 70.0wt%.Purification tower is purified except acrylic acid effect except having, and also has the effect of separating acetic acid, and the acrylic acid solution containing acetic acid of tower top returns to absorption tower, cooling and absorption reaction gas.
Below by specific embodiment, describe the present invention in detail.But should be noted that the present invention is not limited to these specific embodiments, the present invention can be widely used in the absorption removal process of different system.
Embodiment 1
The Main Function of acrylic acid absorption column is absorbing propenoic acid.Fig. 2 is shown in technical process.Absorption agent during experiment is aqueous acetic acid.Test raw material gas (composition and ratio is in table 1) is from vinylformic acid single tube reactor.Absorption tower is entered from tower bottom.Distillate simultaneously from vinylformic acid purification tower top enters absorption tower bottom filling after heating.First phegma is prepared in preparing tank, and after return tank liquid propene acid content is qualified, (<0.5wt%) uses return tank liquid return instead.Control return tank head temperature by evaporator overhead condenser cooling water flow, reach the object of partial condensation.Tower top pressure is controlled by tail gas variable valve.
By regulating tower reactor companion heat, control bottom temperature at 74 ± 1(DEG C), to be operated stable after, sampled every 1-2 hour, analyze tower reactor solution composition and top gaseous phase phlegma composition, after obtaining continuous more than 3 times identical results, every sampling analysis in 4 hours and record, until analyze containing acrylic acid dimer in tower reactor sample, device is out of service, cleans.
During device stable operation, acrylic acid content 66.7wt% ~ 69.0wt% in tower reactor solution., acrylic acid content <0.3wt% in overhead condensation liquid.
Table 1 reactant gases composition (wt%)
| N2 | COx | O2 | Propylene | Vinylformic acid | Acetic acid | Water | Toxilic acid |
| 70.3 | 0.34 | 0.36 | 0.1 | 13.7 | 1.0 | 7.3 | 0.1 |
Embodiment 2
On the basis of embodiment 1, the bottom temperature of adjustment absorption extraction tower.Control the temperature of absorption extraction tower tower reactor at 76 ± 1(DEG C), to be operated stable after, sampled every 1-2 hour, analyze tower reactor solution composition and top gaseous phase phlegma composition, after obtaining continuous more than 3 times identical results, every sampling analysis in 4 hours and record, until analyze containing acrylic acid dimer in tower reactor sample, device is out of service, cleans.
During device stable operation, acrylic acid content 73.0wt% ~ 75.24wt% in tower reactor solution, acrylic acid content <0.3wt% in overhead condensation liquid.
Embodiment 3
On the basis of embodiment 1, the bottom temperature of adjustment absorption extraction tower.Control the temperature of absorption extraction tower tower reactor at 79 ± 1(DEG C), to be operated stable after, sampled every 1-2 hour, analyze tower reactor solution composition and top gaseous phase phlegma composition, after obtaining continuous more than 3 times identical results, every sampling analysis in 4 hours and record, until analyze containing acrylic acid dimer in tower reactor sample, device is out of service, cleans.
During device stable operation, acrylic acid content 79.6wt% ~ 81.01wt% in tower reactor solution, acrylic acid content <0.3wt% in overhead condensation liquid.
Embodiment 4
On the basis of embodiment 1, the bottom temperature of adjustment absorption extraction tower.Control the temperature of absorption extraction tower tower reactor at 81 ± 1(DEG C), to be operated stable after, sampled every 1-2 hour, analyze tower reactor solution composition and top gaseous phase phlegma composition, after obtaining continuous more than 3 times identical results, every sampling analysis in 4 hours and record, until analyze containing acrylic acid dimer in tower reactor sample, device is out of service, cleans.
During device stable operation, acrylic acid content 82.94wt% ~ 84.56wt% in tower reactor solution., acrylic acid content <0.3wt% in overhead condensation liquid.
Embodiment 5
On the basis of embodiment 1, the bottom temperature on adjustment absorption tower.Control the temperature of absorption tower tower reactor at 85 ± 0.5(DEG C), to be operated stable after, sampled every 1-2 hour, analyze tower reactor solution composition and top gaseous phase phlegma composition, after obtaining continuous more than 3 times identical results, every sampling analysis in 4 hours and record, until analyze containing acrylic acid dimer in tower reactor sample, device is out of service, cleans.
During device stable operation, acrylic acid content 87.53wt% ~ 88.06wt% in tower reactor solution., acrylic acid content <0.3wt% in overhead condensation liquid.
Embodiment 6
On the basis of embodiment 1, the bottom temperature on adjustment absorption tower.Control the temperature of absorption extraction tower tower reactor at 86(DEG C), to be operated stable after, sampled every 1-2 hour, analyze tower reactor solution composition and top gaseous phase phlegma composition, after obtaining continuous more than 3 times identical results, every sampling analysis in 4 hours and record, until analyze containing acrylic acid dimer in tower reactor sample, device is out of service, cleans.
During device stable operation, acrylic acid content 88.12wt% ~ 88.24wt% in tower reactor solution., acrylic acid content >0.3wt% in overhead condensation liquid.
As can be seen from the experimental result of embodiment 1 to embodiment 6, tower reactor acrylic acid concentration raises gradually with the rising of bottom temperature, when bottom temperature controls at 85 ± 0.5 DEG C, tower reactor acrylic acid concentration reaches more than 87.0wt%, now tower top acrylic acid concentration <0.3wt%, reaches the test objective of expection.
Results contrast under the different bottom temperature of table 2
Embodiment 7
Vinylformic acid purification tower Main Function is separation of propylene acid solution phase mixture, and Fig. 3 is shown in technical process.Purification tower feed composition is in table 3.Control tower reactor rate of outflow at 1.2-1.3wt%, side take-off vinylformic acid, tower top is without backflow.
Control side line rate of outflow at 25-30wt%, sideline product acrylic acid concentration 99.84wt% ~ 99.85wt%.wt%。
Table 3 purification tower feed composition
| Project | Vinylformic acid | Acetic acid | Water | Toxilic acid |
| Composition | 87.5 | 6.3 | 6.0 | 0.2 |
Embodiment 8
On the basis of embodiment 7, adjustment side line rate of outflow.Control side line rate of outflow at 30-35wt%, sideline product acrylic acid concentration 99.78wt%.。
Embodiment 9
On the basis of embodiment 7, adjustment side line rate of outflow.Control side line rate of outflow at 35-40wt%, sideline product acrylic acid concentration 99.76wt% ~ 99.7wt%.
Embodiment 10
On the basis of embodiment 7, adjustment side line rate of outflow.Control side line rate of outflow at 42wt%, sideline product acrylic acid concentration 99.58wt%.
Embodiment 11
On the basis of embodiment 7, change purification tower feed composition (see table 4), control tower reactor rate of outflow at 1.2-1.4wt%, side take-off vinylformic acid, tower top is without backflow.
Control side line rate of outflow at 20-30wt%, sideline product acrylic acid concentration 99.78wt% ~ 99.74wt%.
Table 4 purification tower feed composition
| Project | Vinylformic acid | Acetic acid | Water | Toxilic acid |
| Composition | 85.5 | 7.3 | 7.0 | 0.2 |
Embodiment 12
On the basis of embodiment 11, adjustment side line rate of outflow.Control side line rate of outflow at 30-35wt%, sideline product acrylic acid concentration 99.64wt% ~ 99.58wt%.
Embodiment 13
On the basis of embodiment 11, adjustment side line rate of outflow.Control side line rate of outflow at 41wt%, sideline product acrylic acid concentration 99.48wt%.
As can be seen from the experimental result of embodiment 7 to embodiment 13, keep purification tower tower reactor recovery ratio constant, purity of acrylic acid product raises with the reduction of side take-off rate and the rising of overhead extraction rate.When vinylformic acid input concentration is 87.5wt%, side take-off rate is elevated to 42.0wt%, side take-off purity of acrylic acid product is 99.58wt%.When vinylformic acid input concentration is 85.5wt%, side take-off rate is 41.0wt%, and the purity of acrylic acid product of side take-off is 99.48wt%.In visible charging, acrylic acid concentration and acetate concentration have remarkably influenced to product purity.In charging, acrylic acid concentration (namely absorbing tower bottoms acrylic acid concentration) selects 87.5wt%, tower top rate of outflow (wt%): tower reactor rate of outflow (wt%): during tower side rate of outflow (wt%)=56.8:1.2:42, has obvious advantage for the quality of product and output.
When table 5 acrylic acid concentration is the feed composition of 87.5wt%, recovery ratio is on the impact of product purity
When table 6 acrylic acid concentration is the feed composition of 85.5wt%, recovery ratio is on the impact of product purity
Claims (1)
1. a process for purifying acrylic acid, it is characterized in that the method comprises absorption tower and purification tower two tower process flow process, from vinylformic acid reactor obtain containing acrylic acid mixed gas in absorbing tower and from purification tower tower top the crude acrylic acid solution containing acetic acid and partially absorb tower the mixing of tower reactor circulation fluid after heated by interchanger after enter Ta Nei and containing acrylic acid mixed gas counter current contact, vinylformic acid in mixed gas, part acetic acid, water are cooled, and become liquid state; Not cooled vinylformic acid, acetic acid, the absorber portion of water on absorbing tower top are absorbed by the aqueous acetic acid of tower top; The acetic acid that absorption tower tower top is discharged with rare gas element and water, enter the gas cooling section at absorbing tower top, by controlling gas cooling section gas outlet temperature, the water of part and acetic acid are condensed, absorption agent as absorption tower returns in tower, the water be not condensed, acetic acid and other rare gas element, participate in except reaction ratio except a part returns vinylformic acid reactor, remaining gas is delivered to emission-control equipment and is processed; After absorption extraction, the acetic acid that reaction generates is discharged from absorption tower tower top, and tower reactor acrylic acid aqueous solution concentration reaches more than 80.0wt%; The high density acrylic acid solution containing part acetic acid and water of absorption tower tower reactor enters from purification tower tower top; The acrylic acid content entered in the liquid phase stream of purification tower is 80.0wt% ~ 87.50wt%; The acrylic acid solution of purification tower top gaseous phase containing acetic acid after condenser condenses returns to absorption tower as cooling fluid, as the gas coolant on absorption tower; Purification tower side line obtains vinylformic acid, and the propylene liquid acid concentration flowed out from purification tower tower side line is 99.50wt% ~ 99.85wt%; Tower reactor obtains the vinylformic acid heavy constituent that purity is 70.0wt%; Absorption tower is divided into absorber portion and the upper and lower two portions of cooling section; Top gaseous phase logistics acrylic acid content < 0.3wt% in the cooled phlegma of cooling section on absorption tower; From the isolated gas of the tower top of purification tower acrylic acid concentration 80.0wt% ~ 87.50wt% through cooled liquid; From the concentration 5.5wt% ~ 10.0wt% of the isolated gas of the tower top of purification tower acetic acid through cooled liquid; Describedly to be obtained through gaseous oxidation by least one acrylic precursor containing acrylic acid mixed gas.
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| CN105435805B (en) * | 2014-08-18 | 2018-03-23 | 上海华谊新材料有限公司 | Catalyst, with the Catalyst Production acrylic acid and reaction system |
| CN113214075B (en) * | 2021-04-14 | 2022-10-18 | 平湖石化有限责任公司 | Device and method for producing high-quality acrylic acid |
| CN115304475A (en) * | 2021-05-08 | 2022-11-08 | 上海华谊新材料有限公司 | Method and system for purifying acrylic acid |
| CN113413626A (en) * | 2021-08-24 | 2021-09-21 | 山东蓝湾新材料有限公司 | Quenching absorption tower for preparing acrylic acid by tower top gas recirculation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1572770A (en) * | 2003-06-05 | 2005-02-02 | 株式会社日本触媒 | Method for production of acrylic acid |
| CN1902154A (en) * | 2003-11-04 | 2007-01-24 | 阿肯马公司 | Process for the purification of (meth)acrylic acid obtained from an oxidation of a gaseous substrate |
| CN101456807A (en) * | 2007-12-13 | 2009-06-17 | 上海华谊丙烯酸有限公司 | Method for producing (methyl) acrylic acid |
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| US7183428B2 (en) * | 2003-06-05 | 2007-02-27 | Nippon Shokubai Co., Inc. | Method for production of acrylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1572770A (en) * | 2003-06-05 | 2005-02-02 | 株式会社日本触媒 | Method for production of acrylic acid |
| CN1902154A (en) * | 2003-11-04 | 2007-01-24 | 阿肯马公司 | Process for the purification of (meth)acrylic acid obtained from an oxidation of a gaseous substrate |
| CN101456807A (en) * | 2007-12-13 | 2009-06-17 | 上海华谊丙烯酸有限公司 | Method for producing (methyl) acrylic acid |
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Effective date of registration: 20170120 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |