CN105772057A - Preparation method of ordered mesoporous catalyst for synthesizing acrylic acid by acetic acid and methanol - Google Patents
Preparation method of ordered mesoporous catalyst for synthesizing acrylic acid by acetic acid and methanol Download PDFInfo
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Abstract
The invention discloses a preparation method of an ordered mesoporous catalyst for synthesizing acrylic acid by acetic acid and methanol. The preparation method includes synthesizing ordered mesoporous molecular sieves SBA-15 according to a hydrothermal synthesis method; dissolving sodium salt, boric acid and assistant in water and mixing evenly to obtain precursor steeping liquor; adding the carrier SBA-15 into the precursor steeping liquor for steeping, evaporating the mixed liquor in water bath to dryness, and putting the mixed liquor in a drying oven; baking the mixed liquor in a muffle furnace at the temperature of 400-600 DEG C for 2-8 hours to obtain the ordered mesoporous catalyst. The preparation method has the advantages that toxic hazard reagents or organic solvents are not used during catalyst preparation, and conditions are easy to control; raw materials are easy to get, production cost is low, and the preparation method is suitable for industrial mass production; due to well-developed ordered mesoporous passages of the prepared catalyst, the catalyst activity of acid-base thermometal active matter to aldol reaction is high, and selectivity and catalyst stability are also high.
Description
Technical field
The present invention relates to the preparation technology of a kind of difunction catalyst, especially relate to the preparation method of the order mesoporous catalyst of a kind of acetic acid and formaldehyde acrylic acid synthesizing.
Background technology
Acrylic acid is simplest unsaturated carboxylic acid, is made up of a vinyl and a carboxyl.Acrylic acid is important organic synthesis raw material and synthetic resin monomer, the polymerization of its excellence and esterification ability, and the synthesis for various fine chemicals provides particularly important intermediate with preparation.Acrylic acid is mainly for the production of the comonomer butyl acrylate of water soluble paint and adhesive and ethyl ester, and is used for producing super absorbent resin.Acrylicacidandesters series of products can be widely used for a lot of fields such as coating, plastics, chemical fibre, weaving, binding agent, and oil.
Acrylic acid and ester, since the thirties in 20th century realizes industrialized production, experienced by cyanoethanol method, REPPE(thunder general) method, ketenes method, acrylonitrile hydrolysis method and oxidation of propylene.Above 4 kinds of technique is eliminated the most substantially because of Technological Economy reason.Oxidation of propylene is the method grown up the sixties in 20th century, is originally divided into one-step method and two-step method.After the eighties in 20th century, newly-built and enlarging acroleic acid device all uses propylene two-step oxidizing process.Acrylic acid production technology is mainly acrylic acid two-step penetration method the most in the world, and its primary raw material is propylene.Along with the growing tension of petroleum resources, propylene feedstocks source is restricted, and therefore develops new alternative techniques route acrylic acid synthesizing and has great importance.
In recent years with basic product acetic acid and the formaldehyde of Coal Chemical Industry basic material synthesis gas, under catalyst action, become study hotspot through aldol reaction one-step synthesis acrylic acid.Current domestic acetic acid, Formaldehyde Production technology maturation, market production capacity surplus and inexpensive, with Coal Chemical Industry product acetic acid and formaldehyde, through aldol reaction acrylic acid synthesizing, new application direction is brought in acetic acid, the formaldehyde market for domestic depression, the sound development of domestic acetic acid, formaldehyde market is had positive effect, and this technology path meets China's coal is many, oily less, gas is lean resource structures and the Chemical Industry policy that country advocates.
Aldol reaction has consequence in chemistry organic synthesis, it is a kind of typical aldol reaction for Material synthesis acrylic acid with acetic acid and formaldehyde, under the effect of catalyst, first the α hydrogen atom on acetic acid is activated and forms the carbonyl of carbanion attack formaldehyde and ultimately generate acrylic acid.Either propylene aoxidizes acrylic acid process processed or aldol condensation acrylic acid process, and its technological core is all the exploitation of effective catalyst.Difunction catalyst the most constantly causes the attention of people because of its more special catalytic action, there are acid centre and basic center on such catalyst simultaneously, acid centre can improve the selectivity of aldol reaction and reactivity is low, and contrary basic center makes reactivity high and selectivity is low.Therefore develop suitable difunction catalyst and can improve activity and the selectivity of reaction simultaneously, reach the effect of concerted catalysis.Recent study shows, in aldol reaction, difunction catalyst is substantially better than the catalyst effect of single acid or base catalyst.
Chinese patent CN102151583A and CN102161005A discloses a kind of vanadium phosphorus catalyst, this catalyst is using vanadium phosphorus as active component, such catalyst preparation time is long, operating process length is the most complicated, activity is the highest, and aldehydic acid is than big, and efficiency is low, simultaneously because its manufacturing process relates to hazardous chemical mostly, deal with improperly in preparation process and environment and operator can be worked the mischief.
Chinese patent CN102941113A discloses a kind of methyl acetate and the catalyst of methylal synthesis acrylic acid methyl ester. and preparation method, this catalyst has soda acid bi-functional, but its main active matter caesium is scarce resource, cost is high, its application is restricted, and is unfavorable for subsequent catalyst huge construction program industrial applications.
Mesoporous material has relatively large aperture and regular pore passage structure, be conducive to reactant molecule particularly macromole diffusion and close to active center, the specific surface area of its superelevation, it is simple to introduce more active center, improves load capacity and the dispersion of active component.The document of comprehensive existing research preparation acrylic acid catalyst is it can be seen that can be applicable to aldol reaction by the difunction catalyst being prepared from introducing acid position, mesoporous material (such as SBA-15, MCM-41, MCM-48 etc.) surface and alkali position.In relevant report; with SBA-15 as catalyst carrier; the method using amido protecting; synthesize containing amino and the bifunctional meso-porous material of sulfonic soda acid; apply in the aldol reaction of nitrobenzaldehyde and acetone; but this catalyst preparation flow is long; need complex protection pre-treatment measure; and nitrobenzaldehyde and acetone reaction system are with acetic acid formaldehyde systems comparatively speaking; in acetic acid, carboxylic group activity is big; acetic acid formaldehyde acrylic acid synthesizing side reaction is more, and the catalyst that therefore exploitation selectivity is higher is particularly important.
Summary of the invention
Solve the technical problem that: for the deficiencies in the prior art, the invention provides a kind of acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing, overcome that existing catalyst preparation process is numerous and diverse, preparation process relates to a large amount of hazardous chemical, the problem that catalyst activity and selectivity is low.
Technical scheme: a kind of acetic acid of present invention offer and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing, catalytic component includes main active component, auxiliary agent and carrier, main active component is sodium salt and boric acid, auxiliary agent is the one in the metal-oxide of Ti, Zr, and carrier is ordered mesoporous molecular sieve SBA-15.
A kind of acetic acid that the present invention provides and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it includes following preparation process:
(1) under 40 DEG C of constant temperatures, by P123(poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer) it is dissolved in hydrochloric acid solution, TEOS(tetraethyl orthosilicate is dripped after stirring and dissolving), then continuous stirring 18-48h, in solution, each material mol ratio is: TEOS:
P123: HCl:H2O= 1:0.017:6:100~162；
(2) step (1) gained solution is moved in stainless steel water thermal crystallisation still, crystallization 24 ~ 72h at 80 ~ 120 DEG C；
(3) by the washing of gained precipitate, sucking filtration after step (2) crystallization, in baking oven, 24 ~ 48h at 80 ~ 120 DEG C, it is dried；
(4) by dried for step (3) gained solid in Muffle furnace at 350 ~ 650 DEG C roasting 4 ~ 10h, obtain carrier ordered mesoporous molecular sieve SBA-15；
(5) sodium salt, boric acid and auxiliary agent being added to the water and be uniformly mixing to obtain presoma impregnation liquid, the mass ratio of described sodium salt, boric acid, auxiliary agent and water is: sodium salt: boric acid: auxiliary agent: water=1 ~ 4:2 ~ 6:1:50 ~ 300；Carrier S BA-15 step (4) obtained adds in presoma impregnation liquid, impregnates 5 ~ 12h, and the mass ratio of described presoma impregnation liquid and carrier is 5 ~ 20:1；
(6) mixed liquor that step (5) obtains is evaporated in 70 ~ 90 DEG C of water-baths, in baking oven, at 80 ~ 120 DEG C, is dried 24 ~ 48h；
(7) solid step (6) obtained i.e. obtains acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing in Muffle furnace at 400 ~ 600 DEG C after roasting 2 ~ 8h.
Step (5) described sodium salt is the one in sodium chloride, sodium carbonate, and described auxiliary agent is a kind of in the metal-oxide containing Ti, Zr, preferably TiO2、ZrO2。
A kind of acetic acid of present invention offer and the formaldehyde acrylic acid synthesizing application process of order mesoporous catalyst, its step is as follows:
Use fixed-bed reactor, take order mesoporous catalyst filling in fixed bed reactors, load by packing section molecular sieve filled for 4A on the fixed bed top being filled with catalyst；According to the ratio that acid aldehyde mol ratio is 4:1, metaformaldehyde being added acetic acid, is directly squeezed in fixed bed reactors by sampling pump after mix homogeneously, catalytic reaction air speed controls at 200 ~ 2000h-1, metaformaldehyde obtains high-purity formaldehyde vapor through the depolymerization at 300 DEG C of 4A molecular sieve filling section；Formaldehyde vapor and acetic acid steam under catalyst action in 280 ~ 420 DEG C, catalyze and synthesize acrylic acid under condition of normal pressure.
Beneficial effect: (1) present invention, in catalyst preparation process, is not directed to severe toxicity class hazardous agents or organic solvent, and condition is easily controllable, and preparation process danger is little；Catalyst is prepared used raw material and is generally easy to get, and production cost is low, and catalyst is suitable for large-scale industrial production；
(2) utilizing catalyst prepared by the present invention due to its mesoporous orderly duct prosperity, soda acid bimetallic active thing is high to aldol reaction catalyst activity, and selectivity is good, and catalyst stabilization performance is good.Using high-purity formaldehyde vapors and acetic acid through aldol condensation acrylic acid, its conversion per pass (in terms of formaldehyde) up to 75%, selectivity reaches 88%.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore protection scope of the present invention is confined to following embodiment, but limited by description and claims of this specification.
Embodiment 1
With acetic acid and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it mainly comprises the steps that
Step one: under 40 DEG C of constant temperatures, by 14g
P123 is dissolved in the 2mol/L hydrochloric acid solution of 420ml, is slowly added dropwise 28g tetraethyl orthosilicate, subsequently continuous stirring 24h after stirring and dissolving.
Step 2: solution step one obtained moves to rustless steel hydrothermal reaction kettle, crystallization 24h at 100 DEG C.
Step 3: precipitate step 2 obtained constantly is washed, sucking filtration, is dried 24h in baking oven at 100 DEG C.
Step 4: solid step 3 obtained roasting 6h at 550 DEG C in Muffle furnace, obtains carrier ordered mesoporous molecular sieve SBA-15.
Step 5: by 2g sodium chloride, 4g boric acid and 2g TiO2It is dissolved in 400g water, mixing and stirring, obtains presoma impregnation liquid；Carrier S BA-15 step 4 obtained weighs 40g and adds in presoma impregnation liquid, impregnates 5h.
Step 6: mixed liquor step 5 obtained is evaporated in 80 DEG C of water-baths, is dried 36h in baking oven at 100 DEG C.
Step 7: solid step 6 obtained i.e. obtains order mesoporous catalyst in Muffle furnace at 400 DEG C after roasting 4h.
Step 8: grained catalyst compression molding step 7 obtained, after crushing, screening obtains 150 mesh granular catalysts.
Use fixed-bed reactor, weigh the above-mentioned catalyst filling of 20g in fixed bed reactors, load by packing section molecular sieve filled for 4A on beds top.According to the ratio that acid aldehyde mol ratio is 4:1, metaformaldehyde being added acetic acid, is directly squeezed in fixed bed reactors by sampling pump after mix homogeneously, Feed space velocities is 500h-1, metaformaldehyde obtains high-purity formaldehyde vapor through the depolymerization at 300 DEG C of 4A molecular sieve filling section.Formaldehyde vapor and acetic acid steam at a temperature of 340 DEG C, catalyze and synthesize acrylic acid under catalyst action under condition of normal pressure, conversion ratio (in terms of formaldehyde) reaches 55%, and acrylic acid selectivity reaches 65%.
Embodiment 2
With acetic acid and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it mainly comprises the steps that
Step one: under 40 DEG C of constant temperatures, by 14g
P123 is dissolved in the 2mol/L hydrochloric acid solution of 420ml, is slowly added dropwise 28g tetraethyl orthosilicate, subsequently continuous stirring 24h after stirring and dissolving.
Step 2: solution step one obtained moves to rustless steel hydrothermal reaction kettle, crystallization 24h at 100 DEG C.
Step 3: precipitate step 2 obtained constantly is washed, sucking filtration, is dried 48h in baking oven at 100 DEG C.
Step 4: solid step 3 obtained roasting 6h at 550 DEG C in Muffle furnace, obtains carrier ordered mesoporous molecular sieve SBA-15.
Step 5: by 8g sodium carbonate, 12g boric acid and 2g ZrO2It is dissolved in 600g water, mixing and stirring, obtains presoma impregnation liquid；Carrier S BA-15 step 4 obtained weighs 40g and adds in presoma impregnation liquid, impregnates 5h.
Step 6: mixed liquor step 5 obtained is evaporated in 80 DEG C of water-baths, is dried 36h in baking oven at 100 DEG C.
Step 7: solid step 6 obtained i.e. obtains order mesoporous catalyst in Muffle furnace at 550 DEG C after roasting 4h.
Step 8: grained catalyst compression molding step 7 obtained, after crushing, screening obtains 150 mesh granular catalysts.
Use fixed-bed reactor, weigh the above-mentioned catalyst filling of 20g in fixed bed reactors, load by packing section molecular sieve filled for 4A on beds top.According to the ratio that acid aldehyde mol ratio is 4:1, metaformaldehyde being added acetic acid, is directly squeezed in fixed bed reactors by sampling pump after mix homogeneously, Feed space velocities is 800h-1, metaformaldehyde obtains high-purity formaldehyde vapor through the depolymerization at 300 DEG C of 4A molecular sieve filling section.Formaldehyde vapor and acetic acid steam at a temperature of 400 DEG C, catalyze and synthesize acrylic acid under catalyst action under condition of normal pressure, conversion ratio (in terms of formaldehyde) reaches 46%, and acrylic acid selectivity reaches 55%.
Embodiment 3
With acetic acid and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it mainly comprises the steps that
Step one: under 40 DEG C of constant temperatures, by 14g
P123 is dissolved in the 2mol/L hydrochloric acid solution of 420ml, is slowly added dropwise 28g tetraethyl orthosilicate, subsequently continuous stirring 24h after stirring and dissolving.
Step 2: solution step one obtained moves to rustless steel hydrothermal reaction kettle, crystallization 24h at 100 DEG C.
Step 3: precipitate step 2 obtained constantly is washed, sucking filtration, is dried 24h in baking oven at 100 DEG C.
Step 4: solid step 3 obtained roasting 6h at 550 DEG C in Muffle furnace, obtains carrier ordered mesoporous molecular sieve SBA-15.
Step 5: by 4g sodium carbonate, 8g boric acid and 4g TiO2It is dissolved in 200g water, mixing and stirring, obtains presoma impregnation liquid；Carrier S BA-15 step 4 obtained weighs 40g and adds in presoma impregnation liquid, impregnates 5h.
Step 6: mixed liquor step 5 obtained is evaporated in 80 DEG C of water-baths, is dried 48h in baking oven at 100 DEG C.
Step 7: solid step 6 obtained i.e. obtains order mesoporous catalyst in Muffle furnace at 450 DEG C after roasting 4h.
Step 8: grained catalyst compression molding step 7 obtained, after crushing, screening obtains 150 mesh granular catalysts.
Use fixed-bed reactor, weigh the above-mentioned catalyst filling of 20g in fixed bed reactors, load by packing section molecular sieve filled for 4A on beds top.According to the ratio that acid aldehyde mol ratio is 4:1, metaformaldehyde being added acetic acid, is directly squeezed in fixed bed reactors by sampling pump after mix homogeneously, Feed space velocities is 300h-1, metaformaldehyde obtains high-purity formaldehyde vapor through the depolymerization at 300 DEG C of 4A molecular sieve filling section.Formaldehyde vapor and acetic acid steam at a temperature of 380 DEG C, catalyze and synthesize acrylic acid under catalyst action under condition of normal pressure, conversion ratio (in terms of formaldehyde) reaches 75%, and acrylic acid selectivity reaches 88%.
Claims (5)
1. an acetic acid and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it is characterised in that include following preparation process:
(1) under 40 DEG C of constant temperatures, being dissolved in hydrochloric acid solution by P123, drip TEOS, then continuous stirring 18-48h after stirring and dissolving, in solution, each material mol ratio is: TEOS:P123:HCl:H2O=
1:0.017:6:100~162；
(2) step (1) gained solution is moved in stainless steel water thermal crystallisation still, crystallization 24 ~ 72h at 80 ~ 120 DEG C；
(3) by the washing of gained precipitate, sucking filtration after step (2) crystallization, in baking oven, 24 ~ 48h at 80 ~ 120 DEG C, it is dried；
(4) by dried for step (3) gained solid in Muffle furnace at 350 ~ 650 DEG C roasting 4 ~ 10h, obtain carrier ordered mesoporous molecular sieve SBA-15；
(5) sodium salt, boric acid and auxiliary agent being added to the water and be uniformly mixing to obtain presoma impregnation liquid, the mass ratio of described sodium salt, boric acid, auxiliary agent and water is: sodium salt: boric acid: auxiliary agent: water=1 ~ 4:2 ~ 6:1:50 ~ 300；Carrier ordered mesoporous molecular sieve SBA-15 step (4) obtained adds dipping 5 ~ 12h in presoma impregnation liquid, and the mass ratio of described presoma impregnation liquid and carrier is 5 ~ 20:1；
(6) mixed liquor that step (5) obtains is evaporated in 70 ~ 90 DEG C of water-baths, in baking oven, at 80 ~ 120 DEG C, is dried 24 ~ 48h；
(7) solid step (6) obtained i.e. obtains acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing in Muffle furnace at 400 ~ 600 DEG C after roasting 2 ~ 8h.
A kind of acetic acid the most according to claim 1 and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it is characterised in that step (5) described sodium salt is the one in sodium chloride, sodium carbonate.
A kind of acetic acid the most according to claim 1 and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it is characterised in that step (5) described auxiliary agent is the one in the metal-oxide of Ti, Zr.
A kind of acetic acid the most according to claim 3 and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, it is characterised in that the metal-oxide of described Ti is TiO2, the metal-oxide ZrO of described Zr2。
A kind of acetic acid the most as claimed in claim 1 and the formaldehyde acrylic acid synthesizing application process of order mesoporous catalyst, it is characterized in that applying step is as follows: use fixed-bed reactor, take order mesoporous catalyst filling in fixed bed reactors, load by packing section molecular sieve filled for 4A on the fixed bed top being filled with catalyst；According to the ratio that acid aldehyde mol ratio is 4:1, metaformaldehyde being added acetic acid, is directly squeezed in fixed bed reactors by sampling pump after mix homogeneously, catalytic reaction air speed controls at 200 ~ 2000h-1, metaformaldehyde obtains high-purity formaldehyde vapor through the depolymerization at 300 DEG C of 4A molecular sieve filling section；Formaldehyde vapor and acetic acid steam under catalyst action in 280 ~ 420 DEG C, catalyze and synthesize acrylic acid under condition of normal pressure.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018094687A1 (en) * | 2016-11-25 | 2018-05-31 | 中国科学院大连化学物理研究所 | Method for preparing low-grade unsaturated fatty acid ester |
| CN108097297A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of catalyst for being used to prepare unsaturated acids or unsaturated acid ester |
| CN108101769A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of technique for preparing olefin(e) acid and/or olefin(e) acid ester |
| CN108101770A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that regeneration prepares the catalyst of unsaturated acids or unsaturated acid ester |
| CN108097299A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of catalyst of molecular sieve with FER configuration modified containing acid and preparation method thereof |
| CN108380201A (en) * | 2018-03-05 | 2018-08-10 | 江苏索普（集团）有限公司 | Solid acid catalyst for aldol condensation acrylic acid and preparation method thereof and application method |
| CN114605252A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for preparing methacrylic acid and methyl ester thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4677225A (en) * | 1984-05-21 | 1987-06-30 | Toagosei Chemical Industry Co., Ltd. | Process for the production of acrylic acid or methacrylic acid |
| CN103230789A (en) * | 2013-04-27 | 2013-08-07 | 江门谦信化工发展有限公司 | Preparation method of nanometer solid super base catalyst applied to synthesis of acrylic acid by utilizing acetic acid and formaldehyde |
| CN103801280A (en) * | 2014-01-26 | 2014-05-21 | 上海华谊（集团）公司 | Cs-supported silica-based catalyst and preparation method and application thereof |
| CN105324172A (en) * | 2013-06-26 | 2016-02-10 | 罗门哈斯公司 | Process for production of methacrylic acid esters |
-
2016
- 2016-05-05 CN CN201610291252.3A patent/CN105772057B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4677225A (en) * | 1984-05-21 | 1987-06-30 | Toagosei Chemical Industry Co., Ltd. | Process for the production of acrylic acid or methacrylic acid |
| CN103230789A (en) * | 2013-04-27 | 2013-08-07 | 江门谦信化工发展有限公司 | Preparation method of nanometer solid super base catalyst applied to synthesis of acrylic acid by utilizing acetic acid and formaldehyde |
| CN105324172A (en) * | 2013-06-26 | 2016-02-10 | 罗门哈斯公司 | Process for production of methacrylic acid esters |
| CN103801280A (en) * | 2014-01-26 | 2014-05-21 | 上海华谊（集团）公司 | Cs-supported silica-based catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| O.H. BAILEY ET AL.: "Methacrylic acid synthesis I. Condensation of propionic acid with formaldehyde over alkali metal cation on silica catalysts", 《APPLIED CATALYSIS A: GENERAL》 * |
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| WO2018094687A1 (en) * | 2016-11-25 | 2018-05-31 | 中国科学院大连化学物理研究所 | Method for preparing low-grade unsaturated fatty acid ester |
| CN108097297A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of catalyst for being used to prepare unsaturated acids or unsaturated acid ester |
| CN108101769A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of technique for preparing olefin(e) acid and/or olefin(e) acid ester |
| CN108101770A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that regeneration prepares the catalyst of unsaturated acids or unsaturated acid ester |
| CN108097299A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of catalyst of molecular sieve with FER configuration modified containing acid and preparation method thereof |
| CN108101770B (en) * | 2016-11-25 | 2020-05-05 | 中国科学院大连化学物理研究所 | Method for regenerating catalyst for preparing unsaturated acid or unsaturated acid ester |
| CN108101769B (en) * | 2016-11-25 | 2020-08-11 | 中国科学院大连化学物理研究所 | Process for preparing olefine acid and/or olefine acid ester |
| CN108097297B (en) * | 2016-11-25 | 2020-09-04 | 中国科学院大连化学物理研究所 | Catalyst for preparing unsaturated acid or unsaturated acid ester |
| US10919832B2 (en) | 2016-11-25 | 2021-02-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing low-grade unsaturated fatty acid ester |
| CN108380201A (en) * | 2018-03-05 | 2018-08-10 | 江苏索普（集团）有限公司 | Solid acid catalyst for aldol condensation acrylic acid and preparation method thereof and application method |
| CN114605252A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for preparing methacrylic acid and methyl ester thereof |
| CN114605252B (en) * | 2020-12-09 | 2023-05-26 | 中国科学院大连化学物理研究所 | Method for preparing methacrylic acid and methyl ester thereof |
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