CN105772057B - A kind of preparation method of acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing - Google Patents
A kind of preparation method of acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
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Abstract
The invention discloses the preparation methods of a kind of acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing, including following preparation process：Using hydrothermal synthesis method synthesizing ordered mesoporous molecular sieve SBA 15；Sodium salt, boric acid and soluble in water be uniformly mixed of auxiliary agent are obtained into presoma maceration extract；Carrier S BA 15 is added in presoma maceration extract and is impregnated, mixed liquor is evaporated in a water bath, in dry in baking oven；Order mesoporous catalyst is obtained after finally roasting 2 ~ 8h at 400 ~ 600 DEG C in Muffle furnace.In catalyst preparation process of the present invention, it is not directed to hypertoxic class hazardous agents or organic solvent, condition is easily-controllable；Raw material is generally easy to get, and production cost is low, is suitble to large-scale industrial production；Catalyst prepared by the present invention is since its mesoporous orderly duct is flourishing, and soda acid bimetallic active object is high to aldol reaction catalyst activity, and selectivity is good, and catalyst stabilization performance is good.
Description
Technical field
The present invention relates to a kind of preparation processes of difunction catalyst, are synthesized more particularly, to a kind of acetic acid and formaldehyde
The preparation method of the order mesoporous catalyst of acrylic acid.
Background technology
Acrylic acid is simplest unsaturated carboxylic acid, is made of a vinyl and a carboxyl.Acrylic acid is important
Organic synthesis raw material and synthetic resin monomer, excellent polymerization and esterification ability are synthesis and the system of various fine chemicals
It is standby to provide particularly important intermediate.Acrylic acid mainly for the production of water soluble paint and adhesive comonomer propylene
Acid butyl ester and ethyl ester, and for producing super absorbent resin.Acrylicacidandesters series of products can be widely used for coating, modeling
Material, chemical fibre, weaving, many fields such as adhesive and oil.
Acrylic acid and ester experienced cyanoethanol method, REPPE since the 1930s realizes industrialized production（Lei Pu）
Method, ketenes method, acrylonitrile hydrolysis method and oxidation of propylene.4 kinds of front technique has been eliminated substantially because of Technological Economy reason.
Oxidation of propylene is the method to grow up the 1960s, is originally divided into one-step method and two-step method.After the 1980s
Newly-built and enlarging acroleic acid device is all made of propylene two-step oxidizing process.Acrylic acid production technology is mainly propylene in the world at present
Sour two-step penetration method, primary raw material are propylene.With the growing tension of petroleum resources, propylene feedstocks source is restricted, because
This develops new alternative techniques route acrylic acid synthesizing and has great importance.
In recent years with the basic product acetic acid and formaldehyde of coal chemical industry basic material synthesis gas, under the action of catalyst through aldol
Condensation reaction one-step synthesis acrylic acid becomes research hotspot.Country's acetic acid, Formaldehyde Production technology maturation at present, market excess capacity
And it is inexpensive, it, will be for domestic sluggish vinegar by aldol reaction acrylic acid synthesizing with coalification chemical product acetic acid and formaldehyde
New application direction is brought in acid, formaldehyde market, has positive effect, and the skill to the sound development of domestic acetic acid, formaldehyde market
Art route meet China's coal is more, oil less, the Chemical Industry policy advocated of the poor resource structures of gas and country.
Aldol reaction has consequence in chemical organic synthesis, using acetic acid and formaldehyde as Material synthesis propylene
Acid is a kind of typical aldol reaction, and under the effect of the catalyst, the α hydrogen atoms on acetic acid are activated and are formed first
The carbonyl of carbanion attack formaldehyde simultaneously ultimately generates acrylic acid.Either propylene aoxidizes acrylic acid process or aldol condensation processed
Acrylic acid process processed, technological core are all the exploitations of effective catalyst.Difunction catalyst is because of its more special catalysis
Effect constantly attracts people's attention in recent years, acid centre and basic center has been existed simultaneously on such catalyst, in acid
The heart can improve the selectivity of aldol reaction and reactivity is low, and opposite basic center keeps reactivity high and selective low.
Therefore the activity and selectivity of reaction can be improved simultaneously by developing suitable difunction catalyst, reach the effect of concerted catalysis
Fruit.Recent study shows that difunction catalyst is substantially better than single acid or base catalyst in aldol reaction
Catalyst effect.
Chinese patent CN102151583A and CN102161005A disclose a kind of vanadium phosphorus catalyst, and the catalyst is with vanadium phosphorus
As active component, such catalyst preparation time is long, and operating process is long and more complex, and activity is not high, and aldehydic acid is than big, efficiency
Low, simultaneously because being related to hazardous chemical mostly in its manufacturing process, being dealt with improperly in preparation process can be to environment and operation
Personnel cause damages.
Chinese patent CN102941113A discloses a kind of catalyst of methyl acetate and methylal synthesis methyl acrylate
And preparation method, the catalyst have soda acid bi-functional, but its main active matter caesium be scarce resource, it is of high cost, application by
To limitation, it is unfavorable for subsequent catalyst huge construction program industrial applications.
Mesoporous material has relatively large aperture and regular pore passage structure, is conducive to especially big point of reactant molecule
The diffusion of son and close to activated centre, the specific surface area of superelevation improves active component convenient for introducing more activated centres
Load capacity and dispersion degree.The document that comprehensive existing research prepares acrylic acid catalyst can be seen that by mesoporous material (such as
SBA-15, MCM-41, MCM-48 etc.) surface introduces the difunction catalyst that sour position and alkali position are prepared and can be applied to hydroxyl
Aldehyde condensation reaction.In relevant report, using SBA-15 as catalyst carrier, using the method for amido protecting, synthesizes and contained amino
With the bifunctional meso-porous material of sulfonic soda acid, apply in the aldol reaction of nitrobenzaldehyde and acetone, but the catalysis
Agent preparation flow is long, needs more complicated protection pre-treatment measure, and nitrobenzaldehyde and acetone reaction system and acetic acid
Formaldehyde systems are compared, and carboxylic group activity is big in acetic acid, and acetic acid formaldehyde acrylic acid synthesizing side reaction is more, therefore develops
The higher catalyst of selectivity is particularly important.
Invention content
The technical issues of solution：In view of the deficiencies of the prior art, the present invention provides a kind of acetic acid and formaldehyde to synthesize propylene
Sour order mesoporous catalyst, overcomes that existing catalyst preparation process is complicated, preparation process is related to a large amount of hazardous chemicals, catalysis
The low problem of agent activity and selectivity.
Technical solution：A kind of acetic acid and formaldehyde acrylic acid synthesizing order mesoporous catalyst, catalyst provided by the invention
Component includes main active component, auxiliary agent and carrier, and main active component is sodium salt and boric acid, the metal oxide of auxiliary agent Ti, Zr
In one kind, carrier be ordered mesoporous molecular sieve SBA-15.
A kind of preparation method of the order mesoporous catalyst of acetic acid and formaldehyde acrylic acid synthesizing provided by the invention comprising
Following preparation process：
（1）Under 40 DEG C of constant temperatures, by P123（Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer
Object）It is dissolved in hydrochloric acid solution, TEOS is added dropwise after stirring and dissolving（Ethyl orthosilicate）, then continuously stir 18-48h, it is each in solution
Material mol ratio is：TEOS: P123: HCl:H2O= 1:0.017:6:100~162；
（2）By step（1）Acquired solution moves in stainless steel water thermal crystallisation kettle, 24 ~ 72h of crystallization at 80 ~ 120 DEG C；
（3）By step（2）Gained sediment washing, suction filtration after crystallization, dry 24 ~ 48h in baking oven 80 ~ 120 DEG C；
（4）By step（3）Obtained solid roasts 4 ~ 10h in Muffle furnace at 350 ~ 650 DEG C after drying, and obtaining carrier has
Sequence mesoporous molecular sieve SBA-15；
（5）Sodium salt, boric acid and auxiliary agent are added to the water and are uniformly mixing to obtain presoma maceration extract, the sodium salt, helps boric acid
The mass ratio of agent and water is：Sodium salt:Boric acid:Auxiliary agent:Water=1 ~ 4:2~6:1:50~300；By step（4）Obtained carrier S BA-15
It is added in presoma maceration extract, 5 ~ 12h of dipping, the mass ratio of the presoma maceration extract and carrier is 5 ~ 20:1；
（6）By step（5）Obtained mixed liquor is evaporated in 70 ~ 90 DEG C of water-baths, dry 24 in baking oven 80 ~ 120 DEG C ~
48h；
（7）By step（6）Obtained solid obtains acetic acid and first after roasting 2 ~ 8h at 400 ~ 600 DEG C in Muffle furnace
The order mesoporous catalyst of aldehyde acrylic acid synthesizing.
Step（5）The sodium salt is one kind in sodium chloride, sodium carbonate, and the auxiliary agent is the metal oxide containing Ti, Zr
Middle one kind, preferably TiO2、ZrO2。
A kind of acetic acid and formaldehyde the acrylic acid synthesizing application process of order mesoporous catalyst provided by the invention, step
It is as follows：
It using fixed-bed reactor, takes order mesoporous catalyst filling in fixed bed reactors, is being filled with catalysis
The fixed bed top of agent is loaded by packing section molecular sieve filled 4A；By metaformaldehyde according to sour aldehyde molar ratio be 4:1 ratio
Acetic acid is added in example, is directly squeezed into fixed bed reactors by sampling pump after mixing, catalysis reaction velocity control 200 ~
2000h-1, through 4A molecular sieve fillings section, the depolymerization at 300 DEG C obtains high-purity formaldehyde vapor to metaformaldehyde；Formaldehyde vapor and acetic acid steam
Vapour catalyzes and synthesizes acrylic acid under 280 ~ 420 DEG C, condition of normal pressure under the action of catalyst.
Advantageous effect：（1）The present invention is not directed to hypertoxic class hazardous agents or organic solvent in catalyst preparation process,
Condition is easily controllable, and preparation process danger is small；Raw material used by catalyst preparation is generally easy to get, and production cost is low, catalyst
It is suitble to large-scale industrial production；
（2）The catalyst prepared using the present invention is since its mesoporous orderly duct is flourishing, and soda acid bimetallic active object is to hydroxyl
Aldehyde condensation catalyst activity is high, and selectivity is good, and catalyst stabilization performance is good.Using high-purity formaldehyde vapors and acetic acid through hydroxyl
Aldehyde is condensed acrylic acid processed, conversion per pass（In terms of formaldehyde）Up to 75%, selectively reach 88%.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but therefore protection scope of the present invention is not confined to
Following embodiments, 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, mainly include the following steps that：
Step 1：Under 40 DEG C of constant temperatures, 14g P123 are dissolved in the 2mol/L hydrochloric acid solutions of 420ml, stirring is molten
28g ethyl orthosilicates are slowly added dropwise after solution, then continuously stir for 24 hours.
Step 2：The solution that step 1 obtains is moved into stainless steel hydrothermal reaction kettle, crystallization is for 24 hours at 100 DEG C.
Step 3：The sediment that step 2 obtains constantly is washed, is filtered, is dried for 24 hours in baking oven 100 DEG C.
Step 4：The solid that step 3 obtains is roasted into 6h at 550 DEG C in Muffle furnace, obtains carrier ordered mesoporous molecule
Sieve SBA-15.
Step 5：By 2g sodium chloride, 4g boric acid and 2g TiO2It is dissolved in 400g water, is mixed evenly, obtain forerunner
Body maceration extract；The carrier S BA-15 that step 4 obtains is weighed 40g to be added in presoma maceration extract, impregnates 5h.
Step 6：The mixed liquor that step 5 obtains is evaporated in 80 DEG C of water-baths, the dry 36h in baking oven 100 DEG C.
Step 7：Order mesoporous urge is obtained after the solid that step 6 obtains is roasted 4h in Muffle furnace at 400 DEG C
Agent.
Step 8：The grained catalyst compression molding that step 7 is obtained sieves after broken and obtains 150 mesh particulate catalysts
Agent.
Using fixed-bed reactor, the above-mentioned catalyst fillings of 20g are weighed in fixed bed reactors, in catalyst bed
Top is loaded by packing section molecular sieve filled 4A.By metaformaldehyde according to sour aldehyde molar ratio be 4:Acetic acid is added in 1 ratio, mixes
It is directly squeezed into fixed bed reactors by sampling pump after closing uniformly, Feed space velocities 500h-1, metaformaldehyde is through 4A molecular sieve fillings
Section depolymerization at 300 DEG C obtains high-purity formaldehyde vapor.Formaldehyde vapor and acetic acid steam are under the action of catalyst in 340 DEG C of temperature
Under, acrylic acid, conversion ratio are catalyzed and synthesized under condition of normal pressure（In terms of formaldehyde）Reach 55%, acrylic acid selectivity reaches 65%.
Embodiment 2
With acetic acid and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, mainly include the following steps that：
Step 1：Under 40 DEG C of constant temperatures, 14g P123 are dissolved in the 2mol/L hydrochloric acid solutions of 420ml, stirring is molten
28g ethyl orthosilicates are slowly added dropwise after solution, then continuously stir for 24 hours.
Step 2：The solution that step 1 obtains is moved into stainless steel hydrothermal reaction kettle, crystallization is for 24 hours at 100 DEG C.
Step 3：The sediment that step 2 obtains constantly is washed, is filtered, the dry 48h in baking oven 100 DEG C.
Step 4：The solid that step 3 obtains is roasted into 6h at 550 DEG C in Muffle furnace, obtains carrier ordered mesoporous molecule
Sieve SBA-15.
Step 5：By 8g sodium carbonate, 12g boric acid and 2g ZrO2It is dissolved in 600g water, is mixed evenly, before obtaining
Drive body maceration extract；The carrier S BA-15 that step 4 obtains is weighed 40g to be added in presoma maceration extract, impregnates 5h.
Step 6：The mixed liquor that step 5 obtains is evaporated in 80 DEG C of water-baths, the dry 36h in baking oven 100 DEG C.
Step 7：Order mesoporous urge is obtained after the solid that step 6 obtains is roasted 4h in Muffle furnace at 550 DEG C
Agent.
Step 8：The grained catalyst compression molding that step 7 is obtained sieves after broken and obtains 150 mesh particulate catalysts
Agent.
Using fixed-bed reactor, the above-mentioned catalyst fillings of 20g are weighed in fixed bed reactors, in catalyst bed
Top is loaded by packing section molecular sieve filled 4A.By metaformaldehyde according to sour aldehyde molar ratio be 4:Acetic acid is added in 1 ratio, mixes
It is directly squeezed into fixed bed reactors by sampling pump after closing uniformly, Feed space velocities 800h-1, metaformaldehyde is through 4A molecular sieve fillings
Section depolymerization at 300 DEG C obtains high-purity formaldehyde vapor.Formaldehyde vapor and acetic acid steam are under the action of catalyst in 400 DEG C of temperature
Under, acrylic acid, conversion ratio are catalyzed and synthesized under condition of normal pressure（In terms of formaldehyde）Reach 46%, acrylic acid selectivity reaches 55%.
Embodiment 3
With acetic acid and the formaldehyde acrylic acid synthesizing preparation method of order mesoporous catalyst, mainly include the following steps that：
Step 1：Under 40 DEG C of constant temperatures, 14g P123 are dissolved in the 2mol/L hydrochloric acid solutions of 420ml, stirring is molten
28g ethyl orthosilicates are slowly added dropwise after solution, then continuously stir for 24 hours.
Step 2：The solution that step 1 obtains is moved into stainless steel hydrothermal reaction kettle, crystallization is for 24 hours at 100 DEG C.
Step 3：The sediment that step 2 obtains constantly is washed, is filtered, is dried for 24 hours in baking oven 100 DEG C.
Step 4：The solid that step 3 obtains is roasted into 6h at 550 DEG C in Muffle furnace, obtains carrier ordered mesoporous molecule
Sieve SBA-15.
Step 5：By 4g sodium carbonate, 8g boric acid and 4g TiO2It is dissolved in 200g water, is mixed evenly, obtain forerunner
Body maceration extract；The carrier S BA-15 that step 4 obtains is weighed 40g to be added in presoma maceration extract, impregnates 5h.
Step 6：The mixed liquor that step 5 obtains is evaporated in 80 DEG C of water-baths, the dry 48h in baking oven 100 DEG C.
Step 7：Order mesoporous urge is obtained after the solid that step 6 obtains is roasted 4h in Muffle furnace at 450 DEG C
Agent.
Step 8：The grained catalyst compression molding that step 7 is obtained sieves after broken and obtains 150 mesh particulate catalysts
Agent.
Using fixed-bed reactor, the above-mentioned catalyst fillings of 20g are weighed in fixed bed reactors, in catalyst bed
Top is loaded by packing section molecular sieve filled 4A.By metaformaldehyde according to sour aldehyde molar ratio be 4:Acetic acid is added in 1 ratio, mixes
It is directly squeezed into fixed bed reactors by sampling pump after closing uniformly, Feed space velocities 300h-1, metaformaldehyde is through 4A molecular sieve fillings
Section depolymerization at 300 DEG C obtains high-purity formaldehyde vapor.Formaldehyde vapor and acetic acid steam are under the action of catalyst in 380 DEG C of temperature
Under, acrylic acid, conversion ratio are catalyzed and synthesized under condition of normal pressure（In terms of formaldehyde）Reach 75%, acrylic acid selectivity reaches 88%.
Claims (2)
1. the preparation method of a kind of acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing, it is characterised in that including following system
Standby step：
（1）Under 40 DEG C of constant temperatures, P123 is dissolved in hydrochloric acid solution, TEOS is added dropwise after stirring and dissolving, then continuously stirs
18-48h, each material mol ratio is in solution：TEOS: P123: HCl:H2O= 1:0.017:6:(100~162)；
（2）By step（1）Acquired solution moves in stainless steel water thermal crystallisation kettle, 24 ~ 72h of crystallization at 80 ~ 120 DEG C；
（3）By step（2）Gained sediment washing, suction filtration after crystallization, dry 24 ~ 48h in baking oven 80 ~ 120 DEG C；
（4）By step（3）Obtained solid roasts 4 ~ 10h in Muffle furnace at 350 ~ 650 DEG C after drying, obtains carrier ordered Jie
Porous molecular sieve SBA-15；
（5）Sodium salt, boric acid and auxiliary agent are added to the water and are uniformly mixing to obtain presoma maceration extract, the sodium salt, boric acid, auxiliary agent and
The mass ratio of water is：Sodium salt:Boric acid:Auxiliary agent:Water=(1 ~ 4):(2~6):1:(50~300)；By step（4）What is obtained is carrier ordered
Mesoporous molecular sieve SBA-15, which is added in presoma maceration extract, impregnates 5 ~ 12h, and the mass ratio of the presoma maceration extract and carrier is
(5~20):1；
（6）By step（5）Obtained mixed liquor is evaporated in 70 ~ 90 DEG C of water-baths, dry 24 ~ 48h in baking oven 80 ~ 120 DEG C；
（7）By step（6）Obtained solid obtains acetic acid after roasting 2 ~ 8h at 400 ~ 600 DEG C in Muffle furnace and formaldehyde closes
At the order mesoporous catalyst of acrylic acid；
The sodium salt is one kind in sodium chloride, sodium carbonate；The auxiliary agent is one kind in the metal oxide of Ti, Zr, described
The metal oxide of Ti is TiO2, the metal oxide ZrO of the Zr2。
2. a kind of application process of acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing as described in claim 1,
It is characterized in that applying step is as follows：Using fixed-bed reactor, take order mesoporous catalyst filling in fixed bed reactors,
It is loaded by packing section molecular sieve filled 4A on the fixed bed top for being filled with catalyst；By metaformaldehyde according to sour aldehyde mole
Than being 4:Acetic acid is added in 1 ratio, is directly squeezed into fixed bed reactors by sampling pump after mixing, is catalyzed reaction velocity control
System is in 200 ~ 2000h-1, through 4A molecular sieve fillings section, the depolymerization at 300 DEG C obtains high-purity formaldehyde vapor to metaformaldehyde；Formaldehyde vapor
With acetic acid steam acrylic acid is catalyzed and synthesized under 280 ~ 420 DEG C, condition of normal pressure under the action of catalyst.
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| JP6770195B2 (en) | 2016-11-25 | 2020-10-14 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Method for producing unsaturated lower fatty 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 |
| 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 |
| CN108097299B (en) * | 2016-11-25 | 2020-09-04 | 中国科学院大连化学物理研究所 | Catalyst containing acid-modified molecular sieve with FER configuration and preparation method thereof |
| 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 |
| 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 |
| 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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| 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 |
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Address after: 212006 Zhen Chang Gang, Xiangshan, Zhenjiang City, Jiangsu Province Applicant after: Jiangsu Sopo (Group) Co., Ltd. Applicant after: Jiangsu Thorpe Engineering Technology Co., Ltd. Address before: 212006 Zhen Chang Gang, Xiangshan, Zhenjiang City, Jiangsu Province Applicant before: Jiangsu Sopo (Group) Co., Ltd. Applicant before: ZHENJIANG THORPE CHEMICAL ENGINEERING DESIGN CO., LTD. |
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Effective date of registration: 20191230 Address after: 212006 No. 88 Qiusuo Road, Jingkou District, Zhenjiang City, Jiangsu Province Co-patentee after: Jiangsu Thorpe Engineering Technology Co., Ltd. Patentee after: Jiangsu Sopo Chemical Co.,Ltd. Address before: Xiangshan mayor of Zhenjiang city in Jiangsu province 212006 Gang Jingkou District Co-patentee before: Jiangsu Thorpe Engineering Technology Co., Ltd. Patentee before: Jiangsu Soap (Group) Co., Ltd. |