CN106582784B - Acrylate catalyst - Google Patents
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Abstract
The present invention relates to acrylate catalyst, mainly solve the problems, such as that acrylate is selectively low in the prior art, the present invention is by using acrylate catalyst, acrylate catalyst, the catalyst is the molecular sieve through metal ion exchanged, and the metal ion is V5+、Cr3+、Mn4+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+And Bi3+At least one of technical solution, preferably solve the technical problem, can be used in the industrial production of acrylate.
Description
Technical field
The present invention relates to acrylate catalyst.
Background technique
Acrylate is important Organic Chemicals, and current main synthetic method is that propylene is successively aoxidized, is esterified
Acrylate is obtained, with biochemical industry, the technological progress in hydrogen esterification reaction of organic acid field, the source of 3- hydroxy propionate is increasingly rich
Richness, the method that 3- hydroxy propionate dehydration prepares acrylate become new feasible selection.
WO2013017904A1 (Improved Process of Dehydration Reactions) discloses hydroxyl carboxylic
The method of acid-catalyzed dehydration acrylic acid and methacrylic acid.Its catalyst used is the composite oxides active group that will contain W
Divide and load on porous carrier, carrier is selected from TiO2、SiO2、Al2O3、ZrO2And Nb2O5At least one of.As preferred
One of embodiment, catalyst activity component include the oxide of W and the oxygen selected from least one of P, Si, Mo and V element
Compound.It is preferred that carrier TiO2, or including TiO2Be selected from SiO2、Al2O3、ZrO2And Nb2O5In at least one
Kind.
But the oxide catalyst of the prior art is selected for 3- hydroxy propionate through acrylate when dehydration acrylate processed
Selecting property is low.
Summary of the invention
The first technical problem to be solved by the present invention is to be currently used for 3- hydroxy propionate dehydration to prepare acrylate anti-
The oxide catalyst the answered problem selectively low to acrylate provides a kind of new acrylate catalyst, the catalyst
Have the advantages that selectively high to acrylate.
The second technical problem to be solved by the present invention is the acrylic acid using catalyst described in one of above-mentioned technical problem
The synthetic method of ester.
One of to solve above-mentioned technical problem, technical solution of the present invention is as follows: acrylate catalyst, and the catalyst is
Molecular sieve through metal ion exchanged, the metal ion are V5+、Cr3+、Mn4+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+And Bi3+In
At least one.The even more preferably described metal ion includes being selected from Fe3+、Cu2+And Bi3+At least one of.
In above-mentioned technical proposal, the molecular sieve is preferably ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-35 molecule
At least one of sieve, Y type molecular sieve and SAPO-34.
In above-mentioned technical proposal, the molecular sieve is preferably hydrogen type molecular sieve.
In above-mentioned technical proposal, the Si:Al molar ratio in the molecular sieve is preferably 20~80.
To solve above-mentioned technical problem two, technical solution of the present invention is as follows: synthesis of conjugated carboxylic alkeneacid is included in above-mentioned
3- hydroxy propionate obtains the propylene through dehydration in the presence of catalyst described in any one technical solution of one of technical problem
Acid esters.
In above-mentioned technical proposal, reaction temperature is preferably 150 DEG C~450 DEG C；More preferable 150~300 DEG C.
In above-mentioned technical proposal, the liquid volume air speed of 3- hydroxy propionate is preferably 0.5~300h-1。
In above-mentioned technical proposal, the 3- hydroxy propionate preferably has HOCH2CH2The structure of COOR, wherein R be C1~
The organic group of C8.
In above-mentioned technical proposal, R be preferably fat-based, aryl, hetero atom replace aryl.
In above-mentioned technical proposal, R is preferably alkyl.
In above-mentioned technical proposal, R is preferably the fat-based containing O or N atom, at this point, the such as, but not limited to described fat
Base contains at least one of ehter bond, ester bond, ketone group, amido.
As unrestricted citing, the particular compound of 3- hydroxy propionate may is that 3- hydroxy methyl propionate, 3- hydroxyl
Base ethyl propionate, 3- hydracrylic acid n-propyl, 3- hydracrylic acid isopropyl ester, 3- hydracrylic acid N-butyl, 3- hydracrylic acid are different pungent
Ester.
In the present invention dehydration of 3- hydroxy propionate prepare acrylate selective calculation method it is as follows:
The acrylate amount (in mol) of selectivity=generation/conversion 3- hydroxy propionate amount (in mol)
Using the present invention, the selectivity that 3- hydroxy propionate dehydration prepares acrylate is up to 96%, has beneficial skill
Art effect, can be used in the industrial production of acrylate.
Below by specific embodiment, the present invention is described in detail.
Specific embodiment
[embodiment 1]
1, the acquisition of catalyst
Silicon source (weight concentration is 40% silica solution), silicon source (sodium metaaluminate), TBABr (tetrabutylammonium bromide) and water is mixed
Conjunction obtains mixture, with molar ratio computing, SiO in the mixture2:Al2O3:TBABr:H2O is 1.000:0.013:0.100:
50.825；With NaOH adjusting pH value to 12, stirs 20 minutes, be fitted into reaction kettle, crystallization 3 days under 170 DEG C of stirrings, chilling,
Filtering, being washed to pH value is 8,12 hours dry in 120 DEG C, and ZSM-5 original powder is made, and through 600 DEG C of Template removals, hydrogen exchange is obtained
HZSM-5.Al is added2O3, field mountain valley with clumps of trees and bamboo powder, 0.3N nitric acid (HZSM-5/Al2O3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1) extruded moulding, 80 DEG C are dry
Dry 5 hours, 500 DEG C roasted 5 hours, and sieve takes the product of 25~35 mesh as H-ZSM-5 catalyst.
Molecular sieve sial atomic molar ratio is 30 in the catalysis.
2, the synthesis of acrylate
Synthetic reaction carries out on fixed-bed reactor, and the stainless steel that the internal diameter of reactor is a length of 600mm of 12mm is anti-
Device is answered, raw material is 3- hydroxy methyl propionate, and the loadings of catalyst are 10mL, and reaction temperature is 250 DEG C, and raw material liq volume is empty
Speed is 60hr-1。
For the property of catalyst and evaluation result are listed in table 1 convenient for comparing.
[embodiment 2]
1, the acquisition of catalyst
Silicon source (weight concentration is 40% silica solution), silicon source (sodium metaaluminate), TBABr (tetrabutylammonium bromide) and water is mixed
Conjunction obtains mixture, with molar ratio computing, SiO in the mixture2:Al2O3:TBABr:H2O is 1.000:0.013:0.100:
50.825；With NaOH adjusting pH value to 12, stirs 20 minutes, be fitted into reaction kettle, crystallization 3 days under 170 DEG C of stirrings, chilling,
Filtering, being washed to pH value is 8,12 hours dry in 120 DEG C, and ZSM-5 original powder is made, and through 600 DEG C of Template removals, hydrogen exchange is obtained
HZSM-5.Al is added2O3, field mountain valley with clumps of trees and bamboo powder, 0.3N nitric acid (HZSM-5/Al2O3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1) extruded moulding, 80 DEG C are dry
Dry 5 hours, 500 DEG C roasted 5 hours, and sieve takes the product of 25~35 mesh as H-ZSM-5 catalyst.
Molecular sieve sial atomic molar ratio is 30 in the catalysis.
Above-mentioned molded molecular sieve is mixed with iron nitrate aqueous solution using equi-volume impregnating, is stored at room temperature 2 hours, is washed
It is in neutrality to cleaning solution, 120 DEG C of dryings obtain Fe in 3 hours3+Modified ZSM-5 catalyst, by weight Fe content in catalyst
It is 3%.
2, the synthesis of acrylate
Synthetic reaction carries out on fixed-bed reactor, and the stainless steel that the internal diameter of reactor is a length of 600mm of 12mm is anti-
Device is answered, raw material is 3- hydroxy methyl propionate, and the loadings of catalyst are 10mL, and reaction temperature is 250 DEG C, and raw material liq volume is empty
Speed is 60hr-1。
For the property of catalyst and evaluation result are listed in table 1 convenient for comparing.
[comparative example 1]
In addition to the catalyst roasts 5 hours for Fe therein through 650 DEG C3+It is converted into Fe2O3In addition, remaining same embodiment
1 is identical.
[embodiment 3]
1, the acquisition of catalyst
Silicon source (weight concentration is 40% silica solution), silicon source (sodium metaaluminate), TBABr (tetrabutylammonium bromide) and water is mixed
Conjunction obtains mixture, with molar ratio computing, SiO in the mixture2:Al2O3:TBABr:H2O is 1.000:0.013:0.100:
50.825；With NaOH adjusting pH value to 12, stirs 20 minutes, be fitted into reaction kettle, crystallization 3 days under 170 DEG C of stirrings, chilling,
Filtering, being washed to pH value is 8,12 hours dry in 120 DEG C, and ZSM-5 original powder is made, and through 600 DEG C of Template removals, hydrogen exchange is obtained
HZSM-5.Al is added2O3, field mountain valley with clumps of trees and bamboo powder, 0.3N nitric acid (HZSM-5/Al2O3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1) extruded moulding, 80 DEG C are dry
Dry 5 hours, 500 DEG C roasted 5 hours, and sieve takes the product of 25~35 mesh as H-ZSM-5 catalyst.
Molecular sieve sial atomic molar ratio is 30 in the catalysis.
Above-mentioned molded molecular sieve is mixed with cobalt nitrate aqueous solution using equi-volume impregnating, is stored at room temperature 2 hours, is washed
It is in neutrality to cleaning solution, 120 DEG C of dryings obtain Co in 3 hours2+Modified ZSM-5 catalyst, by weight Co content in catalyst
It is 3%.
2, the synthesis of acrylate
Synthetic reaction carries out on fixed-bed reactor, and the stainless steel that the internal diameter of reactor is a length of 600mm of 12mm is anti-
Device is answered, raw material is 3- hydroxy methyl propionate, and the loadings of catalyst are 10mL, and reaction temperature is 250 DEG C, and raw material liq volume is empty
Speed is 60hr-1。
For the property of catalyst and evaluation result are listed in table 1 convenient for comparing.
[embodiment 4]
1, the acquisition of catalyst
Silicon source (weight concentration is 40% silica solution), silicon source (sodium metaaluminate), TBABr (tetrabutylammonium bromide) and water is mixed
Conjunction obtains mixture, with molar ratio computing, SiO in the mixture2:Al2O3:TBABr:H2O is 1.000:0.013:0.100:
50.825；With NaOH adjusting pH value to 12, stirs 20 minutes, be fitted into reaction kettle, crystallization 3 days under 170 DEG C of stirrings, chilling,
Filtering, being washed to pH value is 8,12 hours dry in 120 DEG C, and ZSM-5 original powder is made, and through 600 DEG C of Template removals, hydrogen exchange is obtained
HZSM-5.Al is added2O3, field mountain valley with clumps of trees and bamboo powder, 0.3N nitric acid (HZSM-5/Al2O3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1) extruded moulding, 80 DEG C are dry
Dry 5 hours, 500 DEG C roasted 5 hours, and sieve takes the product of 25~35 mesh as H-ZSM-5 catalyst.
Molecular sieve sial atomic molar ratio is 30 in the catalysis.
Above-mentioned molded molecular sieve is mixed with aqueous bismuth nitrate solution using equi-volume impregnating, is stored at room temperature 2 hours, is washed
It is in neutrality to cleaning solution, 120 DEG C of dryings obtain Bi in 3 hours3+Modified ZSM-5 catalyst, by weight Bi content in catalyst
It is 3%.
2, the synthesis of acrylate
Synthetic reaction carries out on fixed-bed reactor, and the stainless steel that the internal diameter of reactor is a length of 600mm of 12mm is anti-
Device is answered, raw material is 3- hydroxy methyl propionate, and the loadings of catalyst are 10mL, and reaction temperature is 250 DEG C, and raw material liq volume is empty
Speed is 60hr-1。
For the property of catalyst and evaluation result are listed in table 1 convenient for comparing.
[comparative example 2]
In addition to the catalyst roasts 5 hours for Bi therein through 650 DEG C3+It is converted into Bi2O3In addition, remaining same embodiment
4 is identical.
[embodiment 5]
1, the acquisition of catalyst
Silicon source (weight concentration is 40% silica solution), silicon source (sodium metaaluminate), TBABr (tetrabutylammonium bromide) and water is mixed
Conjunction obtains mixture, with molar ratio computing, SiO in the mixture2:Al2O3:TBABr:H2O is 1.000:0.013:0.100:
50.825；With NaOH adjusting pH value to 12, stirs 20 minutes, be fitted into reaction kettle, crystallization 3 days under 170 DEG C of stirrings, chilling,
Filtering, being washed to pH value is 8,12 hours dry in 120 DEG C, and ZSM-5 original powder is made, and through 600 DEG C of Template removals, hydrogen exchange is obtained
HZSM-5.Al is added2O3, field mountain valley with clumps of trees and bamboo powder, 0.3N nitric acid (HZSM-5/Al2O3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1) extruded moulding, 80 DEG C are dry
Dry 5 hours, 500 DEG C roasted 5 hours, and sieve takes the product of 25~35 mesh as H-ZSM-5 catalyst.
Molecular sieve sial atomic molar ratio is 30 in the catalysis.
Above-mentioned molded molecular sieve is mixed with nickel nitrate aqueous solution using equi-volume impregnating, is stored at room temperature 2 hours, is washed
It is in neutrality to cleaning solution, 120 DEG C of dryings obtain Ni in 3 hours2+Modified ZSM-5 catalyst, by weight Ni content in catalyst
It is 3%.
2, the synthesis of acrylate
Synthetic reaction carries out on fixed-bed reactor, and the stainless steel that the internal diameter of reactor is a length of 600mm of 12mm is anti-
Device is answered, raw material is 3- hydroxy methyl propionate, and the loadings of catalyst are 10mL, and reaction temperature is 250 DEG C, and raw material liq volume is empty
Speed is 60hr-1。
For the property of catalyst and evaluation result are listed in table 1 convenient for comparing.
[embodiment 6]
1, the acquisition of catalyst
Silicon source (weight concentration is 40% silica solution), silicon source (sodium metaaluminate), TBABr (tetrabutylammonium bromide) and water is mixed
Conjunction obtains mixture, with molar ratio computing, SiO in the mixture2:Al2O3:TBABr:H2O is 1.000:0.013:0.100:
50.825；With NaOH adjusting pH value to 12, stirs 20 minutes, be fitted into reaction kettle, crystallization 3 days under 170 DEG C of stirrings, chilling,
Filtering, being washed to pH value is 8,12 hours dry in 120 DEG C, and ZSM-5 original powder is made, and through 600 DEG C of Template removals, hydrogen exchange is obtained
HZSM-5.Al is added2O3, field mountain valley with clumps of trees and bamboo powder, 0.3N nitric acid (HZSM-5/Al2O3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1) extruded moulding, 80 DEG C are dry
Dry 5 hours, 500 DEG C roasted 5 hours, and sieve takes the product of 25~35 mesh as H-ZSM-5 catalyst.
Molecular sieve sial atomic molar ratio is 30 in the catalysis.
Above-mentioned molded molecular sieve is mixed with copper nitrate aqueous solution using equi-volume impregnating, is stored at room temperature 2 hours, is washed
It is in neutrality to cleaning solution, 120 DEG C of dryings obtain Cu in 3 hours2+Modified ZSM-5 catalyst, by weight Cu content in catalyst
It is 3%.
2, the synthesis of acrylate
Synthetic reaction carries out on fixed-bed reactor, and the stainless steel that the internal diameter of reactor is a length of 600mm of 12mm is anti-
Device is answered, raw material is 3- hydroxy methyl propionate, and the loadings of catalyst are 10mL, and reaction temperature is 250 DEG C, and raw material liq volume is empty
Speed is 60hr-1。
For the property of catalyst and evaluation result are listed in table 1 convenient for comparing.
[comparative example 3]
In addition to the catalyst roasts 5 hours for Cu therein through 650 DEG C2+It is converted into other than CuO, remaining is the same as embodiment 6
It is identical.
[embodiment 7]
1, the acquisition of catalyst
Silicon source (weight concentration is 40% silica solution), silicon source (sodium metaaluminate), TBABr (tetrabutylammonium bromide) and water is mixed
Conjunction obtains mixture, with molar ratio computing, SiO in the mixture2:Al2O3:TBABr:H2O is 1.000:0.013:0.100:
50.825；With NaOH adjusting pH value to 12, stirs 20 minutes, be fitted into reaction kettle, crystallization 3 days under 170 DEG C of stirrings, chilling,
Filtering, being washed to pH value is 8,12 hours dry in 120 DEG C, and ZSM-5 original powder is made, and through 600 DEG C of Template removals, hydrogen exchange is obtained
HZSM-5.Al is added2O3, field mountain valley with clumps of trees and bamboo powder, 0.3N nitric acid (HZSM-5/Al2O3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1) extruded moulding, 80 DEG C are dry
Dry 5 hours, 500 DEG C roasted 5 hours, and sieve takes the product of 25~35 mesh as H-ZSM-5 catalyst.
Molecular sieve sial atomic molar ratio is 30 in the catalysis.
Above-mentioned molded molecular sieve is mixed with zinc nitrate aqueous solution using equi-volume impregnating, is stored at room temperature 2 hours, is washed
It is in neutrality to cleaning solution, 120 DEG C of dryings obtain Zn in 3 hours2+Modified ZSM-5 catalyst, by weight Zn content in catalyst
It is 3%.
2, the synthesis of acrylate
Synthetic reaction carries out on fixed-bed reactor, and the stainless steel that the internal diameter of reactor is a length of 600mm of 12mm is anti-
Device is answered, raw material is 3- hydroxy methyl propionate, and the loadings of catalyst are 10mL, and reaction temperature is 250 DEG C, and raw material liq volume is empty
Speed is 60hr-1。
For the property of catalyst and evaluation result are listed in table 1 convenient for comparing.
The metal ion-modified catalyst obtained by ion exchange, reaction selectivity are apparently higher than unmodified urge
Agent, and the catalyst of the metal oxide modified roasted after ion exchange, reaction selectivity is significantly lower than unmodified
Catalyst.
Table 1
| Catalyst | 3- hydroxy methyl propionate conversion ratio, % | Methyl acrylate selectivity, % | |
| Embodiment 1 | H-ZSM-5 | 90.1% | 84.7% |
| Embodiment 2 | H-ZSM-5/Fe3+ | 90.5% | 95.2% |
| Comparative example 1 | H-ZSM-5/Fe2O3 | 85.6% | 79.0% |
| Embodiment 3 | H-ZSM-5/Co2+ | 89.7% | 85.1% |
| Embodiment 4 | H-ZSM-5/Bi3+ | 91.4% | 96.7% |
| Comparative example 2 | H-ZSM-5/Bi2O3 | 86.3% | 80.5% |
| Embodiment 5 | H-ZSM-5/Ni2+ | 90.2% | 85.2% |
| Embodiment 6 | H-ZSM-5/Cu2+ | 90.8% | 94.6% |
| Comparative example 3 | H-ZSM-5/CuO | 84.9% | 80.1% |
| Embodiment 7 | H-ZSM-5/Zn2+ | 90.5% | 85.3% |
Claims (8)
1. a kind of synthetic method of acrylate, 3- hydroxy propionate is obtained through dehydration in the presence of being included in acrylate catalyst
The acrylate；The acrylate catalyst is the molecular sieve through metal ion exchanged, and the metal ion is Fe3+、Cu2 +And Bi3+At least one of, molecular sieve is after ion exchange without calcination process.
2. synthetic method according to claim 1, it is characterized in that the molecular sieve is ZSM-5 molecular sieve, ZSM-11 points
At least one of sub- sieve, ZSM-35 molecular sieve, Y type molecular sieve and SAPO-34.
3. synthetic method according to claim 1, it is characterized in that the Si:Al molar ratio in the molecular sieve is 20~80.
4. synthetic method according to claim 1, it is characterized in that the liquid volume air speed of 3- hydroxy propionate be 0.5~
300h-1。
5. synthetic method according to claim 1, it is characterized in that the 3- hydroxy propionate has HOCH2CH2The knot of COOR
Structure, wherein R is the organic group of C1~C8.
6. synthetic method according to claim 5, it is characterized in that the aryl that R is fat-based, aryl, hetero atom replace.
7. synthetic method according to claim 6, it is characterized in that R is alkyl.
8. synthetic method according to claim 6, feature R is the fat-based containing O or N atom.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594263A (en) * | 2004-06-24 | 2005-03-16 | 复旦大学 | Method for preparing acrylic acid and its esters |
| CN101186576A (en) * | 2007-11-26 | 2008-05-28 | 南京工业大学 | Preparation method of acrylic ester |
| CN101703944A (en) * | 2009-11-13 | 2010-05-12 | 江苏工业学院 | Molecular sieve modified catalyst, preparation method and application thereof to preparation of acrylic ester |
| CN104159883A (en) * | 2012-03-07 | 2014-11-19 | 麦兰特公司 | Preparation of alpha, beta-unsaturated carboxylic acids and esters thereof |
-
2015
- 2015-10-14 CN CN201510662105.8A patent/CN106582784B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594263A (en) * | 2004-06-24 | 2005-03-16 | 复旦大学 | Method for preparing acrylic acid and its esters |
| CN101186576A (en) * | 2007-11-26 | 2008-05-28 | 南京工业大学 | Preparation method of acrylic ester |
| CN101703944A (en) * | 2009-11-13 | 2010-05-12 | 江苏工业学院 | Molecular sieve modified catalyst, preparation method and application thereof to preparation of acrylic ester |
| CN104159883A (en) * | 2012-03-07 | 2014-11-19 | 麦兰特公司 | Preparation of alpha, beta-unsaturated carboxylic acids and esters thereof |
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| "过渡金属离子交换分子筛催化空气氧化环己醇制备环己酮";牛宗辉，等;《湖北大学学报(自然科学版)》;20120930;第276-278页 * |
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