CN110465324A - A kind of preparation and application of modified SBA-15 molecular sieve - Google Patents
A kind of preparation and application of modified SBA-15 molecular sieve Download PDFInfo
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- CN110465324A CN110465324A CN201910757821.2A CN201910757821A CN110465324A CN 110465324 A CN110465324 A CN 110465324A CN 201910757821 A CN201910757821 A CN 201910757821A CN 110465324 A CN110465324 A CN 110465324A
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- molecular sieve
- sba
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 46
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 46
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims abstract description 34
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract 5
- 238000009833 condensation Methods 0.000 claims abstract 2
- 230000005494 condensation Effects 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- -1 glycerine-polyethylene Chemical group 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005882 aldol condensation reaction Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000013335 mesoporous material Substances 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- ZHUWIYQJHBMTCY-UHFFFAOYSA-N 3-[ethoxy(2,2,2-triethoxyethoxy)silyl]propan-1-amine Chemical compound NCCC[SiH](OCC(OCC)(OCC)OCC)OCC ZHUWIYQJHBMTCY-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides the preparation methods of modified SBA-15 molecular sieve, the catalyst introduces amino or carboxylic group using direct method or rear grafting on SBA-15 meso-porous molecular sieve material, which can be used for formaldehyde and propionic aldehyde condensation and prepare in the reacting of methacrolein.During the reaction, which remains solid-state, easily separates from reaction system, has the characteristics that Ke Xunhuanliyong, stability is good and is not easy to expand, and preparation process is easy, Yi Chongfu.
Description
Technical field
The invention belongs to a kind of preparation of modified SBA-15 mesoporous molecular sieve and its applications, belong to inorganic functional material preparation
And catalytic applications technical field.
Background technique
In the epoch that this advocates " Green Chemistry ", the hot spot of current catalyst area research is to prepare high efficiency, nontoxic
Harmful catalyst.Wherein ordered mesoporous material is because with adjustable aperture, pore structure abundant and the inner surface etc. for being easy to modify,
Rapidly become a research hotspot of material and biochemical industry.Mesoporous silicon oxide nanomaterial have it is from a wealth of sources, cheap,
The advantages that preferable hydrothermal stability, especially SBA-15, are the most prominent.SBA-15 contains on surface a large amount of silicone hydroxyl, but only certainly
By silicone hydroxyl just there is chemical activity, this disadvantage greatly limits the application potential of SBA-15, is needed thus to its surface
Carry out chemical modification.Using mesoporous material, so that catalyst is remained solid-state in chemical reaction, be easy to divide from liquid phase
From, can repeatedly recycle, stability is good and is not easy to expand, and the cellular structure that can easily be accommodated using mesoporous material can be into
Row shape selective catalysis.So exploitation has the characteristics that high activity and recyclable recycling, it is taken seriously.
CN106622148A discloses a kind of preparation method of modified SBA-15, it is characterised in that: with silane coupling agent and
Polyamines is modifying agent, is made after carrying out hydrothermal synthesis reaction with SBA-15.The silane coupling agent is three ethoxy of 3- chloropropyl
Base silane, 3- r-chloropropyl trimethoxyl silane, 3- aminopropyltriethoxy diethoxy silane, 3- dredge its of propyl-triethoxysilicane
Middle one kind.The polyamines be diethylamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine one of which.
CN102009983A discloses a kind of thin base modified SBA-15 molecular sieve and its preparation and application, the invention it
Thin base is distributed in SBA-15 molecular sieve pore passage inner surface in molecular sieve.Preparation method are as follows: it is water-soluble to configure thin base modifying agent ethyl alcohol
Liquid, ethanol water are 5.-60% in volumetric concentration, and it is water-soluble that SBA-15 molecular sieve is added to the thin base modifying agent ethyl alcohol configured
In liquid, stirring at normal temperature 36-48 hours, obtains and dredge base modified SBA-15 molecular sieve product.
But the modification method of foregoing invention is cumbersome, complicated for operation, and condition is harsh, causes serious pollution to the environment, preparation changes
Property material absorption property is barely satisfactory.
Summary of the invention
The present invention provides a kind of method of modifying of SBA-15 mesoporous material, method of modifying passes through optimization reaction condition and original
Material proportion, so that reaction process is mildly efficient, the modified material of preparation has preferable catalytic performance to aldol reaction, and begins
Remain eventually solid-state, be easy separate, can repeatedly recycle from liquid phase, stability it is good, widened answering for SBA-15 mesoporous material
With field and range, there is extensive market value and application prospect.
The specific preparation method of the present invention includes the following steps:
(1) polyethylene glycol glycerine-polyethylene glycol triblock polymer (P123) is made into mass fraction is 1-10%
Aqueous solution；
(2) inorganic acid and 3- cyanogen propyl diethyl oxosilane and ethyl orthosilicate (TEOS) are dissolved in step under agitation
(1) in solution, it is warming up to 20-100 DEG C, is stirred 5-40 hours；
(3) it transfers the solution into the autoclave with polytetrafluoroethyllining lining crystallization 5-30 hours at 80-150 DEG C, room
Temperature lower cooled and filtered, drying, obtain original powder mesopore molecular sieve；
(4) the original powder mesopore molecular sieve that process (3) obtains is immersed in the sulfuric acid solution that concentration is 30%-60%, 50-
It is stirred 10-40 hours at 120 DEG C, is filtered, washed, is dried, obtain the SBA-15 molecular sieve containing carboxylic group；
(5) the carboxy-modified SBA-15 molecular sieve for obtaining process (4) is immersed in toluene solution, and suitable silicon is added
Glue coupling agent KH-550 (APS) is stirred 5-10 hours at room temperature, is then filtered, washed, dries, and obtains carboxyl and amino modified
SBA-15 molecular sieve；
Wherein, the molar ratio of each component are as follows:
Inorganic acid: polyethylene glycol glycerine-polyethylene glycol triblock polymer: 3- cyanogen propyl diethyl oxosilane: positive silicon
Acetoacetic ester: water=4-6.5:0.01-0.025:X:1-X:180-200, X=0.02-0.08
The invention has the following advantages over the prior art:
1, easy to make, reaction condition is mild.
2, molecular sieve specific surface be 450-600m2/ g, average Kong Rongwei 0.9-1.0cm3/ g, average pore size 7.5-
7.6nm。
3, it is applied in the reaction of aldol condensation preparation methacrolein, the conversion ratio that can obtain propionic aldehyde is 75-95%, methyl
The selectivity of methacrylaldehyde is 60-80%, and catalyst is easily recycled, rate of recovery 80-95%.
Specific embodiment
The present invention is illustrated with embodiment below, but the scope of the present invention should not be limited by the examples.
Embodiment 1
(a) preparation of modified SBA-15 molecular sieve
The P123 of 1g is made into the aqueous solution that mass fraction is 3%, 5.75g concentrated hydrochloric acid (38%) and 0.12g3- cyanogen is added
Propyl diethyl oxosilane is warming up to 45 DEG C, stirs 40min；The TEOS of 2.08g is added dropwise, is filled after continuing stirring at 45 DEG C 18 hours
Enter 150ml in the autoclave of polytetrafluoroethyllining lining, brilliant China 22 hours at 100 DEG C, taking-up is filtered, is dried to obtain
1.3g original powder mesopore molecular sieve.
Obtained original powder mesopore molecular sieve is immersed in the sulfuric acid solution that concentration is 42%, is stirred 24 hours at 90 DEG C,
Then plus deionized water dilution vacuum filtration after, 80 DEG C drying 12 hours, obtain 0.63g mesopore molecular sieve A.
Obtained mesopore molecular sieve A is immersed in 15ml toluene solution, the APS of 0.01ml is added, it is small to stir 7 at room temperature
When；Then it is filtered, washed respectively with toluene and deionized water, is 12 hours dry at 40 DEG C, obtaining mesopore molecular sieve B；
Mesopore molecular sieve B obtained above is subjected to Analysis of Physical: specific surface 484m2/g, average Kong Rongwei
0.97cm3/g, average pore size 7.5889nm.
(b) formaldehyde is condensed reacting for preparation methacrolein with propionic aldehyde
Weigh 0.5g modified SBA-15 molecular sieve, the polymerization inhibitor of 8.7g formalin and 0.01g, under conditions of 40 DEG C,
The reaction was continued 30min after 5.98g propionic aldehyde solution is added dropwise.
(c) catalyst recycles
By after reaction catalyst filtration, it is dry after weigh quality.
Propionic aldehyde conversion ratio is defined as follows:
X (propionic aldehyde) %=[amount of the substance of 1- (amount of the substance of unreacted propionic aldehyde)/supply propionic aldehyde] * 100%
Methacrolein selectivity of product is defined as follows:
S (propionic aldehyde) %=[amount of the substance of the methacrolein of generation/(amount-of the substance of the propionic aldehyde of supply is unreacted
The amount of the substance of propionic aldehyde)] * 100%
Quality/original quality * 100% after rate of recovery %=is dry
It through gas-chromatography on-line analysis and calculates, experimental result is that the conversion ratio of propionic aldehyde is 85%, the choosing of methacrolein
Selecting property is 62%, and the rate of recovery of molecular sieve catalyst is 89%.
Embodiment 2
(a) preparation of modified SBA-15 molecular sieve
The P123 of 1g is made into the aqueous solution that mass fraction is 3.5%, 5.95g concentrated hydrochloric acid (38%) and 0.14g3- is added
Cyanogen propyl diethyl oxosilane is warming up to 45 DEG C, stirs 50min；The TEOS of 2.12g is added dropwise, after continuing stirring at 45 DEG C 18 hours
150ml is fitted into in the autoclave of polytetrafluoroethyllining lining, brilliant China 22 hours at 100 DEG C, taking-up is filtered, is dried to obtain
1.45g original powder mesopore molecular sieve.
Obtained original powder mesopore molecular sieve is immersed in the sulfuric acid solution that concentration is 42%, is stirred 24 hours at 90 DEG C,
Then plus deionized water dilution vacuum filtration after, 80 DEG C drying 12 hours, obtain 0.68g mesopore molecular sieve A.
Obtained mesopore molecular sieve A is immersed in 15ml toluene solution, the APS of 0.02ml is added, it is small to stir 7 at room temperature
When；Then it is filtered, washed respectively with toluene and deionized water, is 12 hours dry at 40 DEG C, obtaining mesopore molecular sieve B；
Mesopore molecular sieve B obtained above is subjected to Analysis of Physical: specific surface 492m2/g, average Kong Rongwei
0.97cm3/g, average pore size 7.6052nm.
The reaction for carrying out aldol condensation preparation methacrolein in the same manner as shown in Example 1, exists through gas-chromatography
Line analysis simultaneously calculates, and experimental result is that the conversion ratio of propionic aldehyde is 87%, and the selectivity of methacrolein is 65%, molecular sieve catalytic
The rate of recovery of agent is 87%.
Embodiment 3
(a) preparation of modified SBA-15 molecular sieve
The P123 of 1g is made into the aqueous solution that mass fraction is 2.5%, 5.85g concentrated hydrochloric acid (38%) and 0.13g3- is added
Cyanogen propyl diethyl oxosilane is warming up to 45 DEG C, stirs 50min；The TEOS of 2.10g is added dropwise, after continuing stirring at 45 DEG C 20 hours
150ml is fitted into in the autoclave of polytetrafluoroethyllining lining, brilliant China 24 hours at 100 DEG C, taking-up is filtered, is dried to obtain
1.35g original powder mesopore molecular sieve.
Obtained original powder mesopore molecular sieve is immersed in the sulfuric acid solution that concentration is 40%, is stirred 24 hours at 90 DEG C,
Then plus deionized water dilution vacuum filtration after, 80 DEG C drying 12 hours, obtain 0.65g mesopore molecular sieve A.
Obtained mesopore molecular sieve A is immersed in 15ml toluene solution, the APS of 0.02ml is added, it is small to stir 7 at room temperature
When；Then it is filtered, washed respectively with toluene and deionized water, is 12 hours dry at 40 DEG C, obtaining mesopore molecular sieve B；
Mesopore molecular sieve B obtained above is subjected to Analysis of Physical: specific surface 490m2/g, average Kong Rongwei
0.98cm3/g, average pore size 7.6289nm.
The reaction for carrying out aldol condensation preparation methacrolein in the same manner as shown in Example 1, exists through gas-chromatography
Line analysis simultaneously calculates, and experimental result is that the conversion ratio of propionic aldehyde is 91%, and the selectivity of methacrolein is 72%, molecular sieve catalytic
The rate of recovery of agent is 85%.
Embodiment 4
(a) preparation of modified SBA-15 molecular sieve
The P123 of 1g is made into the aqueous solution that mass fraction is 2.5%, 5.85g concentrated hydrochloric acid (38%) and 0.13g3- is added
Cyanogen propyl diethyl oxosilane is warming up to 45 DEG C, stirs 50min；The TEOS of 2.50g is added dropwise, after continuing stirring at 45 DEG C 20 hours
150ml is fitted into in the autoclave of polytetrafluoroethyllining lining, brilliant China 24 hours at 100 DEG C, taking-up is filtered, is dried to obtain
1.38g original powder mesopore molecular sieve.
Obtained original powder mesopore molecular sieve is immersed in the sulfuric acid solution that concentration is 40%, is stirred 24 hours at 90 DEG C,
Then plus deionized water dilution vacuum filtration after, 80 DEG C drying 12 hours, obtain 0.66g mesopore molecular sieve A.
Obtained mesopore molecular sieve A is immersed in 15ml toluene solution, the APS of 0.04ml is added, it is small to stir 7 at room temperature
When；Then it is filtered, washed respectively with toluene and deionized water, is 12 hours dry at 40 DEG C, obtaining mesopore molecular sieve B；
Mesopore molecular sieve B obtained above is subjected to Analysis of Physical: specific surface 498m2/g, average Kong Rongwei
0.99cm3/g, average pore size 7.6563nm.
The reaction for carrying out aldol condensation preparation methacrolein in the same manner as shown in Example 1, exists through gas-chromatography
Line analysis simultaneously calculates, and experimental result is that the conversion ratio of propionic aldehyde is 95%, and the selectivity of methacrolein is 81.5%, and molecular sieve is urged
The rate of recovery of agent is 87%.
Embodiment 5
(a) preparation of modified SBA-15 molecular sieve
The P123 of 1g is made into the aqueous solution that mass fraction is 2.5%, 5.85g concentrated hydrochloric acid (38%) and 0.15g3- is added
Cyanogen propyl diethyl oxosilane is warming up to 45 DEG C, stirs 50min；The TEOS of 2.50g is added dropwise, after continuing stirring at 45 DEG C 24 hours
150ml is fitted into in the autoclave of polytetrafluoroethyllining lining, brilliant China 24 hours at 100 DEG C, taking-up is filtered, is dried to obtain
1.38g original powder mesopore molecular sieve.
Obtained original powder mesopore molecular sieve is immersed in the sulfuric acid solution that concentration is 40%, is stirred 24 hours at 90 DEG C,
Then plus deionized water dilution vacuum filtration after, 80 DEG C drying 12 hours, obtain 0.67g mesopore molecular sieve A.
Obtained mesopore molecular sieve A is immersed in 20ml toluene solution, the APS of 0.04ml is added, it is small to stir 7 at room temperature
When；Then it is filtered, washed respectively with toluene and deionized water, is 12 hours dry at 40 DEG C, obtaining mesopore molecular sieve B；
Mesopore molecular sieve B obtained above is subjected to Analysis of Physical: specific surface 496m2/g, average Kong Rongwei
0.96cm3/g, average pore size 7.5325nm.
The reaction for carrying out aldol condensation preparation methacrolein in the same manner as shown in Example 1, exists through gas-chromatography
Line analysis simultaneously calculates, and experimental result is that the conversion ratio of propionic aldehyde is 93%, and the selectivity of methacrolein is 79%, molecular sieve catalytic
The rate of recovery of agent is 90%.
Claims (8)
1. a kind of modified SBA-15 molecular sieve catalyst for formaldehyde and propionic aldehyde condensation preparation methacrolein, feature exist
In the SBA-15 molecular sieve surface of acquisition has amino abundant and carboxylic group.
2. catalyst according to claim 1, which is characterized in that the catalyst is existed using direct method or rear grafting
Amino or carboxyl are introduced on SBA-15 molecular sieve.
3. the method according to claim 1, wherein the method for preparing catalyst includes the following steps
(1) polyethylene glycol glycerine-polyethylene glycol triblock polymer (P123) is made into aqueous solution；
(2) inorganic acid, 3- cyanogen propyl diethyl oxosilane and ethyl orthosilicate (TEOS) are mixed into the solution of step (1) and is stirred
It mixes；
(3) crystallization in the autoclave with polytetrafluoroethyllining lining or polytetrafluoroethylene (PTFE) bottle is transferred the solution into, is cooled down at room temperature
It filters afterwards, is dry, obtaining original powder mesopore molecular sieve；
(4) the original powder mesopore molecular sieve that process (3) obtains is immersed in sulfuric acid solution, is filtered, washed, is dried after stirring,
Obtain the SBA-15 molecular sieve containing carboxylic group；
(5) the carboxy-modified SBA-15 molecular sieve for obtaining process (4) is immersed in toluene solution, and it is even that suitable silica gel is added
Join agent KH-550 (APS), stirs at room temperature, be then filtered, washed, dry, obtain carboxyl and amino modified SBA-15 molecule
Sieve.
4. a kind of molecular sieve preparation method of modified SBA-15 according to claim 3, which is characterized in that the inorganic acid
One of concentrated nitric acid, the concentrated sulfuric acid or concentrated hydrochloric acid can be selected.
5. a kind of molecular sieve preparation method of modified SBA-15 according to claim 3, which is characterized in that raw materials used nothing
Machine acid, polyethylene glycol glycerine-polyethylene glycol triblock polymer, 3- cyanogen propyl diethyl oxosilane, ethyl orthosilicate and water
Molar ratio be 4-6.5:0.01-0.025:X:1-X:180-200, wherein the optional range of X be 0.01-0.1.
6. a kind of molecular sieve preparation method of modified SBA-15 according to claim 3, which is characterized in that detergent used
One of methanol, n-heptanol, ethyl alcohol, toluene, n-hexane, hexamethylene and ionized water or a variety of can be selected.
7. according to the method described in claim 3, it is characterized in that, forced air drying, vacuum drying, microwave can be selected in drying mode
Dry and spray drying, for drying temperature at 30-90 DEG C, drying time is 5-20 hours.
8. a kind of preparation method of aldol condensation preparation methacrolein, it is characterised in that: contained using described in claim 1
The SBA-15 molecular sieve catalyst of amino and carboxyl.
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| US20050049353A1 (en) * | 2003-08-27 | 2005-03-03 | Ryong Ryoo | Nanoporous organic polymer composite and preparation method thereof and its application for catalyst |
| CN102659542A (en) * | 2012-05-02 | 2012-09-12 | 中国科学院过程工程研究所 | Method for preparing methyl acrolein by catalyzing condensation of formaldehyde and propionaldehyde by utilizing ionic liquid |
| CN104475061A (en) * | 2014-12-14 | 2015-04-01 | 苏州大学 | Method for preparing mesoporous material for adsorbing heavy metal ions and dye pollutants |
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| US20050049353A1 (en) * | 2003-08-27 | 2005-03-03 | Ryong Ryoo | Nanoporous organic polymer composite and preparation method thereof and its application for catalyst |
| CN102659542A (en) * | 2012-05-02 | 2012-09-12 | 中国科学院过程工程研究所 | Method for preparing methyl acrolein by catalyzing condensation of formaldehyde and propionaldehyde by utilizing ionic liquid |
| CN104475061A (en) * | 2014-12-14 | 2015-04-01 | 苏州大学 | Method for preparing mesoporous material for adsorbing heavy metal ions and dye pollutants |
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Application publication date: 20191119 |