CN105498832B - The preparation method of the catalyst of 1,2- epoxy butane is prepared for 1- butylene epoxidation - Google Patents
The preparation method of the catalyst of 1,2- epoxy butane is prepared for 1- butylene epoxidation Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of catalyst for epoxidation 1- butylene preparation 1,2- epoxy butane, and template is added in solvent, is stirred at 20~100 DEG C, and it is 2-9 that suitable acid for adjusting pH, which is added,；Silicon source and titanium source are mixed to join to scale in above-mentioned solution, by solution, crystallization obtains gel mixed liquor under stiring；Gel mixed liquor 12h~48h is stood at 40~100 DEG C；Separating gel product obtains white solid precipitating, after washing and drying, obtains the original powder of catalyst, and then at Muffle kiln roasting, obtained catalyst is in the method for epoxidation 1- butylene.The present invention solves that traditional butylene epoxidation catalyst activity is lower, and titanium source utilization rate is low, low, the not high disadvantage of epoxy butane product yield of selectivity.It avoids because titanium source hydrolysis causes to be formed by the shortcomings that active constituent has been lost in Ti -Si zeolite, is efficiently used for epoxidation 1- butylene preparation 1,2- epoxy butane.
Description
Technical field
The present invention relates to a kind of methods of the catalyst preparation of epoxidation 1- butylene.
Background technique
China's 1- butylene be mainly derived from ethylene unit and refinery catalytic cracking device by-product C 4 fraction and ethylene dimerization and
, with the development that MTBE (methyl tertiary butyl ether(MTBE)) synthesizes, 1- butylene and MTBE combined production device are more and more.China 1- fourth at present
Alkene production capacity is up to 120,000 tons/year, by 1- butenc be important organic chemical industry's intermediate epoxy butane be improve product
Added value efficiently uses the bold imagination of 1- butylene.
The industrial production more successful method of epoxides mainly has chlorohydrination and conjugated oxidation, and chlorohydrination technique is relatively answered
With extensive, but a large amount of waste water are generated in process of production, energy consumption is high, pollution environment；Conjugated oxidation is mainly in epoxidation propylene side
Face shows advantage more outstanding, not yet has been reported that the production for epoxy butane.Patent CN101348472A discloses one
The method that kind is used to prepare epoxides, by using organic amine as template, using organic alcohol and water as solvent, in indifferent gas
Under atmosphere by grafting inorganic titanium into silicon dioxide skeleton.Although obtaining preferable catalytic activity by improving mass transfer effect,
It is the easy autohemagglutination of reactant in reaction process, effective product yield is relatively low, it is often more important that post-processing of this method in catalyst
In carried out silanization treatment, lead to catalyst preparation process is tedious complicated, repeatability is lower.
Patent CN1418876A is carried on alumina support by the Titanium Sieve Molecular Sieve for synthesizing hydro-thermal method, in catalyst
Middle addition alkali and alkaline earth metal ions oxide component, obtains higher reactivity and selectivity, but this method is only applicable in
In using hydrogen peroxide as oxidant, when selecting common CHP as oxidant, effect is undesirable；Further, since this method is
Active component is carried on alumina support, active component is unavoidably caused to be easy the problem of being lost.And this method is urged
It, can not be by the optimal degree of catalytic activity raising still without solving the problems, such as that organic titanium source hydrolyzes in agent preparation process.
Summary of the invention
The mesoporous molecular sieve catalyst that the present invention uses alcohol process for thermosynthesizing to obtain, for epoxidation 1- butylene preparation 1,2-
Epoxy butane has good catalytic activity, hence it is evident that better than traditional hydrothermal synthesis method.Deionized water is replaced using organic solvent
The molecular sieve catalyst that titanium silicon ordered arrangement is prepared as solvent carries out evaluating catalyst in 5ml continuous tubular reactor
Test, reaction pressure 2.0MPa, 80 DEG C of reaction temperature, the yield of reaction product epoxy butane is up to 90% or so, is better than patent
Catalyst described in CN1418876A.
Catalyst involved in the present invention has using the more alkyl polyoxyethylene ethers of nonionic surface active agent as template
Machine silicon source and titanium source are synthesized at specific pH, and detailed process is as follows:
(1) template is added in solvent, is stirred at 20~100 DEG C, and it is 2-9 that acid for adjusting pH, which is added,；
(2) silicon source and titanium source are mixed to join to scale in above-mentioned solution, by solution, crystallization is obtained under stiring
Gel mixed liquor；
(3) gel mixed liquor 12h~48h is stood at 40~100 DEG C；
(4) separating gel product obtains white solid precipitating, after washing and drying, obtains the original powder of catalyst, then
In Muffle kiln roasting, obtained catalyst is in the method for epoxidation 1- butylene
The wherein mass ratio of each material of the raw material are as follows: silicon source/titanium source=10~150, organic solvent/silicon source=5-10,
Template/silicon source=0.5-1.4.
Step (4) the Muffle kiln roasting obtains titanium-silicone metapore molecular sieve (powder in 350~800 DEG C of roasting 5h or more
Shape), after extrusion or compression molding, it is ground into required granularityIt obtains in the present invention and is used for epoxidation 1-
The titanium-silicon molecular sieve catalyst of butylene.
The titanium source of catalyst is tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid orthocarbonate, butyl titanate, four isopropyl of metatitanic acid
One of ester；Or inorganic ti sources are one of titanium tetrachloride, titanium tetrabromide, titanium tetra iodide.
Catalyst silicon source is one of quanmethyl silicate, tetraethyl orthosilicate, silicic acid orthocarbonate.
The solvent of titanium source and silicon source is dissolved for one in ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, cyclohexanol
Kind.
One of dilute sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, hydrofluoric acid regulation system acidity is added.
Template is more alkyl polyoxyethylene ethers, is dodecyl polyoxyethylene ether, cetyl polyoxyethylene ether and ten
One of eight alkyl polyoxyethylene ethers.
The present invention has the advantage that
(1) method used in the present invention has a significant effect for epoxidation 1- butylene, and reaction condition is mild, target
Product yield high；
(2) present invention with organic solvent process for thermosynthesizing directly prepare it is regular orderly, large specific surface area, Ti content it is big
Mesoporous molecular sieve catalyst, catalytic effect are better than conventional method.
(3) present invention crystallizes the later period in molecular sieve catalyst, and insertion stands step, gives sufficient amorphous ti silica polymerization
Time, the good inner hole of diffusivity is formed, activated centre is more.
(4) replace water to avoid the hydrolysis of butyl titanate with organic solvent dehydrated alcohol in the synthesis process, ensure that
The utilization rate of titanium source.
Specific embodiment
Specific embodiment catalyticing research: the epoxidation assessment that catalyst involved in this method is used for 1- butylene is urged
The reactivity of agent.For the ease of comparing reaction, deionization water as solvent preparation reference catalyst and inorganic titanium is respectively adopted
Source prepares reference catalyst.
(1) template is added in solvent, is stirred at 20~100 DEG C, and it is 2-9 that acid for adjusting pH, which is added,；
(2) silicon source and titanium source are mixed to join to scale in above-mentioned solution, by solution, crystallization is obtained under stiring
Gel mixed liquor；
(3) gel mixed liquor 12h~48h is stood at 40~100 DEG C；
(4) separating gel product obtains white solid precipitating, after washing and drying, obtains the original powder of catalyst, then
In Muffle kiln roasting, obtained catalyst is in the method for epoxidation 1- butylene
The wherein mass ratio of each material of the raw material are as follows: silicon source/titanium source=10~150, organic solvent/silicon source=5-10,
Template/silicon source=0.5-1.4.
Step (4) the Muffle kiln roasting obtains titanium-silicone metapore molecular sieve (powder in 350~800 DEG C of roasting 5h or more
Shape), after extrusion or compression molding, it is ground into required granularityIt obtains in the present invention and is used for epoxidation 1-
The titanium-silicon molecular sieve catalyst of butylene.
Gel separates the filter of vacuum available pumping, and drying can carry out in baking oven, and roasting can be in Muffle furnace under air atmosphere
It carries out, to remove the template on mesopore molecular sieve.The pH can be with dilute sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid or hydrofluoric acid in thunder magnetic
Accurate pH meter instruction is lower to be adjusted；Wherein the silicon source be organo-silicon ester compound, organo-silicon ester compound can for quanmethyl silicate,
Tetraethyl orthosilicate or silicic acid orthocarbonate；Wherein the organic solvent can be methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, uncle
Butanol or cyclohexanol；Wherein the titanium source is organic titanium ester compounds or inorganic titanium compound, and the organic titanium can be different for metatitanic acid
Propyl ester or butyl titanate, the inorganic titanium are titanium trichloride, titanium tetrachloride or titanium sulfate；Wherein the template is dodecyl
Polyoxyethylene ether, cetyl polyoxyethylene ether and Steareth.
[embodiment 1]
23.0g ethyl orthosilicate, 1.0g butyl titanate, 20.3g dodecyl polyoxyethylene ether are weighed respectively；By 24.5g
Dodecyl polyoxyethylene ether stirring and dissolving is in 100ml dehydrated alcohol, heating stirring 1h；To three mouthfuls under stirring
23.0g ethyl orthosilicate is slowly added in flask dropwise；4.0 butyl titanates are slowly added to after half of h dropwise, are finally not added anhydrous
Ethyl alcohol is to 220ml.It is 2.0 with the pH that thunder magnetic pH meter measures reaction system, control temperature stirs for 24 hours at 75 DEG C.Cooling is quiet
Crystallized product is isolated after setting 3 h；After 110 DEG C of dryings, 550 DEG C of roasting 6h, obtain titanium-silicon molecular sieve catalyst in Muffle furnace
Original powder.
Take 20~40 mesh particle packings to catalyst test apparatus Titanium Sieve Molecular Sieve original powder tabletting obtained above screening
In fixed bed reactors, carry out catalyst investigation.The Relative mole content of each component in catalyst preparation process:
SiO2/TiO2=32 templates/SiO2=0.37
[embodiment 2]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 3]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 2g.
The Relative mole content of component are as follows:
SiO2/TiO2=16 templates/SiO2=0.37
[embodiment 4]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 5]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 6.0.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 6]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 9.0.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 7]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 45 DEG C.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 8]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 9]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 100 DEG C.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 10]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, and dodecyl polyoxyethylene ether takes 5.49g.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.1
[embodiment 11]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, and dodecyl polyoxyethylene ether takes 43.9g.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.8
[embodiment 12]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, solvent absolute ethyl alcohol 145ml.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 13]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, solvent absolute ethyl alcohol 290ml.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 14]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, and solvent selects normal propyl alcohol.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 15]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, and solvent selects n-butanol.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 16]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, and solvent selects the tert-butyl alcohol.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 17]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Butyl titanate takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C, and solvent selects cyclohexanol.
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[embodiment 18]
Titanium Sieve Molecular Sieve the preparation method is the same as that of Example 1 operation.Tetramethoxy titanate ester takes 1.4g, pH to be adjusted to 2.0, stirring temperature
Degree is set as 80 DEG C.Solvent selects isopropanol
The Relative mole content of component are as follows:
SiO2/TiO2=23 templates/SiO2=0.37
[comparative example 1]
Ethyl orthosilicate 20.0g, butyl titanate 1.0g, dodecyl polyoxyethylene ether 20.3g, ethyl alcohol 6.7ml are weighed,
Deionized water 300ml.Dodecyl polyoxyethylene ether is dissolved in deionized water in 500ml three-necked flask, 65 DEG C of water-bath
Heating stirring 1h, adjusting pH is 2.45, and ethyl orthosilicate is injected while being vigorously stirred；It is added after stirring 0.5h and is dissolved in nothing
The butyl titanate of water-ethanol, heating stirring is for 24 hours at 70 DEG C.It is washed with deionized after standing cooling, and isolates crystallization and produce
Object；Most of moisture is dried and removed at 110 DEG C, then 350 DEG C of hours of high-temperature roasting in Muffle furnace, 550 DEG C of 4 hours,
Titanium Sieve Molecular Sieve original powder is obtained, takes 20~40 mesh particles to be packed into the fixed bed reactors of catalyst test apparatus after tabletting and examines
Look into catalytic activity and selectivity.
The Relative mole content of component are as follows:
SiO2/TiO2=32 templates/SiO2=0.37
[comparative example 2]
Typical experimental procedure includes tetraethyl orthosilicate dissolution for deionized water aqueous solution, and accompanies by mild stir
It mixes.The ethanol solution (mixing ten minutes at room temperature to uniformly) of n-hexadecyl polyoxyethylene ether is added later, then adjusts
PH=2.45 is saved, 75 DEG C is heated and stirs 24 hours.It is washed with deionized after standing cooling, and isolates crystallized product；110
DEG C most of moisture is dried and removed, impregnates the ethanol solution of titanium tetrachloride to saturation state；Muffle furnace high-temperature roasting forms titanium silicon
Oxide crystal.
[embodiment 19~36]
Catalyst made from above-mentioned each embodiment 1~18 is carried out on catalyst test apparatus to 1- butylene epoxy respectively
Change reaction to investigate.Its evaluation condition are as follows: using the isopropylbenzene containing 10~30%CHP as oxidant, reaction pressure 2.0MPa, instead
Answer temperature control at 80.0 DEG C, loaded catalyst 5ml, molar ratio (CHP/1- butylene) 0.05~1.Feed rate: 1- fourth
Alkene (liquid)=0.5~5ml/min, CHP (30%)=0.5~3ml/min.Average reaction result is taken to comment as catalyst performance
Valence mumber evidence, reaction result are shown in Table 1.
[comparative example 3~4]
The catalyst of comparative example 1~2 is checked and rated according to embodiment 19~35, reaction result is shown in Table 1
One 1- butylene epoxidation reaction result of table
As it can be seen from table 1 the catalyst prepared using alcohol thermal synthesis method involved in the present invention, with cumyl hydroperoxide
For oxidant, successfully (80 DEG C and 2.0Mpa) turns to 1- butylene epoxy in epoxy butane under low-temp low-pressure, raw material conversion
Rate can reach 92.8%, and the selectivity of epoxy butane reaches as high as 88.9%, hence it is evident that better than in reference catalyst.It can be seen that should
The activity of catalyst preferably, has achieved the purpose that effectively prevent butylene autohemagglutination side reaction have preferable technical effect.
Claims (4)
1. one kind prepares the preparation method of the catalyst of 1,2 epoxy butanes, the catalyst being directed to for epoxidation 1- butylene
Specific preparation process is as follows:
(1) template is added in solvent, solvent is ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, one in cyclohexanol
Kind, template is more alkyl polyoxyethylene ethers, is dodecyl polyoxyethylene ether, cetyl polyoxyethylene ether and octadecyl
One of polyoxyethylene ether stirs at 20~100 DEG C, and it is 2-9 that suitable acid for adjusting pH, which is added,；
(2) silicon source and titanium source are mixed to join to scale in above-mentioned solution, by solution, crystallization obtains gel under stiring
Mixed liquor stands gel mixed liquor 12h~48h at 40~100 DEG C；
(3) separating gel product obtains white solid precipitating, after washing and drying, the original powder of catalyst is obtained, then at horse
Not kiln roasting, obtained catalyst are used for epoxidation 1- butylene epoxidation reaction；
The mass ratio of each material are as follows: silicon source/titanium source be 10~150, solvent/silicon source be 5~10, template/silicon source be 0.5~
1.4。
2. method for preparing catalyst according to claim 1, it is characterised in that the titanium source of catalyst is tetramethoxy titanate ester, metatitanic acid
One of tetra-ethyl ester, metatitanic acid orthocarbonate, butyl titanate, tetraisopropyl titanate；Or inorganic ti sources are titanium tetrachloride, tetrabormated
One of titanium, titanium tetra iodide.
3. method for preparing catalyst according to claim 1, it is characterised in that catalyst silicon source is quanmethyl silicate, silicic acid four
One of ethyl ester, silicic acid orthocarbonate.
4. method for preparing catalyst according to claim 1, it is characterised in that be added dilute sulfuric acid, hydrochloric acid, phosphoric acid, boric acid,
One of hydrofluoric acid regulation system acidity.
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| CN107930610B (en) * | 2017-11-29 | 2019-09-20 | 万华化学集团股份有限公司 | A kind of preparation method of olefin epoxidation catalysts and the catalyst thus prepared |
| CN109020927A (en) * | 2018-09-07 | 2018-12-18 | 南京合之盛化工科技有限公司 | A kind of production method of epoxy butane |
| CN109675566A (en) * | 2019-01-30 | 2019-04-26 | 兰州城市学院 | A kind of order mesoporous catalyst of Co-Ti bimetallic and its preparation method and application |
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| US20010025008A1 (en) * | 1999-06-01 | 2001-09-27 | Yatao Hu | Titanium on silica catalysts with controlled distributions |
| US20030152510A1 (en) * | 2001-11-15 | 2003-08-14 | Ernest Senderov | TS-PQ titano-silicate molecular sieves and methods for synthesis and use thereof |
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| CN104098532A (en) * | 2014-07-18 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing epoxybutane through butene epoxidation |
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| US20010025008A1 (en) * | 1999-06-01 | 2001-09-27 | Yatao Hu | Titanium on silica catalysts with controlled distributions |
| US20030152510A1 (en) * | 2001-11-15 | 2003-08-14 | Ernest Senderov | TS-PQ titano-silicate molecular sieves and methods for synthesis and use thereof |
| CN101012063A (en) * | 2007-02-07 | 2007-08-08 | 中国日用化学工业研究院 | Method for preparing titanium-containing molecular sieve |
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