CN105498832A - Preparation method for catalyst used for preparing 1,2-epoxybutane through epoxidation of 1-butene - Google Patents
Preparation method for catalyst used for preparing 1,2-epoxybutane through epoxidation of 1-butene Download PDFInfo
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Abstract
The invention relates to a preparation method for a catalyst used for preparing 1,2-epoxybutane through epoxidation of 1-butene. The preparation method comprises adding a template into a solvent, stirring at 20-100 DEG C, and adding proper amount of an acid to adjust pH to 2-9; mixing a silicon source and a titanium source according to a prescribed ratio, adding into the above solution, and crystallizing the solution with stirring, so as to obtain a gel mixed solution; standing the gel mixed solution at 40-100 DEG C for 12 h-48 h; and separating the gel product to obtain a white solid precipitate, performing washing and drying to obtain a catalyst raw powder, then roasting in muffle furnace, so as to obtain the catalyst applied to epoxidation of 1-butene. The method solves the disadvantages that a conventional butene epoxidation catalyst is relatively low in activity, low in titanium-source utilization rate, low in selectivity and not high in epoxybutane product yield. The method avoids the disadvantage that active compositions in the formed silicon-titanium molecular sieve lose due to hydrolysis of the titanium source, and is effectively applied to prepare 1,2-epoxybutane through epoxidation of 1-butene.
Description
Technical field
The present invention relates to a kind of method of catalyst preparing of epoxidation 1-butylene.
Background technology
China's 1-butylene is mainly derived from ethylene unit and refinery catalytic cracking device by-product C 4 fraction and ethylene dimerization and obtains, the development of synthesizing along with MTBE (methyl tertiary butyl ether(MTBE)), and 1-butylene and MTBE combined production device get more and more.Current China 1-butylene production capacity is up to 120,000 tons/year, and to be important organic chemical industry's intermediate epoxy butane by 1-butenc be improves added value of product, effectively utilizes the bold imagination of 1-butylene.
The more successful method of industrial production epoxides mainly contains chlorohydrination and conjugated oxidation, and chlorohydrination technique is comparatively widely used, but produces a large amount of waste water in process of production, and energy consumption is large, contaminated environment; Conjugated oxidation mainly shows comparatively outstanding advantage in epoxidation propylene, not yet has report for the production of epoxy butane.Patent CN101348472A discloses a kind of method for the preparation of epoxides, by adopt organic amine as template, with organic alcohol and water for solvent, under an inert atmosphere by grafting inorganic titanium in silicon dioxide skeleton.Although obtain good catalytic activity by improving mass transfer effect, but the easy autohemagglutination of reactant in course of reaction, effective product yield is on the low side, the more important thing is that the method has carried out silanization treatment in the post processing of catalyst, cause catalyst preparing operation very complicated, repeatability is lower.
Patent CN1418876A is by being carried on alumina support by the HTS of water heat transfer, add alkali and alkaline earth metal ions oxide component in the catalyst, obtain higher reactivity and selective, but the method is only applicable to take hydrogen peroxide as oxidant, when selecting conventional CHP as oxidant, effect is undesirable; In addition, due to the method just by active constituent loading on alumina support, unavoidably cause the problem that active component easily runs off.And still do not solve the problem of organic titanium source hydrolysis in the method catalyst preparation process, the degree of the best that catalytic activity cannot be improved.
Summary of the invention
The mesoporous molecular sieve catalyst that the present invention adopts alcohol process for thermosynthesizing to obtain, prepares 1,2-epoxy butane for epoxidation 1-butylene, has good catalytic activity, be obviously better than traditional hydrothermal synthesis method.Organic solvent is adopted to replace deionized water to prepare the molecular sieve catalyst of titanium silicon ordered arrangement as solvent, Catalyst Evaluation Test is carried out in 5ml continuous tubular reactor, reaction pressure 2.0MPa, reaction temperature 80 DEG C, the yield of product epoxy butane, up to about 90%, is better than the catalyst described in patent CN1418876A.
Catalyst involved in the present invention is with the many alkyl polyoxyethylene ethers of nonionic surface active agent for template, and organosilicon source and titanium source are synthesized under specific pH, and detailed process is as follows:
(1) template is added in solvent, stir at 20 ~ 100 DEG C, and to add acid for adjusting pH be 2-9;
(2) silicon source and titanium source are mixed to join in above-mentioned solution to scale, by solution under agitation crystallization obtain gel mixed liquor;
(3) at 40 ~ 100 DEG C, gel mixed liquor 12h ~ 48h is left standstill;
(4) separating gel product, obtains white solid precipitation, after washing and drying, obtains the former powder of catalyst, then roasting in Muffle furnace, and obtained catalyst is used in the method for epoxidation 1-butylene
The mass ratio of each material of wherein said raw material is: silicon source/titanium source=10 ~ 150, organic solvent/silicon source=5-10, template/silicon source=0.5-1.4.
In described step (4) Muffle furnace, roasting is at 350 ~ 800 DEG C of more than roasting 5h, obtains titanium-silicone metapore molecular sieve (powdery), after extrusion or compression molding, is ground into required granularity
namely the titanium-silicon molecular sieve catalyst for epoxidation 1-butylene in obtained the present invention.
The titanium source of catalyst is the one in metatitanic acid four methyl esters, tetraethyl titanate, metatitanic acid orthocarbonate, butyl titanate, tetraisopropyl titanate; Or inorganic ti sources is the one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide.
Catalyst silicon source is the one in quanmethyl silicate, tetraethyl orthosilicate, silicic acid orthocarbonate.
The solvent in dissolving titanium source and silicon source is the one in ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, the tert-butyl alcohol, cyclohexanol.
Add a kind of regulation system acidity in dilute sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, hydrofluoric acid.
Template is many alkyl polyoxyethylene ethers, is the one in alkylpolyoxyethylene, ceteth and Steareth.
Tool of the present invention has the following advantages:
(1) method used in the present invention has a significant effect for epoxidation 1-butylene, and reaction condition is gentle, and target product yield is high;
(2) the present invention's organic solvent process for thermosynthesizing directly prepare regular in order, specific area is large, Ti content is large mesoporous molecular sieve catalyst, catalytic effect is better than conventional method.
(3) the present invention is in the molecular sieve catalyst crystallization later stage, inserts stating step, gives sufficient amorphous ti silica polymerization time, and form the endoporus that diffusivity is good, activated centre is more.
(4) in building-up process, replace with organic solvent absolute ethyl alcohol the hydrolysis that water avoids butyl titanate, ensure that the utilization rate in titanium source.
Detailed description of the invention
Detailed description of the invention catalyticing research: reactivity catalyst involved in the method being used for the epoxidation assessment catalyst of 1-butylene.For the ease of comparing reaction, deionization water as solvent is adopted to prepare reference catalyst respectively and inorganic ti sources prepares reference catalyst.
(1) template is added in solvent, stir at 20 ~ 100 DEG C, and to add acid for adjusting pH be 2-9;
(2) silicon source and titanium source are mixed to join in above-mentioned solution to scale, by solution under agitation crystallization obtain gel mixed liquor;
(3) at 40 ~ 100 DEG C, gel mixed liquor 12h ~ 48h is left standstill;
(4) separating gel product, obtains white solid precipitation, after washing and drying, obtains the former powder of catalyst, then roasting in Muffle furnace, and obtained catalyst is used in the method for epoxidation 1-butylene
The mass ratio of each material of wherein said raw material is: silicon source/titanium source=10 ~ 150, organic solvent/silicon source=5-10, template/silicon source=0.5-1.4.
In described step (4) Muffle furnace, roasting is at 350 ~ 800 DEG C of more than roasting 5h, obtains titanium-silicone metapore molecular sieve (powdery), after extrusion or compression molding, is ground into required granularity
namely the titanium-silicon molecular sieve catalyst for epoxidation 1-butylene in obtained the present invention.
Gel is separated vacuum available pump suction filtration, and drying can be carried out in baking oven, and roasting can be carried out in Muffle furnace under air atmosphere, to remove the template on mesopore molecular sieve.Described pH can use dilute sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid or hydrofluoric acid to regulate under the accurate pH meter instruction of thunder magnetic; Wherein said silicon source is organo-silicon ester compound, and organo-silicon ester compound can be quanmethyl silicate, tetraethyl orthosilicate or silicic acid orthocarbonate; Wherein said organic solvent can be methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, the tert-butyl alcohol or cyclohexanol; Wherein said titanium source is organic titanium ester compounds or inorganic titanium compound, and described organic titanium can be isopropyl titanate or butyl titanate, and described inorganic titanium is titanium trichloride, titanium tetrachloride or titanium sulfate; Wherein said template is alkylpolyoxyethylene, ceteth and Steareth.
[embodiment 1]
Take 23.0g ethyl orthosilicate respectively, 1.0g butyl titanate, 20.3g alkylpolyoxyethylene; By 24.5g alkylpolyoxyethylene stirring and dissolving in 100ml absolute ethyl alcohol, add thermal agitation 1h; Dropwise 23.0g ethyl orthosilicate is slowly added in the there-necked flask be under stirring; Dropwise slowly add 4.0 butyl titanates after half h, finally do not add absolute ethyl alcohol to 220ml.The pH measuring reaction system with thunder magnetic pH meter is 2.0, and control temperature stirs 24h at 75 DEG C.Cooling isolates crystallized product after leaving standstill 3 h; After 110 DEG C of dryings, 550 DEG C of roasting 6h in Muffle furnace, obtain the former powder of titanium-silicon molecular sieve catalyst.
Former for HTS obtained above powder compressing tablet screening is got 20 ~ 40 order particle packings to the fixed bed reactors in catalyst test apparatus, carries out catalyst investigation.The Relative mole content of each component in catalyst preparation process:
SiO
2/ TiO
2=32 templates/SiO
2=0.37
[embodiment 2]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 3]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 2g.
The Relative mole content of component is:
SiO
2/ TiO
2=16 templates/SiO
2=0.37
[embodiment 4]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 5]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 6.0.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 6]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 9.0.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 7]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 45 DEG C.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 8]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 9]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 100 DEG C.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 10]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, and alkylpolyoxyethylene gets 5.49g.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.1
[embodiment 11]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, and alkylpolyoxyethylene gets 43.9g.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.8
[embodiment 12]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, solvent absolute ethyl alcohol 145ml.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 13]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, solvent absolute ethyl alcohol 290ml.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 14]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, and normal propyl alcohol selected by solvent.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 15]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, and n-butanol selected by solvent.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 16]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, and the tert-butyl alcohol selected by solvent.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 17]
The preparation method of HTS operates with embodiment 1.Butyl titanate gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C, and cyclohexanol selected by solvent.
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[embodiment 18]
The preparation method of HTS operates with embodiment 1.Metatitanic acid four methyl esters gets 1.4g, and pH is adjusted to 2.0, and whipping temp is set to 80 DEG C.Isopropyl alcohol selected by solvent
The Relative mole content of component is:
SiO
2/ TiO
2=23 templates/SiO
2=0.37
[comparative example 1]
Take ethyl orthosilicate 20.0g, butyl titanate 1.0g, alkylpolyoxyethylene 20.3g, ethanol 6.7ml, deionized water 300ml.Be dissolved in deionized water in 500ml there-necked flask by alkylpolyoxyethylene, water-bath 65 DEG C adds thermal agitation 1h, regulates pH to be 2.45, while vigorous stirring, inject ethyl orthosilicate; Add the butyl titanate being dissolved in absolute ethyl alcohol after stirring 0.5h, at 70 DEG C, add thermal agitation 24h.Spend deionized water after leaving standstill cooling, and isolate crystallized product; 110 DEG C of dry removing most of moisture, then high-temperature roasting 350 DEG C hour in Muffle furnace, 550 DEG C 4 hours, obtain the former powder of HTS, get after compressing tablet in fixed bed reactors that 20 ~ 40 order particles load catalyst test apparatus and check catalytic activity and selective.
The Relative mole content of component is:
SiO
2/ TiO
2=32 templates/SiO
2=0.37
[comparative example 2]
Typical experimental procedure comprises tetraethyl orthosilicate and dissolves for the deionized water aqueous solution, and accompanies by gentle stirring.Add the ethanol solution (mixing ten minutes under room temperature to even) of n-hexadecyl APEO afterwards, then regulate pH=2.45, heat 75 DEG C and stir 24 hours.Spend deionized water after leaving standstill cooling, and isolate crystallized product; 110 DEG C of dry removing most of moisture, the ethanolic solution of dipping titanium tetrachloride is to saturation state; Muffle furnace high-temperature roasting forms amorphous ti silica crystal.
[embodiment 19 ~ 36]
Catalyst obtained for each embodiment 1 ~ 18 above-mentioned is carried out 1-butylene epoxidation reaction respectively on catalyst test apparatus investigate.Its appreciation condition is: using the isopropylbenzene containing 10 ~ 30%CHP as oxidant, reaction pressure is 2.0MPa, and reaction temperature controls at 80.0 DEG C, and loaded catalyst is 5ml, mol ratio (CHP/1-butylene) 0.05 ~ 1.Feed rate: 1-butylene (liquid state)=0.5 ~ 5ml/min, CHP (30%)=0.5 ~ 3ml/min.Be averaged reaction result as catalyst performance evaluation data, reaction result is in table 1.
[comparative example 3 ~ 4]
Checked and rated according to embodiment 19 ~ 35 by the catalyst of comparative example 1 ~ 2, reaction result is in table 1
Table one 1-butylene epoxidation reaction result
As can be seen from Table 1, use catalyst prepared by alcohol thermal synthesis method involved in the present invention, take hydrogen phosphide cumene as oxidant, successfully under low-temp low-pressure, 1-butylene epoxy turns in epoxy butane by (80 DEG C and 2.0Mpa), the most high energy of feed stock conversion reaches 92.8%, the selective of epoxy butane reaches as high as 88.9%, is obviously better than in reference catalyst.The activity of this catalyst visible is better, reaches the object that effectively prevent the side reaction of butylene autohemagglutination, has good technique effect.
Claims (6)
1. prepare a preparation method for the catalyst of Isosorbide-5-Nitrae epoxy butane for epoxidation 1-butylene, the concrete preparation process of the catalyst wherein related to is as follows:
(1) template is added in solvent, stir at 20 ~ 100 DEG C, and to add appropriate acid for adjusting pH be 2-9;
(2) silicon source and titanium source are mixed to join in above-mentioned solution to scale, by solution under agitation crystallization obtain gel mixed liquor;
(3) at 40 ~ 100 DEG C, gel mixed liquor 12h ~ 48h is left standstill;
(4) separating gel product, obtains white solid precipitation, after washing and drying, obtains the former powder of catalyst, then roasting in Muffle furnace, and obtained catalyst is used in the method for epoxidation 1-butylene
The mass ratio of each material is: silicon source/titanium source is 10 ~ 150, and solvent/silicon source is 5 ~ 10, and template/silicon source is 0.5 ~ 1.4.
2. method for preparing catalyst according to claim 1, is characterized in that the titanium source of catalyst is the one in metatitanic acid four methyl esters, tetraethyl titanate, metatitanic acid orthocarbonate, butyl titanate, tetraisopropyl titanate; Or inorganic ti sources is the one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide.
3. method for preparing catalyst according to claim 1, is characterized in that catalyst silicon source is the one in quanmethyl silicate, tetraethyl orthosilicate, silicic acid orthocarbonate.
4. method for preparing catalyst according to claim 1, is characterized in that the solvent in dissolving titanium source and silicon source is the one in ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, the tert-butyl alcohol, cyclohexanol.
5. method for preparing catalyst according to claim 1, is characterized in that a kind of regulation system acidity added in dilute sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, hydrofluoric acid.
6. method for preparing catalyst according to claim 1, is characterized in that template is many alkyl polyoxyethylene ethers, is the one in alkylpolyoxyethylene, ceteth and Steareth.
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| CN201410559387.4A CN105498832B (en) | 2014-10-20 | 2014-10-20 | The preparation method of the catalyst of 1,2- epoxy butane is prepared for 1- butylene epoxidation |
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|---|---|---|---|
| CN201410559387.4A CN105498832B (en) | 2014-10-20 | 2014-10-20 | The preparation method of the catalyst of 1,2- epoxy butane is prepared for 1- butylene epoxidation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107930610A (en) * | 2017-11-29 | 2018-04-20 | 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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Cited By (4)
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| CN107930610A (en) * | 2017-11-29 | 2018-04-20 | 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 |
| 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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