CN105170176A - Olefin epoxidation catalyst as well as preparation method and application thereof - Google Patents
Olefin epoxidation catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an olefin epoxidation catalyst as well as a preparation method and an application thereof. The catalysts comprises 0.01wt%-0.1wt% of gold, 0.01wt%-0.1wt% of rhodium and 99.8wt%-99.98wt% of a supporter on the basis of the total weight of the catalyst, wherein the supporter is a Ti-SBA-15 molecular sieve modified by gallium, boron and alkali metal together. The catalyst is used for catalyzing propylene epoxidation with TBHP (tert-butyl hydroperoxide) used as an oxidizing agent for generation of epoxy propane, and the catalyst has the good stability. The effective selectivity of the epoxy propane ranges from 90% to 92%, and the conversion rate of propylene is up to 3.5%.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and purposes, specifically a kind of catalyst of catalyzing expoxidation of olefines, especially a kind of catalyst of catalysis liquid phase preparing epoxypropane by epoxidation of propene.
Background technology
Generate the method for expoxy propane as the carrier of oxygen and propylene cooxidation at employing hydroperoxides, namely in HALCON method (Halcon method), industrial catalyst often adopts homogeneous phase molybdenum series catalyst.When hydroperoxides are TBHP (hereinafter referred to as TBHP), the homogeneous phase molybdenum catalyst of employing is ammonium dimolybdate ethylene glycol complex compound.Because homogeneous phase molybdenum catalyst cannot pass through polishing purification direct reuse after the reaction, molybdenum wherein preparation feedback catalyst again again can only be reclaimed by burning disposal, therefore when adopting this type of homogeneous phase molybdenum catalyst catalytic epoxidation of propone, technical process relative complex, and relatively block because of the recovery of catalyst, process, technology of preparing, cause catalyst cost higher.
As everyone knows, adopt heterogeneous catalysis, the recycling cost of catalyst will far below the technique adopting homogeneous catalyst.But because TBHP compares with ethylbenzene hydroperoxide with hydrogen peroxide, the chemical property of TBHP is relatively stable, the bond energy of peroxide double bond is higher, general heterogeneous catalysis is difficult to cross its reaction energy levels, reach the object of the activation energy reducing itself and epoxidation reaction of olefines, and in the presently used homogeneous catalyst process of reacting at catalysis TBHP and propylene, TBHP is about about 80% to the selective of expoxy propane, the side reaction occurred the mainly decomposition reaction of TBHP self and TBHP and propylene reaction etherification reaction generates PGTBE (propylene glycol t-butyl ether), equation is as follows:
The generation of side reaction result in TBHP and propylene two kinds of reactants optionally reduce expoxy propane.
Up to now, both at home and abroad existing numerous researcher has delivered the document prepared about catalyzing expoxidation of olefines heterogeneous catalysis, but does not substantially relate to patent and document that TBHP catalyzing expoxidation of olefines prepares expoxy propane.Wherein Liu is just prosperous waits people to adopt hydro-thermal one-pot synthesis to synthesize Au-Ti-SBA-15 molecular sieve, and be successfully applied to epoxidation of styrene and prepare in the course of reaction of phenyl ring oxidative ethane, cinnamic conversion ratio is 37%, cinnamic selective be 82.6%, but this catalyst is being reused in process, when repeating to for the third time about selectivity of styrene rapid drawdown to 50%, illustrate that poor effect reused by catalyst.
Opening superfine people adopts metal Ga to carry out modification to TS-1 molecular sieve carrier, Au catalyst has been prepared with deposition-precipitation method, and for the epoxidation reaction of gas-phase propene, compare the impact of different Ga doping on catalyst structure and catalytic performance, make the conversion ratio of propylene improve close to one percentage point, bring up to 2.7% by original 1.8%; Selectively also bring up to 91.9% by original 86.2%, and try to explain to catalytic mechanism, they think that the increase of catalyst activity may or make gold grain distribution more even because of mixing of Ga, but because adding of Ga causes the acidic site of catalyst surface to increase, acidity of catalyst is increased, easily there is side reaction in product, therefore also brings no small negative effect in acid condition.
Although numerous about the research of the heterogeneous catalysis of catalyzing expoxidation of olefines, it is high to seek a kind of catalytic activity, reuses effective catalyst and is used for catalytic epoxidation of propone and prepares the emphasis that expoxy propane remains research at present.
Summary of the invention
For solving above technical problem, one object of the present invention is to provide a kind of olefin epoxidation catalysts, this catalyst belongs to heterogeneous catalysis, its easy and product separation, reusable, and it is active high, using it for preparing epoxypropane by epoxidation of propene, is especially the preparing epoxypropane by epoxidation of oxidant, liquid propylene with TBHP, can realize propylene conversion up to 3.5wt%, expoxy propane is selective up to 92wt%.
Another object of the present invention is the preparation method providing above-mentioned catalyst, and this preparation method is succinctly easy to get, and step sequence is few, and cost is low.
For reaching above goal of the invention, the technical solution used in the present invention is as follows:
A kind of olefin epoxidation catalysts, described catalyst comprises carrier, gold and rhodium, and based on overall catalyst weight, gold content is 0.01 ~ 0.1wt%, preferably 0.03 ~ 0.07wt%; Rhodium content is 0.01 ~ 0.1wt%, preferably 0.05 ~ 0.09wt%; Vector contg is 99.8 ~ 99.98wt%, preferably 99.85 ~ 99.92wt%; Described carrier is the Ti-SBA-15 molecular sieve after gallium, boron and alkali metal are modified jointly.
In the present invention, in described carrier, each component weight percent content is: gallium content is 0.01% ~ 1wt%, preferably 0.05% ~ 0.8wt%; Boron contents is 0.001% ~ 0.5wt%, preferably 0.005% ~ 0.3wt%; Alkali metal content is 0.01% ~ 1wt%, and preferably 0.05% ~ 0.8wt%, Ti-SBA-15 content is 97.5% ~ 99.88wt%, preferably 98.1% ~ 99.5wt%, and said components content is all based on carrier gross weight.In described Ti-SBA-15, Ti content is 0.1% ~ 20wt%, preferably 3% ~ 10wt%, based on Ti-SBA-15 gross weight.
In the present invention, described alkali metal be selected from lithium, sodium, potassium, rubidium and caesium one or more.
For solving the technical problem run in epoxidation of propylene process described in background technology, catalyst of the present invention with the Ti-SBA-15 molecular sieve after jointly modifying through gallium, boron and alkali metal for carrier, by deposition-precipitation method thereon carried noble metal Au and Rh prepare gained.Catalyst mode is Au-Rh/Ga-B-M-Ti-SBA-15 (M represents alkali metal), use Ti-SBA-15 molecular sieve can provide a specific area larger than common HTS for catalyst, make the load capacity of Precious Metals-Gold-rhodium low, improve the decentralization of precious metal atom, ensure the content of catalyst activity component.Due to the atomic radius that Ga is larger, mixing of Ga makes to make the distribution of active component particles on carrier more even, effectively increases the catalytic activity of catalyst.But because adding of Ga makes the acidic site of catalytic inner increase, and alkali-metally add the impact effectively can eliminating acidic site.Because boron is lacked electron atom, it has stronger electrophilic performance, more will be conducive to the adding of boron TBHP to be adsorbed to catalyst surface and to react, and owing to there is stronger suction-operated between Ti-SBA-15 molecular sieve and boron atom, B atom will preferentially occupy disorderly in molecular sieve or irregular space all the time, and this will be conducive to the aperture of molecular sieve and the stable of pore volume.
In addition, due to the mutual synergy of Au and Rh, make the side reaction product propylene glycol t-butyl ether of TBHP and propylene have remarkable minimizing, TBHP is improved to the selective of expoxy propane.
The preparation method of catalyst of the present invention comprises the steps:
The preparation of carrier: under 30 ~ 50 DEG C of temperature conditions, to join in 30 ~ 50 parts of aqueous hydrochloric acid solutions by mass parts 10 ~ 20 parts of surfactants, then 10 parts of tetraethyl orthosilicates are added, add 2 ~ 8 portions of mixed liquors be made up of tetrabutyl titanate, organic solvent, solubility gallium salt and alkali borate simultaneously, stir after white gels to appear, aging, filter, dry, roasting obtains Ga-B-M-Ti-SBA-15 molecular sieve carrier;
Catalyst preparing: the gold chloride of finite concentration ratio and soluble rhodium salting liquid are heated to 40 ~ 90 DEG C, aqueous slkali adjust ph is used to be 6 ~ 8, add carrier subsequently, aging rear separation is dry at such a temperature, obtains catalyst A u-Rh/Ga-B-M-Ti-SBA-15.
In preparation method of the present invention, in carrier preparation, occur stirring 18 ~ 30h, aging 18 ~ 30h at 80 ~ 120 DEG C after white gels, described drying be drying 3 ~ 8 hours under 80 ~ 120 DEG C of conditions.
In preparation method of the present invention, described sintering temperature is 350 ~ 600 DEG C, and roasting time is 4 ~ 8h.
In preparation method of the present invention, described tetrabutyl titanate: organic solvent: solubility gallium salt: the mass ratio of alkali borate is: 0.5 ~ 3:3 ~ 5:0.005 ~ 0.1:0.01 ~ 0.05, is preferably 0.6 ~ 2.6:3 ~ 5:0.0057 ~ 0.065:0.014 ~ 0.04.
In preparation method of the present invention, in catalyst preparing, ageing time is 0.5 ~ 2h.
In preparation method of the present invention, in catalyst preparing, drying condition is vacuum drying 3 ~ 5 hours under 50 ~ 70 DEG C of water bath condition.
In preparation method of the present invention, the molar concentration of described chlorauric acid solution is: 1 ~ 10mmol/L, preferably 2 ~ 5mmol/L.The molar concentration of described rhodium nitrate solution is: 1 ~ 10mmol/L, preferably 2 ~ 5mmol/L.Described chlorauric acid solution and rhodium nitrate solution are the aqueous solution.The molar concentration of described aqueous hydrochloric acid solution is: 0.5mol/L ~ 4mol/L.Described aqueous slkali is one or more in NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate solution, and the molar concentration scope of described aqueous slkali is: 0.02mol/L ~ 0.5mol/L.
In preparation method of the present invention, the alkali borate in described carrier preparation is one or more in lithium borate, Boratex, potassium borate, boric acid rubidium and boric acid caesium.
In the preparation method of catalyst of the present invention, preferably, described solubility gallium salt is gallium nitrate, and soluble rhodium salt is rhodium nitrate.
In preparation method of the present invention, described organic solvent is the one in acetylacetone,2,4-pentanedione, isopropyl alcohol, DMF, ethanol.
In preparation method of the present invention, described surfactant is one or more in TPAOH, TBAH and PEO-PPOX-PEO triblock copolymer (P123).
Adopt catalyst preparing epoxypropane by epoxidation of propene of the present invention, adopt in tank reactor, with the t-butanol solution of TBHP for oxidant, TBHP concentration is 30wt%-70wt%, propylene: TBHP mol ratio=1.5:1 ~ 10:1, under temperature 110 DEG C-150 DEG C, absolute pressure 1.0Mpa ~ 4.5Mpa, reaction 10min ~ 5h, obtains expoxy propane.
Adopt catalyst preparing epoxypropane by epoxidation of propene of the present invention also can carry out on fixed bed reactors, propylene: TBHP flow mol ratio=1.5:1 ~ 10:1 reactor air speed is 4000-7000h
-1.
The catalyst of the application of the invention is used for catalytic epoxidation of propone and prepares expoxy propane, and the effective selectivity of expoxy propane is 90-92%, and the conversion ratio of propylene is up to 3.5%.
Detailed description of the invention
Set forth the present invention further below by way of example, but be never only limitted to following examples.
Product analytical conditions for gas chromatography is as follows:
The preparation of embodiment 1:Ga-B-M-Ti-SBA-15 catalyst carrier
Prepared by carrier A:
(1) under 30 DEG C of conditions, 20g TPAOH is joined in the aqueous hydrochloric acid solution of 50g0.5mol/L, then 10g tetraethyl orthosilicate is added, add the mixed liquor (wherein tetrabutyl titanate: acetylacetone,2,4-pentanedione: gallium nitrate: the quality of Boratex is respectively: 0.668g, 5g, 0.0057g, 0.014g) containing tetrabutyl titanate and acetylacetone,2,4-pentanedione and gallium nitrate and Boratex simultaneously, after white gels to appear, stir 18h continuously and healthily, aging 18h at 80 DEG C;
(2) take out product, filter, under 100 DEG C of conditions after dry 5h by gained desciccate roasting 4h at 350 DEG C, obtain Ga-B-Na-Ti-SBA-15 molecular sieve carrier.Related property parameter detecting is carried out in table one to carrier, is mainly composition, BET specific surface area, aperture.
BET specific surface area, aperture and pore volume measure and adopt specific area and porosity measuring instrument to measure, and instrument is U.S. Kang Ta company QuadrasorbSI type specific area and porosity measuring instrument degassing temperature is 300 DEG C.
Element composition measuring adopts inductively coupled plasma atomic emission spectrometer to measure.Instrument is U.S. Agilent company 700SeriesICP-OES type inductively coupled plasma atomic emission spectrometer.
Prepared by carrier B:
(1) under 40 DEG C of conditions, by 15g part PEO-PPOX-PEO triblock copolymer (P123) joins in the aqueous hydrochloric acid solution of 40g2mol/L, then 10g tetraethyl orthosilicate is added, add the mixed liquor (wherein tetrabutyl titanate: isopropyl alcohol: gallium nitrate: the quality of potassium borate is respectively: 1.55g, 4g, 0.0365g, 0.035g) containing tetrabutyl titanate and isopropyl alcohol and gallium nitrate and potassium borate simultaneously, after white gels to appear, after stirring 24h continuously and healthily, aging 24h at 100 DEG C.
(2) take out product, filter, under 90 DEG C of conditions after dry 6h by gained desciccate roasting 6h at 450 DEG C, obtain Ga-B-K-Ti-SBA-15 molecular sieve carrier.Related property parameter detecting is carried out in table one to carrier, is mainly composition, BET specific surface area, aperture.
Prepared by support C:
(1) under 50 DEG C of conditions, 20g TBAH is joined in the aqueous hydrochloric acid solution of 30g4mol/L, then 10g tetraethyl orthosilicate is added, add containing tetrabutyl titanate and N simultaneously, mixed liquor (the wherein tetrabutyl titanate: N of dinethylformamide and gallium nitrate and lithium borate, dinethylformamide: gallium nitrate: the quality of lithium borate is respectively: 2.58g, 3g, 0.065g, 0.04g), after white gels to appear, after stirring 30h continuously and healthily, aging 30h at 120 DEG C.
(2) take out product, filter, under 110 DEG C of conditions after dry 4h by gained desciccate roasting 8h at 600 DEG C, obtain Ga-B-Li-Ti-SBA-15 molecular sieve carrier.Related property parameter detecting is carried out in table one to carrier, is mainly composition, BET specific surface area, aperture.
Table one: the related property of three kinds of carriers detects
| Project | Carrier A | Carrier B | Support C |
| BET/(㎡/g) | 630 | 652 | 617 |
| Aperture/nm | 7.3 | 7.8 | 7.5 |
| Pore volume/(cm 3/g) | 1.05 | 1.05 | 1.03 |
| Gallium content/wt% | 0.051 | 0.303 | 0.498 |
| Boron contents/wt% | 0.052 | 0.142 | 0.287 |
| Alkali metal content/wt% | 0.055 | 0.152 | 0.305 |
| Ti-SBA-15 content/wt% | 99.842 | 99.403 | 98.910 |
The preparation of embodiment 2:Au-Rh/Ga-B-M-Ti-SBA-15 catalyst
Prepared by catalyst I:
(1) by 1.53ml concentration be the gold chloride (HAuCl of 3mmol/L
4) and 4.96ml concentration be 3mmol/L rhodium nitrate (Rh (NO
3)
3) solution mixes and be heated to 70 DEG C, uses sodium hydroxide solution to regulate pH value to be 6;
(2) 3g carrier A is joined in the solution that (1) step obtains, continue aging 1h at such a temperature;
(3) centrifugation, under 50 DEG C of water bath condition, vacuum drying 5h, obtains catalyst I.Catalyst composition is in table two.
Prepared by catalyst I I:
(1) by 1.91ml concentration be the gold chloride (HAuCl of 4mmol/L
4) and 5.1ml concentration be 4mmol/L rhodium nitrate (Rh (NO
3)
3) solution mixes and be heated to 80 DEG C, uses potassium hydroxide solution to regulate pH value to be 7;
(2) 3g carrier B is joined in the solution that (1) obtain, continue aging 1h at such a temperature;
(3) centrifugation, under 60 DEG C of water bath condition, vacuum drying 3h, obtains catalyst I I.Catalyst composition is in table two.
Prepared by catalyst I II:
(1) by 2.14ml concentration be the gold chloride (HAuCl of 5mmol/L
4) and 5.88ml concentration be 5mmol/L rhodium nitrate (Rh (NO
3)
3) solution mixes and be heated to 90 DEG C, uses sodium carbonate liquor to regulate pH value to be 8;
(2) 3g carrier A is joined in the solution that (1) obtain, continue aging 1h at such a temperature;
(3) centrifugation, under 70 DEG C of water bath condition, vacuum drying 4h, obtains catalyst I II.Catalyst composition is in table two.
The composition of table two catalyst I ~ III
| Project | Gold content/wt% | Rhodium content/wt% | Vector contg/wt% |
| Catalyst I | 0.03 | 0.05 | 99.92 |
| Catalyst I I | 0.05 | 0.07 | 99.88 |
| Catalyst I II | 0.07 | 0.10 | 99.83 |
Embodiment 3: with TBHP (TBHP) for oxidant, liquid propylene preparing epoxypropane by epoxidation
The catalytic performance test of Au-Rh/Ga-B-M-Ti-SBA-15 catalyst carries out on fixed bed reactors, tube inner diameter is 10mm, external diameter 25mm, long 500mm, reaction tube outer wall uses heat-conducting oil heating, catalyst bed is placed on reaction tube stage casing, respectively has porcelain ball and quartz sand place mat up and down, has thermocouple measurement reaction temperature in the middle part of beds.
Catalyst amount is 3g, and propylene flow is the flow of 0.77g/min, TBHP solution is 2g/min, and both are accurately regulated by mass flowmenter by flow respectively, and reactor air speed is 5000h
-1, obtain after the equal question response of active appraisal experiment data reaches stable state, product carries out on-line analysis by gas-chromatography, Therapy lasted 100 hours, test propylene conversion and selective.
Table three: the Activity evaluation of three kinds of catalyst
| Project | Catalyst I | Catalyst I I | Catalyst I II |
| Reaction temperature | 135℃ | 135℃ | 135℃ |
| Reaction pressure | 4.3Mpa | 4.3Mpa | 4.3Mpa |
| Propylene conversion | 3.2％ | 3.5％ | 3.5％ |
| Expoxy propane is selective | 90％ | 92％ | 92％ |
| Propylene conversion during 100h | 3.0％ | 3.5％ | 3.5％ |
| During 100h, expoxy propane is selective | 90％ | 92％ | 92％ |
Claims (10)
1. an olefin epoxidation catalysts, is characterized in that: described catalyst comprises carrier, gold and rhodium, and based on overall catalyst weight, gold content is 0.01 ~ 0.1wt%, preferably 0.03 ~ 0.07wt%; Rhodium content is 0.01 ~ 0.1wt%, preferably 0.05 ~ 0.09wt%; Vector contg is 99.8 ~ 99.98wt%, preferably 99.85 ~ 99.92wt%; Described carrier is the Ti-SBA-15 molecular sieve after gallium, boron and alkali metal are modified jointly.
2. catalyst according to claim 1, is characterized in that: in carrier, each component weight percent content is: gallium content is 0.01% ~ 1wt%, preferably 0.05% ~ 0.8wt%; Boron contents is 0.001% ~ 0.5wt%, preferably 0.005% ~ 0.3wt%; Alkali metal content is 0.01% ~ 1wt%, preferably 0.05% ~ 0.8wt%; Ti-SBA-15 content is 97.5% ~ 99.88wt%, preferably 98.1% ~ 99.5wt%; Said components content is all based on carrier gross weight.
3. catalyst according to claim 1 and 2, is characterized in that: described alkali metal be selected from lithium, sodium, potassium, rubidium, caesium one or more.
4. the preparation method of the catalyst according to any one of claim 1-3, is characterized in that: comprise the steps
The preparation of carrier: under 30 ~ 50 DEG C of temperature conditions, to join in 30 ~ 50 parts of aqueous hydrochloric acid solutions by mass parts 10 ~ 20 parts of surfactants, then 10 parts of tetraethyl orthosilicates are added, add 2 ~ 8 portions of mixed liquors be made up of tetrabutyl titanate, organic solvent, solubility gallium salt and alkali borate simultaneously, stir after white gels to appear, aging, filter, dry, roasting obtains Ga-B-M-Ti-SBA-15 molecular sieve carrier;
The gold chloride of finite concentration ratio and soluble rhodium salting liquid are heated to 40 ~ 90 DEG C, and adjust ph is 6 ~ 8, adds carrier subsequently, and aging rear separation is dry at such a temperature, obtains catalyst A u-Rh/Ga-B-M-Ti-SBA-15.
5. the preparation method of catalyst according to claim 4, is characterized in that, tetrabutyl titanate: organic solvent: solubility gallium salt: the mass ratio of alkali borate is: 0.5 ~ 3:3 ~ 5:0.005 ~ 0.1:0.01 ~ 0.05.
6. the preparation method of catalyst according to claim 4, it is characterized in that, the molar concentration of described chlorauric acid solution is: 1 ~ 10mmol/L, the molar concentration of described soluble rhodium salting liquid is: 1 ~ 10mmol/L, and the molar concentration of described aqueous hydrochloric acid solution is: 0.5mol/L ~ 4mol/L.
7. the preparation method of catalyst according to claim 4, it is characterized in that, described alkali borate is one or more in lithium borate, Boratex, potassium borate, boric acid rubidium and boric acid caesium, and solubility gallium salt is gallium nitrate, and soluble rhodium salt is rhodium nitrate.
8. the preparation method of catalyst according to claim 4, it is characterized in that, described surfactant is one or more in TPAOH, TBAH and PEO-PPOX-PEO triblock copolymer.
9. the preparation method of the catalyst according to claim 4 or 5, is characterized in that, described organic solvent is the one in acetylacetone,2,4-pentanedione, isopropyl alcohol, DMF, ethanol.
10. the application of catalyst prepared of the catalyst according to any one of claim 1-3 or the method according to any one of claim 4-9, it is characterized in that, this catalyst is used for catalytic epoxidation of propone and prepares expoxy propane, being preferred for take TBHP as the preparing epoxypropane by epoxidation of oxidant, liquid propylene.
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| CN107879897A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | The method of one-step synthesis method vicinal diamines class compound |
| 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 |
| CN109529927A (en) * | 2019-01-06 | 2019-03-29 | 福州大学 | A kind of propylene gas-phase epoxidation catalyst and preparation method thereof |
| CN111377951A (en) * | 2018-12-28 | 2020-07-07 | 万华化学集团股份有限公司 | Rare earth metal compound, preparation method, composition and method for catalyzing olefin epoxidation |
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