CN105170176B - 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 catalyst and its production and use, specifically a kind of catalyzing expoxidation of olefines
Catalyst, especially a kind of catalyst of catalysis liquid phase preparing epoxypropane by epoxidation of propene.
Background technology
In the method for generating expoxy propane as the carrier of oxygen and propylene cooxidation using hydroperoxides, i.e. HALCON methods
In (Halcon method), industrial catalyst is frequently with homogeneous molybdenum series catalyst.When hydroperoxides be tert-butyl hydroperoxide (below
Abbreviation TBHP) when, the homogeneous molybdenum catalyst for adopting is ammonium dimolybdate ethylene glycol complex.Due to homogeneous molybdenum catalyst after the reaction
Molybdenum therein cannot can only be reclaimed by burning disposal and prepare reaction use again again by polishing purification direct reuse
Catalyst, therefore when using such homogeneous molybdenum catalyst catalysis epoxidation of propylene, technical process is relative complex, and because of catalyst
Recovery, process, technology of preparing is relative blocks, and causes catalyst relatively costly.
It is well known that using heterogeneous catalysis, the recycling cost of catalyst will be far below and adopt homogeneous catalyst
Technique.But because TBHP is compared with hydrogen peroxide with ethylbenzene hydroperoxide, the chemical property of TBHP is relatively stable, peroxide double bond
Bond energy is higher, and general heterogeneous catalysis is difficult to cross its reaction energy levels, reduces its activation with epoxidation reaction of olefines
The purpose of energy, and presently used homogeneous catalyst, during catalysis TBHP with propylene reaction, TBHP is to epoxy third
The selectivity of alkane is about 80% or so, and the side reaction for occurring is mainly the decomposition reaction of TBHP itself and TBHP and propylene is anti-
Etherification reaction is answered to generate PGTBE (propylene glycol t-butyl ether), equation is as follows：
The generation of side reaction result in two kinds of reactants of TBHP and propylene to the selective reduction of expoxy propane.
Up to now, both at home and abroad existing numerous researchers have been delivered with regard to catalyzing expoxidation of olefines heterogeneous catalysis
The document of preparation, but patent and document that TBHP catalyzing expoxidation of olefines prepares expoxy propane are not related to substantially.Wherein Liu is just prosperous
Et al. Au-Ti-SBA-15 molecular sieves have been synthesized using hydro-thermal one-pot synthesis, and be successfully applied to epoxidation of styrene
In preparing the course of reaction of phenyl ring oxidative ethane, cinnamic conversion ratio is 37%, and cinnamic selectivity is 82.6%, but should
During reuse, selectivity of styrene rapid drawdown when repeating to third time illustrates catalyst weight to catalyst to 50% or so
Multiple using effect is not good.
Open superfine people to be modified TS-1 molecular sieve carriers using metal Ga, with deposition-precipitation method golden catalysis is prepared for
Agent, and it has been used for the epoxidation reaction of gas-phase propene, different Ga dopings are compared to catalyst structure and the shadow of catalytic performance
Ring, the conversion ratio for making propylene improves close one percentage point, by original 1.8% 2.7% has been brought up to；Selectivity is also by original
86.2% for coming has brought up to 91.9%, and catalytic mechanism is tried to be explained, and they think the increase of catalyst activity
The incorporation of Ga may be also because makes gold grain distribution more uniform, but because the addition of Ga causes the acidity of catalyst surface
Position increases, and increases acidity of catalyst, and product easily occurs in acid condition side reaction, therefore also brings no small negative
Face effect.
Although the research with regard to the heterogeneous catalysis of catalyzing expoxidation of olefines is numerous, seek a kind of catalysis activity height,
Reuse the good catalyst of effect to be used for being catalyzed the emphasis that preparing epoxypropane by epoxidation of propene remains current research.
The content of the invention
To solve above technical problem, it is an object of the present invention to provide a kind of olefin epoxidation catalysts, this is urged
Agent belongs to heterogeneous catalysis, and it is easily separated with product, reusable, and activity is high, uses it for epoxidation of propylene system
Standby expoxy propane, especially with tert-butyl hydroperoxide as oxidant, the preparing epoxypropane by epoxidation of liquid propylene, Ke Yishi
Existing propylene conversion is up to 3.5wt%, and expoxy propane selectivity is up to 92wt%.
Further object is that providing the preparation method of above-mentioned catalyst, the preparation method is succinctly easy to get, step
Sequence is few, low cost.
To reach above goal of the invention, the technical solution used in the present invention is as follows：
A kind of olefin epoxidation catalysts, the catalyst includes carrier, gold and rhodium, based on overall catalyst weight, gold content
For 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 common for Jing galliums, boron and alkali metal
With the Ti-SBA-15 molecular sieves after modification.
In the present invention, each component weight percent content is in described carrier：Gallium content is 0.01%~1wt%, excellent
Select 0.05%~0.8wt%；Boron contents are 0.001%~0.5wt%, preferably 0.005%~0.3wt%；Alkali metal content is
0.01%~1wt%, preferably 0.05%~0.8wt%, Ti-SBA-15 contents be 97.5%~99.88wt%, preferably 98.1%
~99.5wt%, said components content is based on carrier gross weight.Ti content is 0.1%~20wt% in the Ti-SBA-15, excellent
3%~10wt% is selected, based on Ti-SBA-15 gross weights.
In the present invention, described alkali metal is selected from one or more in lithium, sodium, potassium, rubidium and caesium.
For the technical problem for solving to be run into during epoxidation of propylene described in background technology, catalyst of the present invention with
Ti-SBA-15 molecular sieves Jing after gallium, boron and alkali metal jointly modification are carrier, and your gold loaded thereon by deposition-precipitation method
Category Au and Rh prepares gained.Catalyst mode is Au-Rh/Ga-B-M-Ti-SBA-15 (M represents alkali metal), using Ti-SBA-
15 molecular sieves can provide the common HTS of ratio bigger specific surface area for catalyst so that noble metal gold-rhodium
Load capacity is low, improves the dispersion of precious metal atom, it is ensured that the content of catalyst activity component.Due to Ga larger atom half
Footpath, the incorporation of Ga makes that distribution of the active component particles on carrier can be made more uniform, and the catalysis for being effectively increased catalyst is lived
Property.But because the addition of Ga causes the acidic site of catalytic inner to increase, and alkali-metal addition can effectively eliminate acidic site
Impact.Because boron is lacked electron atom, it has stronger electron-withdrawing energy, and the addition of boron would be even more beneficial to TBHP and be adsorbed
React to catalyst surface, and due to there is stronger adsorption between Ti-SBA-15 molecular sieves and boron atom,
B atoms will preferentially occupy all the time in molecular sieve disorderly or irregular space, and this is beneficial to the aperture of molecular sieve and pore volume
Stablize.
Further, since the mutual synergism of both Au and Rh so that the side reaction product glycol tertiary of TBHP and propylene
Butyl ether has and substantially reduces, and TBHP is improved to the selectivity 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 conditionss, 30 will be added to by 10~20 parts of surfactants of mass parts
In~50 parts of aqueous hydrochloric acid solutions, 10 parts of tetraethyl orthosilicates are subsequently adding, while adding 2~8 parts by tetrabutyl titanate, You Jirong
Agent, solubility gallium salt and alkali borate composition mixed liquor, after white gels to appear stir, it is aging, filter, be dried,
Roasting obtains Ga-B-M-Ti-SBA-15 molecular sieve carriers；
Catalyst preparation：The gold chloride of finite concentration ratio and soluble rhodium saline solution are heated to into 40~90 DEG C, are used
It is 6~8 that aqueous slkali adjusts pH value, is subsequently added carrier, and at such a temperature aging rear separation drying, obtains catalyst Au-Rh/
Ga-B-M-Ti-SBA-15。
In preparation method of the present invention, in prepared by carrier, occur stirring 18~30h after white gels, it is old at 80~120 DEG C
Change 18~30h, described drying is to be dried 3~8 hours under the conditions of 80~120 DEG C.
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：Alkali borate
Mass ratio is：0.5~3:3~5:0.005~0.1:0.01~0.05, preferably 0.6~2.6：3~5：0.0057~0.065：
0.014~0.04.
In preparation method of the present invention, in catalyst preparation, ageing time is 0.5~2h.
In preparation method of the present invention, in catalyst preparation, drying condition is to be vacuum dried 3 under 50~70 DEG C of water bath conditions
~5 hours.
In the 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 gold chloride
Solution and rhodium nitrate solution are aqueous solution.The molar concentration of described aqueous hydrochloric acid solution is：0.5mol/L~4mol/L.It is described
Aqueous slkali be one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate solution, described aqueous slkali
Molar concentration scope is：0.02mol/L~0.5mol/L.
In the preparation method of the present invention, the alkali borate in prepared by described carrier is Lithium biborate, sodium borate, boric acid
One or more in potassium, boric acid rubidium and boric acid caesium.
In the preparation method of catalyst of the present invention, it is preferable that described solubility gallium salt is Ganite (Fujisawa)., soluble rhodium salt is
Rhodium nitrate.
In the preparation method of the present invention, described organic solvent be acetylacetone,2,4-pentanedione, isopropanol, DMF,
One kind in ethanol.
In the preparation method of the present invention, described surfactant be TPAOH, TBAH with
And one or more in poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (P123).
Using catalyst preparing epoxypropane by epoxidation of propene of the present invention, using tank reactor in, with the tert-butyl group
The t-butanol solution of hydrogen peroxide be oxidant, TBHP concentration be 30wt%-70wt%, propylene：TBHP mol ratio=1.5:1~
10:1, under 110 DEG C -150 DEG C of temperature, absolute pressure 1.0Mpa~4.5Mpa, 10min~5h is reacted, obtain expoxy propane.
Also can be carried out on fixed bed reactors using catalyst preparing epoxypropane by epoxidation of propene of the present invention, third
Alkene：TBHP flows mol ratio=1.5:1~10:1 reactor air speed is 4000-7000h-1。
It is used to be catalyzed preparing epoxypropane by epoxidation of propene, effective choosing of expoxy propane by using the catalyst of the present invention
Selecting property is 90-92%, and the high conversion rate of propylene is up to 3.5%.
Specific embodiment
The present invention is expanded on further below by way of example, but is not restricted to following examples.
Product analytical conditions for gas chromatography is as follows：
Embodiment 1：The preparation of Ga-B-M-Ti-SBA-15 catalyst carriers
It is prepared by carrier A：
(1) under the conditions of 30 DEG C, 20g TPAOHs are added in the aqueous hydrochloric acid solution of 50g0.5mol/L, so
10g tetraethyl orthosilicates are added afterwards, while adding the mixing containing tetrabutyl titanate and acetylacetone,2,4-pentanedione and Ganite (Fujisawa). and sodium borate
Liquid (wherein tetrabutyl titanate：Acetylacetone,2,4-pentanedione：Ganite (Fujisawa).：The quality of sodium borate is respectively：0.668g、5g、0.0057g、
0.014g), after white gels to appear, 18h is stirred continuously and healthily, the aging 18h at 80 DEG C；
(2) take out product, filter, be dried 5h under the conditions of 100 DEG C after by gained desciccate at 350 DEG C roasting 4h,
Obtain Ga-B-Na-Ti-SBA-15 molecular sieve carriers.Related property parameter detecting is carried out to carrier and is shown in Table one, predominantly constitute,
BET specific surface area, aperture.
BET specific surface area, aperture and pore volume are determined and determined using specific surface area and porosity measuring instrument, and instrument is U.S.'s health
Tower company Quadrasorb SI types specific surface areas and porosity measuring instrument degassing temperature are 300 DEG C.
Elementary composition measure is determined using inductively coupled plasma atomic emission spectrometer.Instrument is that U.S.'s Agilent is public
Department's 700Series ICP-OES type inductively coupled plasma atomic emission spectrometers.
It is prepared by carrier B：
(1) under the conditions of 40 DEG C, by 15g parts poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer
(P123) it is added in the aqueous hydrochloric acid solution of 40g2mol/L, is subsequently adding 10g tetraethyl orthosilicates, while add contains metatitanic acid
Mixed liquor (the wherein tetrabutyl titanate of N-butyl and isopropanol and Ganite (Fujisawa). and potassium borate：Isopropanol：Ganite (Fujisawa).：Potassium borate
Quality is respectively：1.55g, 4g, 0.0365g, 0.035g), after white gels to appear, stir continuously and healthily after 24h, 100
Aging 24h at DEG C.
(2) take out product, filter, be dried 6h under the conditions of 90 DEG C after by gained desciccate at 450 DEG C roasting 6h, obtain
To Ga-B-K-Ti-SBA-15 molecular sieve carriers.Related property parameter detecting is carried out to carrier and is shown in Table one, predominantly composition, BET
Specific surface area, aperture.
It is prepared by support C：
(1) under the conditions of 50 DEG C, 20g TBAH is added in the aqueous hydrochloric acid solution of 30g4mol/L, then
10g tetraethyl orthosilicates are added, while adding containing tetrabutyl titanate and DMF and Ganite (Fujisawa). and Lithium biborate
Mixed liquor (wherein tetrabutyl titanate：N,N-dimethylformamide：Ganite (Fujisawa).：The quality of Lithium biborate is respectively:2.58g、3g、
0.065g, 0.04g), after white gels to appear, stir continuously and healthily after 30h, the aging 30h at 120 DEG C.
(2) take out product, filter, be dried 4h under the conditions of 110 DEG C after by gained desciccate at 600 DEG C roasting 8h,
Obtain Ga-B-Li-Ti-SBA-15 molecular sieve carriers.Related property parameter detecting is carried out to carrier and is shown in Table one, predominantly constitute,
BET specific surface area, aperture.
Table one：The related property detection of three kinds of carriers
| Project | Carrier A | Carrier B | Support C |
| BET/(㎡/g) | 630 | 652 | 617 |
| Aperture/nm | 7.3 | 7.8 | 7.5 |
| Pore volume/(cm3/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 contents/wt% | 99.842 | 99.403 | 98.910 |
Embodiment 2：The preparation of Au-Rh/Ga-B-M-Ti-SBA-15 catalyst
It is prepared by catalyst I：
(1) by 1.53ml concentration for 3mmol/L gold chloride (HAuCl4) and 4.96ml concentration be 3mmol/L rhodium nitrates
(Rh(NO3)3) solution mix homogeneously and it is heated to 70 DEG C, it is 6 to adjust pH value using sodium hydroxide solution；
(2) 3g carrier A are added in the solution obtained by (1) step, aging 1h is continued at such a temperature；
(3) centrifugation, under 50 DEG C of water bath conditions 5h is vacuum dried, and obtains catalyst I.Catalyst composition is shown in Table two.
It is prepared by catalyst II：
(1) by 1.91ml concentration for 4mmol/L gold chloride (HAuCl4) and 5.1ml concentration be 4mmol/L rhodium nitrate (Rh
(NO3)3) solution mix homogeneously and it is heated to 80 DEG C, it is 7 to adjust pH value using potassium hydroxide solution；
(2) 3g carrier Bs are added in the solution obtained by (1), aging 1h is continued at such a temperature；
(3) centrifugation, under 60 DEG C of water bath conditions 3h is vacuum dried, and obtains catalyst II.Catalyst composition is shown in Table two.
It is prepared by catalyst III：
(1) by 2.14ml concentration for 5mmol/L gold chloride (HAuCl4) and 5.88ml concentration be 5mmol/L rhodium nitrates
(Rh(NO3)3) solution mix homogeneously and it is heated to 90 DEG C, it is 8 to adjust pH value using sodium carbonate liquor；
(2) 3g carrier A are added in the solution obtained by (1), aging 1h is continued at such a temperature；
(3) centrifugation, under 70 DEG C of water bath conditions 4h is vacuum dried, and obtains catalyst III.Catalyst composition is shown in Table
Two.
The composition of the catalyst I of table two~III
| Project | Gold content/wt% | Rhodium content/wt% | Vector contg/wt% |
| Catalyst I | 0.03 | 0.05 | 99.92 |
| Catalyst II | 0.05 | 0.07 | 99.88 |
| Catalyst III | 0.07 | 0.10 | 99.83 |
Embodiment 3：With tert-butyl hydroperoxide (TBHP) as oxidant, liquid propylene preparing epoxypropane by epoxidation
The catalytic performance test of Au-Rh/Ga-B-M-Ti-SBA-15 catalyst is carried out on fixed bed reactors, reaction tube
Internal diameter is 10mm, external diameter 25mm, long 500mm, and reaction pipe outer wall uses heat-conducting oil heating, catalyst bed to be placed in reaction tube
Section, respectively there is up and down porcelain ball and quartz sand place mat, and beds middle part has thermocouple to determine reaction temperature.
Catalyst amount is 3g, and propylene flow is 0.77g/min, and the flow of TBHP solution is 2g/min, and both flows divide
Accurately do not adjusted by mass flowmenter, reactor air speed is 5000h-1, the equal question response of active appraisal experiment data reached after stable state
Obtain, product carries out on-line analyses, Therapy lasted 100 hours, test propylene conversion and selectivity by gas chromatogram.
Table three：Three kinds of activity rating of catalyst results
| Project | Catalyst I | Catalyst II | Catalyst III |
| Reaction temperature | 135℃ | 135℃ | 135℃ |
| Reaction pressure | 4.3Mpa | 4.3Mpa | 4.3Mpa |
| Propylene conversion | 3.2% | 3.5% | 3.5% |
| Expoxy propane selectivity | 90% | 92% | 92% |
| Propylene conversion during 100h | 3.0% | 3.5% | 3.5% |
| Expoxy propane selectivity during 100h | 90% | 92% | 92% |
Claims (13)
1. a kind of olefin epoxidation catalysts, it is characterised in that：The catalyst includes carrier, gold and rhodium, total based on catalyst
Weight, gold content is 0.01~0.1wt%；Rhodium content is 0.01~0.1wt%；Vector contg is 99.8~99.98wt%；It is described
Carrier be the Ti-SBA-15 molecular sieves Jing after gallium, boron and alkali metal jointly modification.
2. catalyst according to claim 1, it is characterised in that：Based on overall catalyst weight, gold content is 0.03~
0.07wt%；Rhodium content is 0.05~0.09wt%；Vector contg is 99.85~99.92wt%.
3. catalyst according to claim 1, it is characterised in that：Each component weight percent content is in carrier：Gallium contains
Measure as 0.01%~1wt%；Boron contents are 0.001%~0.5wt%；Alkali metal content is 0.01%~1wt%；Ti-SBA-
15 contents are 97.5%~99.88wt%；Said components content is based on carrier gross weight.
4. catalyst according to claim 3, it is characterised in that：Each component weight percent content is in carrier：Gallium contains
Measure as 0.05%~0.8wt%；Boron contents are 0.005%~0.3wt%；Alkali metal content is 0.05%~0.8wt%；Ti-
SBA-15 contents are 98.1%~99.5wt%；Said components content is based on carrier gross weight.
5. the catalyst according to any one of claim 1-4, it is characterised in that：Described alkali metal selected from lithium, sodium,
One or more in potassium, rubidium, caesium.
6. the preparation method of the catalyst according to any one of claim 1-5, it is characterised in that：Comprise the steps
The preparation of carrier：Under 30~50 DEG C of temperature conditionss, 30~50 will be added to by 10~20 parts of surfactants of mass parts
In part aqueous hydrochloric acid solution, be subsequently adding 10 parts of tetraethyl orthosilicates, at the same add 2~8 parts by tetrabutyl titanate, organic solvent,
The mixed liquor of solubility gallium salt and alkali borate composition, stirs after white gels to appear, aging, filtration, dry, roasting
Obtain Ga-B-M-Ti-SBA-15 molecular sieve carriers；
The gold chloride of finite concentration ratio and soluble rhodium saline solution are heated to into 40~90 DEG C, it is 6~8 to adjust pH value, subsequently
Carrier is added, at such a temperature aging rear separation drying, obtains catalyst Au-Rh/Ga-B-M-Ti-SBA-15.
7. the preparation method of catalyst according to claim 6, it is characterised in that tetrabutyl titanate：Organic solvent：It is solvable
Property gallium salt：The mass ratio of alkali borate is：0.5~3:3~5:0.005~0.1:0.01~0.05.
8. the preparation method of catalyst according to claim 6, it is characterised in that described chlorauric acid solution it is mole dense
Spend and be：1~10mmol/L, the molar concentration of described soluble rhodium saline solution is：1~10mmol/L, described hydrochloric acid is water-soluble
The molar concentration of liquid is：0.5mol/L~4mol/L.
9. the preparation method of catalyst according to claim 6, it is characterised in that described alkali borate is boric acid
One or more in lithium, sodium borate, potassium borate, boric acid rubidium and boric acid caesium, solubility gallium salt is Ganite (Fujisawa)., and soluble rhodium salt is
Rhodium nitrate.
10. the preparation method of catalyst according to claim 6, it is characterised in that described surfactant is 4 third
In base ammonium hydroxide, TBAH and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer
One or more.
The preparation method of 11. catalyst according to claim 6 or 7, it is characterised in that described organic solvent is acetyl
One kind in acetone, isopropanol, N,N-dimethylformamide, ethanol.
Method system any one of 12. catalyst or claim 6-11 according to any one of claim 1-5
The application of standby catalyst, it is characterised in that the catalyst is used to be catalyzed preparing epoxypropane by epoxidation of propene.
13. applications according to claim 12, it is characterised in that the catalyst is used for tert-butyl hydroperoxide as oxidation
Agent, the preparing epoxypropane by epoxidation of liquid propylene.
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| CN107879897B (en) * | 2016-09-29 | 2022-11-22 | 中国石油化工股份有限公司 | One-step method for synthesizing o-diol compound |
| CN106582809B (en) * | 2016-12-22 | 2019-08-30 | 红宝丽集团股份有限公司 | A kind of olefin epoxidation catalysts and preparation method thereof |
| 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 |
| CN111377951B (en) * | 2018-12-28 | 2022-09-20 | 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 |
| CN109529927A (en) * | 2019-01-06 | 2019-03-29 | 福州大学 | A kind of propylene gas-phase epoxidation catalyst and preparation method thereof |
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