CN105709829A - Heteropoly acid catalyst and preparation method thereof - Google Patents
Heteropoly acid catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heteropoly acid catalyst and a preparation method thereof. The catalyst adopts alumina as the carrier, uses heteropoly acid as the active component, and takes boron oxide as the assistant, wherein the surface of the alumina carrier is coated with silica. The preparation method consists of: coating the surface of the alumina carrier with an appropriate amount of silica, and then loading heteropoly acid and the assistant component. The catalyst has high activity and selectivity when used for preparation of ethylene by ethanol dehydration.
Description
Technical field
The present invention relates to a kind of heteropoly acid catalyst and preparation method thereof, particularly relate to a kind of carried heteropoly acid catalyst for producing ethylene from dehydration of ethanol and preparation method thereof.
Background technology
Ethylene is as the flagship product of basic Organic Chemicals and petro chemical industry, and the chemical products of about 75% prepare with ethylene for raw material, and therefore the size of ethylene yield has become as the important symbol weighing a national oil development of chemical industry level.Traditional ethylene obtains mainly by light petroleum fraction cracking, heavy dependence petroleum resources.Along with the day of international energy situation is becoming tight, petroleum resources are increasingly exhausted, and developing new renewable alternative energy source has been the task of top priority.
Many-sided advantages such as recently, ethanol particularly recyclable organism preparing ethylene by dehydrating ethanol is increasingly subject to people's attention, and it has green, sustainable, reaction condition is gentle and product ethylene purity is high.Bio-ethanol is mainly derived from the fermentation of agricultural byproducts, can avoid the dependence to petroleum resources, continues to use this method in the country that some petroleum resources such as Brazil, India, Pakistan are deficient always and produces ethylene, and more there is realistic meaning in the country of oil-poor and few oil by this point.Preparing ethylene by dehydrating ethanol has the great potential partly or entirely replacing obtaining ethylene from oil.Therefore, research producing ethylene from dehydration of ethanol has great economic worth and strategic importance.
Catalyst for ethanol delydration to ethylene report is a lot, mainly activated alumina, molecular sieve and heteropoly acid etc..Activated alumina is as catalyst low price, and activity and selectivity is better, but reaction temperature is high, and reaction velocity is low, and energy consumption is high, and utilization rate of equipment and installations is low.The catalysis activity and selectivity of molecular sieve is high, stable；Reaction temperature is low, and reaction velocity is big, but catalyst life is short, and amplification is little, limits its industrialized production.Heteropoly acid is with certain structure oxygen-containing polyprotic acid by oxygen atom ligand bridging by central atom and coordination atom, has the advantages such as highly acid.In producing ethylene from dehydration of ethanol reacts, it is low that heteropolyacid catalyst has reaction temperature, the feature that selectivity is high and yield is high.
CN200910057539.X discloses the catalyst of a kind of producing ethylene from dehydration of ethanol.This catalyst is with aluminium oxide for carrier, and active component is heteropoly acid, adopts kneading method to prepare.With concentration be 5 ~ 100% ethanol water for raw material, catalyst shows higher ethanol conversion and ethylene selectivity, but reaction temperature requires higher, and the activity of catalyst also needs further raising.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of heteropoly acid catalyst and preparation method thereof.This catalyst has higher activity and selectivity.
Heteropoly acid catalyst of the present invention, adopt alumina support, with heteropoly acid for active component, auxiliary agent is boron oxide, wherein alumina carrier surface coated silica, the weight of silicon dioxide accounts for the 5% ~ 20% of the carrying alumina body weight of coated with silica, it is preferably 8% ~ 18%, with the weight of catalyst for benchmark, the content of heteropoly acid is 3% ~ 25%, it is preferably 8% ~ 20%, more preferably 12% ~ 20%, much further preferably from 15% ~ 20%, the content that auxiliary agent is counted with oxide is for 2% ~ 8%, the content of the alumina support of coated with silica is 67% ~ 95%, it is preferably 72% ~ 90%, more preferably 72% ~ 86%, much further preferably from 72% ~ 83%.
The preparation method of heteropoly acid catalyst of the present invention, including:
(1) alumina support is prepared；
(2) alumina support of coated with silica is prepared；
(3) carrier that step (2) prepares is joined in the mixed solution of heteropoly acid and auxiliary agent presoma, stir at 50 DEG C ~ 90 DEG C to solution and be evaporated；
(4) solid step (3) obtained, drying and roasting, obtain catalyst.
In step (1), described alumina support is to be obtained through molding, dry and roasting by boehmite.Described boehmite can adopt conventional method to prepare, such as: Alchlor process, aluminum sulfate method, carbonizatin method etc..Described roasting condition: sintering temperature is 400 DEG C ~ 700 DEG C, and roasting time is 2h ~ 10h.The shape of alumina support can be determined according to actual needs, such as can adopt spherical, and the particle diameter making gained catalyst is 0.1mm ~ 0.5mm.
In step (2), the method of the alumina support of preparation coated with silica is as follows: organic acid, dispersion aids is mixed with water and is made into mixed solution, silicon source is joined in mixed solution, after mix homogeneously, adds alumina support, 2h ~ 6h is stirred at 50 DEG C ~ 90 DEG C, then stir to becoming gel at 50 DEG C ~ 90 DEG C, aging 5h ~ 12h at 20 DEG C ~ 50 DEG C, at 90 DEG C ~ 120 DEG C dry 5h ~ 12h, at 300 DEG C ~ 600 DEG C roasting 2h ~ 6h, obtain the alumina support of coated with silica.Described organic acid is one or more in citric acid, tartaric acid and malic acid, and the mol ratio that organic acid and silicon source are counted with silicon dioxide is for 0.05 ~ 0.25；Dispersion aids is molecular weight is one or more in the Polyethylene Glycol of 200 ~ 2000, and the mol ratio that Polyethylene Glycol and silicon source are counted with silicon dioxide is for 0.05 ~ 0.20.Silicon source is one or more in tetraethyl orthosilicate, Ludox.Adopt the silica particles that said method can make carrier surface be coated with suitable and uniform, be uniformly dispersed.
In step (3), described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；Auxiliary agent presoma is boric acid.
In step (4), described dry be at 90 DEG C ~ 120 DEG C dry 5h ~ 12h, roasting is at 300 DEG C ~ 450 DEG C roasting 2h ~ 6h.
A kind of method that present invention also offers preparing ethylene by dehydrating ethanol, wherein adopts the catalyst of the present invention.In the present invention, the reaction condition of preparing ethylene by dehydrating ethanol is as follows: with concentration be 5wt% ~ 100wt% ethanol water for raw material, mass space velocity 0.5h-1~15h-1, reaction temperature 280 DEG C ~ 400 DEG C.
Compared with prior art, catalyst of the present invention has the following advantages and feature:
In catalyst of the present invention, the silicon dioxide that alumina carrier surface cladding is appropriate, then carried heteropoly acid and adjuvant component again, so not only will not change the overall pore structure of alumina support, and be conducive to improving the total acid content of catalyst, and have adjusted the heteropoly acid of catalyst and the distribution of adjuvant component and the cooperation effect of active component and adjuvant component, finally make catalyst have higher activity and selectivity and coking resistivity.
Detailed description of the invention
Embodiment 1
(1) preparation of carrier:
2.9g citric acid and 3.0g polyethylene glycol 200 are joined in deionized water, it is made into mixed solution, it is subsequently adding 33.2mL tetraethyl orthosilicate, after stirring, joining the 79.2g particle diameter prepared is in 0.1mm ball-aluminium oxide, 2h is stirred at 60 DEG C, then stir at 80 DEG C to becoming gel, aging 8h at 40 DEG C, then at 110 DEG C of dry 8h, at 550 DEG C of roasting 3h, obtain the alumina support of coated with silica, wherein silicon oxide accounts for the 10% of vehicle weight, the mol ratio of citric acid and silicon oxide is 0.1, the mol ratio of polyethylene glycol 200 and silicon oxide is 0.1.
(2) preparation of catalyst: catalyst adopts supersaturation infusion process to prepare, and step is as follows:
7.1g boric acid and 8.3g phosphotungstic acid are joined in deionized water, is configured to mixed solution；The carrier prepared is joined in mixed solution, stirs at 60 DEG C to solution and be evaporated；Then solid dry 8h, the roasting 3h at 350 DEG C at 110 DEG C that will obtain, prepares H3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 4wt%, H3PW12O40Content is 8wt%, SiO2Content is the 10wt% of the alumina support of coated with silica.
(3) catalyst characterization:
Surrounding and centre in catalyst granules cross section take a little, by SEM, each point are carried out elementary analysis, and result shows: the heteropoly acid content at each point place is substantially suitable, and the catalyst adopting the method to prepare, the dispersion that its heteropoly acid has had on a catalyst are described.
(4) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 50wt% ethanol water, mass space velocity 6h-1, reaction temperature 340 DEG C.Before reaction, catalyst is at N2Activating 2h in 400 DEG C under protection, be then down to after reaction temperature starts to react 2 hours, product is analyzed by gas chromatogram, calculates ethanol conversion and ethylene selectivity, and result is in Table 2.
Embodiment 2
(1) preparation of carrier:
4.8g citric acid and 15.0g Macrogol 600 are joined in deionized water, it is made into mixed solution, it is subsequently adding 37.8mL tetraethyl orthosilicate, after stirring, joining the 73.0g particle diameter prepared is in 0.5mm ball-aluminium oxide, 2h is stirred at 60 DEG C, then stir at 80 DEG C to becoming gel, aging 8h under at 40 DEG C, then at 110 DEG C of dry 8h, at 550 DEG C of roasting 3h, obtain the alumina support of coated with silica, wherein silicon oxide accounts for the 12% of vehicle weight, the mol ratio of citric acid and silicon oxide is 0.15, the mol ratio of Macrogol 600 and silicon oxide is 0.15.
(2) preparation of catalyst: catalyst adopts supersaturation infusion process to prepare, and step is as follows:
8.9g boric acid and 12.5g phosphotungstic acid are joined in deionized water, is configured to mixed solution；The carrier prepared is joined in mixed solution, stirs at 60 DEG C to solution and be evaporated；Then solid dry 8h, the roasting 3h at 350 DEG C at 110 DEG C that will obtain, prepares H3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 5wt%, H3PW12O40Content is 12wt%, SiO2Content is the 12wt% of the alumina support of coated with silica.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 50wt% ethanol water, mass space velocity 8h-1, reaction temperature 340 DEG C.Before reaction, catalyst is at N2Activating 2h in 400 DEG C under protection, be then down to after reaction temperature starts to react 2 hours, product is analyzed by gas chromatogram, calculates ethanol conversion and ethylene selectivity, and result is in Table 2.
Embodiment 3
(1) preparation of carrier:
7.6g citric acid and 14.3g PEG400 are joined in deionized water, it is made into mixed solution, it is subsequently adding 44.9mL tetraethyl orthosilicate, after stirring, joining the 67.2g particle diameter prepared is in 0.3mm ball-aluminium oxide, 2h is stirred at 60 DEG C, then stir at 80 DEG C to becoming gel, aging 8h at 40 DEG C, then at 110 DEG C of dry 8h, at 550 DEG C of roasting 3h, obtain the alumina support of coated with silica, wherein silicon oxide accounts for the 15% of vehicle weight, the mol ratio of citric acid and silicon oxide is 0.2, the mol ratio of PEG400 and silicon oxide is 0.18.
(2) preparation of catalyst: catalyst adopts supersaturation infusion process to prepare, and step is as follows:
10.6g boric acid and 15.6g phosphotungstic acid are joined in deionized water, is configured to mixed solution；The carrier prepared is joined in mixed solution, 60oStir under C to solution and be evaporated；Then by the solid that obtains 110oDry 8h under C, 350oRoasting 3h under C, prepares H3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 6wt%, H3PW12O40Content is 15wt%, SiO2Content is the 15wt% of the alumina support of coated with silica, and catalyst property is listed in table 1.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 50wt% ethanol water, mass space velocity 8h-1, reaction temperature 330 DEG C.Before reaction, catalyst is at N2Activating 2h in 400 DEG C under protection, be then down to after reaction temperature starts to react 2 hours, product is analyzed by gas chromatogram, calculates ethanol conversion and ethylene selectivity, and result is in Table 2.
Embodiment 4
In embodiment 3, citric acid changing 5.8g tartaric acid into, phosphotungstic acid changes silico-tungstic acid into, and all the other are with embodiment 3, and gained catalyst is H4SiW12O40-B2O3/Al2O3-SiO2, wherein B2O3Content is 6wt%, H4SiW12O40Content is 15wt%, SiO2Content is the 15wt% of the alumina support of coated with silica.
The evaluation of catalyst with embodiment 3, ethanol conversion and ethylene selectivity result in Table 2.
Embodiment 5
(1) carrier of embodiment 3 preparation is selected；
(2) preparation of catalyst: catalyst adopts supersaturation infusion process to prepare, and step is as follows:
12.4g boric acid and 18.7g phosphotungstic acid are joined in deionized water, is configured to mixed solution；The carrier prepared is joined in mixed solution, 60oStir under C to solution and be evaporated；Then by the solid that obtains 110oDry 8h under C, 350oRoasting 3h under C, prepares H3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 7wt%, H3PW12O40Content is 18wt%, SiO2Content is the 15wt% of the alumina support of coated with silica.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 50% ethanol water, mass space velocity 10h-1, reaction temperature 340 DEG C.Before reaction, catalyst is at N2Activating 2h in 400 DEG C under protection, be then down to after reaction temperature starts to react 2 hours, product is analyzed by gas chromatogram, calculates ethanol conversion and ethylene selectivity, and result is in Table 2.
Comparative example 1
Alumina support extruded moulding process adds tetraethyl orthosilicate, prepares Al2O3-SiO2Carrier, wherein SiO2Content is the 15wt% of carrier.All the other are with embodiment 3, and gained catalyst is H3PW12O40-B2O3/Al2O3-SiO2, wherein B2O3Content is 6wt%, H3PW12O40Content is 15wt%, SiO2Content is Al2O3-SiO2The 15wt% of carrier.
The evaluation of catalyst with embodiment 3, ethanol conversion and ethylene selectivity result in Table 2.
Comparative example 2
In embodiment 3, changing carrier into aluminium oxide, all the other are with embodiment 3, and gained catalyst is H3PW12O40-B2O3/Al2O3, wherein B2O3Content is 6wt%, H3PW12O40Content is 15wt%, and catalyst property is listed in table 1.
The evaluation of catalyst with embodiment 3, ethanol conversion and ethylene selectivity result in Table 2.
Comparative example 3
In embodiment 3, citric acid changing 1.5g, polyethylene glycol 200 changes 2.9g into, tetraethyl orthosilicate changes 9.1mL into into, aluminium oxide changes 76.6g into, and all the other are with embodiment 3, and gained catalyst is H3PW12O40-B2O3/Al2O3-SiO2, wherein B2O3Content is 6wt%, H3PW12O40Content is 15wt%, SiO2Content is the 3wt% of the alumina support of coated with silica.
The evaluation of catalyst with embodiment 3, ethanol conversion and ethylene selectivity result in Table 2.
Comparative example 4
In embodiment 3, tetraethyl orthosilicate changing 75mL into, aluminium oxide changes 59.2g into, and all the other are with embodiment 3, and gained catalyst is H3PW12O40-B2O3/Al2O3-SiO2, wherein B2O3Content is 6wt%, H3PW12O40Content is 15wt%, SiO2Content is the 25wt% of the alumina support of coated with silica.
The evaluation of catalyst with embodiment 3, ethanol conversion and ethylene selectivity result in Table 2.
Comparative example 5
In embodiment 3, without auxiliary agent boron oxide, all the other are with embodiment 3, and gained catalyst is H3PW12O40/Al2O3-SiO2, H3PW12O40Content is 15wt%, SiO2Content is the 15wt% of the alumina support of coated with silica.
The evaluation of catalyst with embodiment 3, ethanol conversion and ethylene selectivity result in Table 2.
Table 1 catalyst property
| Embodiment | Specific surface area, m2/g | Pore volume, mL/g | Average pore diameter, nm | Relatively infrared total acid content |
| Embodiment 3 | 255 | 0.62 | 9.7 | 130 |
| Comparative example 2 | 215 | 0.55 | 10.2 | 100 |
The conversion ratio of each example catalyst of table 2 and selectivity
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 1 | 99.3 | 98.2 |
| Embodiment 2 | 99.3 | 98.4 |
| Embodiment 3 | 99.2 | 98.6 |
| Embodiment 4 | 99.0 | 98.5 |
| Embodiment 5 | 99.1 | 98.6 |
| Comparative example 1 | 94.8 | 92.6 |
| Comparative example 2 | 93.5 | 90.6 |
| Comparative example 3 | 94.2 | 91.6 |
| Comparative example 4 | 94.4 | 91.5 |
| Comparative example 5 | 95.1 | 93.7 |
From table 2 result, the activity of catalyst of the present invention, selectivity are significantly better than comparative example catalyst.
Claims (14)
1. a heteropoly acid catalyst, adopt alumina support, with heteropoly acid for active component, auxiliary agent is boron oxide, wherein alumina carrier surface coated silica, and the weight of silicon dioxide accounts for the 5% ~ 20% of the carrying alumina body weight of coated with silica, with the weight of catalyst for benchmark, the content of heteropoly acid is 3% ~ 25%, and the content of the alumina support of coated with silica is 67% ~ 95%, and the content that auxiliary agent is counted with oxide is for 2% ~ 8%.
2. the catalyst described in claim 1, it is characterised in that the weight of described silicon dioxide accounts for the 8% ~ 18% of the carrying alumina body weight of coated with silica.
3. the catalyst described in claim 1, it is characterised in that with the weight of catalyst for benchmark, the content of heteropoly acid is 8% ~ 20%, and the content of the alumina support of coated with silica is 72% ~ 90%, and the content that auxiliary agent is counted with oxide is for 2% ~ 8%.
4. the catalyst described in claim 1, it is characterised in that with the weight of catalyst for benchmark, the content of heteropoly acid is 12% ~ 20%, and the content of the alumina support of coated with silica is 72% ~ 86%, and the content that auxiliary agent is counted with oxide is for 2% ~ 8%.
5. the catalyst described in claim 1, it is characterised in that being shaped as of catalyst is spherical, its particle diameter 0.1mm ~ 0.5mm.
6. the preparation method of the arbitrary described catalyst of claim 1 ~ 5, including:
(1) alumina support is prepared；
(2) alumina support of coated with silica is prepared；
(3) carrier that step (2) prepares is joined in the mixed solution of heteropoly acid and auxiliary agent presoma, stir at 50 DEG C ~ 90 DEG C to solution and be evaporated；
(4) solid step (3) obtained, drying and roasting, obtain catalyst.
7. in accordance with the method for claim 6, it is characterised in that in step (1), described alumina support is to be obtained through molding, dry and roasting by boehmite；Described roasting condition: sintering temperature is 400 DEG C ~ 700 DEG C, and roasting time is 2h ~ 10h.
8. in accordance with the method for claim 6, it is characterized in that in step (2), the method of the alumina support of preparation coated with silica is as follows: organic acid, dispersion aids is mixed with water and is made into mixed solution, silicon source is joined in mixed solution, after mix homogeneously, add alumina support, 2h ~ 6h is stirred at 50 DEG C ~ 90 DEG C, then stir to becoming gel at 50 DEG C ~ 90 DEG C, aging 5h ~ 12h at 20 DEG C ~ 50 DEG C, at 90 DEG C ~ 120 DEG C dry 5h ~ 12h, at 300 DEG C ~ 600 DEG C roasting 2h ~ 6h, obtain the alumina support of coated with silica.
9. the mol ratio that in accordance with the method for claim 8, it is characterised in that described organic acid is one or more in citric acid, tartaric acid and malic acid, organic acid and silicon source are counted with silicon dioxide is for 0.05 ~ 0.25；Dispersion aids is molecular weight is one or more in the Polyethylene Glycol of 200 ~ 2000, and the mol ratio that Polyethylene Glycol and silicon source are counted with silicon dioxide is for 0.05 ~ 0.20.
10. in accordance with the method for claim 8, it is characterised in that described silicon source is one or more in tetraethyl orthosilicate, Ludox.
11. in accordance with the method for claim 6, it is characterised in that in step (3), described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；Auxiliary agent presoma is boric acid.
12. in accordance with the method for claim 6, it is characterised in that in step (4), described dry be at 90 DEG C ~ 120 DEG C dry 5h ~ 12h, roasting is at 300 DEG C ~ 450 DEG C roasting 2h ~ 6h.
13. the method for a preparing ethylene by dehydrating ethanol, it is characterised in that adopt the arbitrary described catalyst of claim 1 ~ 4.
14. in accordance with the method for claim 13, it is characterised in that: the reaction condition of preparing ethylene by dehydrating ethanol is as follows: with concentration be 5wt% ~ 100wt% ethanol water for raw material, mass space velocity 0.5h-1~15h-1, reaction temperature 280 DEG C ~ 400 DEG C.
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| CN109926092A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | Heteropoly acid ammonium salt catalyst and its preparation method |
| CN109926073A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of high-selective and hydrogenating Cracking catalyst and preparation method thereof |
| CN109926073B (en) * | 2017-12-15 | 2021-10-08 | 中国石油化工股份有限公司 | High-selectivity hydrocracking catalyst and preparation method thereof |
| CN109926093B (en) * | 2017-12-15 | 2021-10-08 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN109926092B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Heteropolyacid ammonium salt catalyst and preparation method thereof |
| CN109926093A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN109926091B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Heteropolyacid ammonium salt catalyst and preparation method thereof |
| WO2019197987A1 (en) * | 2018-04-09 | 2019-10-17 | Sabic Global Technologies B.V. | Selective production of monoaromatic hydrocarbons from pyrolysis oil |
| CN108772109B (en) * | 2018-07-06 | 2020-11-24 | 中国科学院合肥物质科学研究院 | Nanowire spherical molybdenum-tungsten heteropoly acid salt catalyst and preparation method and application thereof |
| CN108772109A (en) * | 2018-07-06 | 2018-11-09 | 中国科学院合肥物质科学研究院 | A kind of spherical molybdenum heteropoly tungstic acid salt catalyst of nano wire and the preparation method and application thereof |
| CN111375434A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Supported heteropoly acid catalyst and preparation method thereof |
| CN111375434B (en) * | 2018-12-29 | 2022-07-12 | 中国石油化工股份有限公司 | Supported heteropoly acid catalyst and preparation method thereof |
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