CN105709829B - A kind of heteropoly acid catalyst and preparation method thereof - Google Patents
A kind of heteropoly acid catalyst and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of heteropoly acid catalyst and preparation method thereof.The catalyst uses alumina support, and using heteropoly acid as active component, auxiliary agent is boron oxide, wherein alumina carrier surface coated silica, and its preparation method is to coat appropriate silica in alumina carrier surface, then carried heteropoly acid and adjuvant component again.With higher activity and selectivity when the catalyst is used for producing ethylene from dehydration of ethanol.
Description
Technical field
The present invention relates to a kind of heteropoly acid catalyst and preparation method thereof, is used for ethanol dehydration more particularly to one kind
Carried heteropoly acid catalyst of ethene and preparation method thereof.
Background technology
Ethene is as basic Organic Chemicals and the flagship product of petro chemical industry, about 75% chemical products
It is prepared by raw material of ethene, therefore the size of ethylene yield has become one national oil development of chemical industry water of measurement
Flat important symbol.Traditional ethene mainly by light petroleum fraction crack made from, heavy dependence petroleum resources.With
The day of international energy situation is becoming tight, and petroleum resources are increasingly exhausted, and it has been the task of top priority to develop new renewable alternative energy source.
Recently, ethanol particularly recyclable organism preparing ethylene by dehydrating ethanol is increasingly valued by people, and it has
Green, sustainable, reaction condition is gentle and many advantages such as product ethylene purity height.Bio-ethanol is mainly derived from agriculture
The fermentation of byproduct, the dependence to petroleum resources can be avoided, deficient in some petroleum resources such as Brazil, India, Pakistan
Country continues to use this method production ethene always, and this point more has realistic meaning to the country of oil-poor and few oil.Ethanol dehydration prepares second
Alkene, which has, partly or entirely replaces the great potential that ethene is obtained from oil.Therefore, research producing ethylene from dehydration of ethanol has great
Economic value and strategic importance.
Catalyst for ethanol delydration to ethylene report is a lot, mainly activated alumina, molecular sieve and heteropoly acid etc..It is living
Property aluminum oxide is cheap as catalyst, and activity and selectivity is preferable, but reaction temperature is high, and reaction velocity is low, energy
Consumption is high, and utilization rate of equipment and installations is low.The catalytic activity and selectivity of molecular sieve are high, stable；Reaction temperature is low, and reaction velocity is big, but
Catalyst life is short, and multiplication factor is small, limits its industrialized production.Heteropoly acid is with one by central atom and coordination atom
The oxygen-containing polyacid that fixed structure is formed by oxygen atom ligand bridging, has the advantages that highly acid.In producing ethylene from dehydration of ethanol
In reaction, heteropolyacid catalyst has the characteristics of reaction temperature is low, selectivity height and high income.
CN200910057539.X discloses a kind of catalyst of producing ethylene from dehydration of ethanol.The catalyst is using aluminum oxide as load
Body, active component are heteropoly acid, are prepared using kneading method.It is 5 ~ 100% ethanol water for raw material using concentration, catalyst table
Reveal higher ethanol conversion and ethylene selectivity, but reaction temperature requires higher, and the activity of catalyst also needs further to carry
It is high.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of heteropoly acid catalyst and its preparation side
Method.The catalyst has higher activity and selectivity.
Heteropoly acid catalyst of the present invention, using alumina support, using heteropoly acid as active component, auxiliary agent is boron oxide,
Wherein alumina carrier surface coated silica, the weight of silica account for the carrying alumina body weight of coated with silica
5% ~ 20%, preferably 8% ~ 18%, on the basis of the weight of catalyst, the content of heteropoly acid is 3% ~ 25%, preferably 8% ~ 20%, is entered
One step is preferably 12% ~ 20%, and much further preferably from 15% ~ 20%, auxiliary agent is using the content that oxide is counted as 2% ~ 8%, silica
The content of the alumina support of cladding is 67% ~ 95%, and preferably 72% ~ 90%, more preferably 72% ~ 86% are further excellent
Elect 72% ~ 83% as.
The preparation method of heteropoly acid catalyst of the present invention, including：
（1）Prepare alumina support；
（2）Prepare the alumina support of coated with silica；
（3）By step（2）Obtained carrier is added in the mixed solution of heteropoly acid and auxiliary agent presoma, 50 DEG C ~ 90
Stirring to solution is evaporated at DEG C；
（4）By step（3）Obtained solid, through drying and being calcined, produce catalyst.
Step（1）In, described alumina support be by boehmite through being molded, dry and roasting and obtain.Described
Boehmite can be made using conventional method, 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 the h of 2 h ~ 10.The shape of alumina support can be according to being actually needed
It to determine, for example can use spherical, the particle diameter for making gained catalyst is the mm of 0.1 mm ~ 0.5.
Step（2）In, the method for preparing the alumina support of coated with silica is as follows：By organic acid, dispersion aids with
Water mixing is made into mixed solution, and silicon source is added in mixed solution, after being well mixed, alumina support is added, 50 DEG C ~ 90
The h of 2 h ~ 6 is stirred at DEG C, then stirring is into gel at 50 DEG C ~ 90 DEG C, the h of the h of aging 5 ~ 12 at 20 DEG C ~ 50 DEG C, 90
DEG C ~ h of 120 DEG C of 5 h of drying ~ 12, the h of 2 h ~ 6 is calcined at 300 DEG C ~ 600 DEG C, obtains the alumina support of coated with silica.Institute
The organic acid stated be citric acid, tartaric acid and malic acid in one or more, organic acid rubbing in terms of silica with silicon source
You are than being 0.05 ~ 0.25；Dispersion aids is the one or more in the polyethylene glycol that molecular weight is 200 ~ 2000, polyethylene glycol with
Silicon source is using the mol ratio that silica is counted as 0.05 ~ 0.20.Silicon source is the one or more in tetraethyl orthosilicate, Ludox.Adopt
The silica particles that carrier surface can in aforementioned manners coated are suitable and uniform, are uniformly dispersed.
In step（3）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；Auxiliary agent forerunner
Body is boric acid.
In step（4）In, described drying is that roasting is 300 DEG C ~ 450 in the h of 90 DEG C ~ 120 DEG C 5 h of drying ~ 12
DEG C roasting 2 h ~ 6 h.
Present invention also offers a kind of method of preparing ethylene by dehydrating ethanol, wherein the catalyst using the present invention.This hair
In bright, the reaction condition of preparing ethylene by dehydrating ethanol is as follows：It is 5wt% ~ 100wt% ethanol water for raw material using concentration, matter
Measure the h of air speed 0.5-1~15 h-1, 280 DEG C ~ 400 DEG C of reaction temperature.
Compared with prior art, catalyst of the present invention has advantages below and feature：
In catalyst of the present invention, alumina carrier surface coats appropriate silica, then carried heteropoly acid and helps again
Agent component, so not but not change alumina support overall pore structure, and be advantageous to improve catalyst total acid content, and
The distribution and active component and the cooperation of adjuvant component that have adjusted the heteropoly acid and adjuvant component of catalyst act on, and finally make
Catalyst has higher activity and selectivity and coking resistivity.
Embodiment
Embodiment 1
（1）The preparation of carrier：
2.9g citric acids and 3.0g polyethylene glycol 200s are added in deionized water, mixed solution is made into, then adds
33.2mL tetraethyl orthosilicates, after stirring, it is in 0.1mm ball-aluminium oxides, at 60 DEG C to be added to the 79.2g particle diameters prepared
2 h of lower stirring, then stirring is into gel at 80 DEG C, the h of aging 8 at 40 DEG C, then in 110 DEG C of dry 8 h, 550
DEG C 3 h of roasting, obtain the alumina support of coated with silica, and wherein silica accounts for the 10% of vehicle weight, citric acid and oxidation
The mol ratio of silicon is 0.1, and the mol ratio of polyethylene glycol 200 and silica is 0.1.
（2）The preparation of catalyst：Catalyst is prepared using supersaturated infusion process, and step is as follows：
7.1g boric acid and 8.3g phosphotungstic acids are added in deionized water, are configured to mixed solution；The carrier that will be prepared
It is added in mixed solution, stirring to solution is evaporated at 60 DEG C；Then obtained solid is dried into 8 h at 110 DEG C,
3 h are calcined at 350 DEG C, H is made3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 4wt%, H3PW12O40Contain
Measure as 8wt%, SiO2Content is the 10wt% of the alumina support of coated with silica.
（3）Catalyst characterization：
Taken a little in the surrounding in catalyst granules section and centre, elementary analysis carried out to each point by SEM, the results showed that：
Heteropoly acid content at each point is substantially suitable, illustrates the catalyst prepared using the method, and its heteropoly acid has on a catalyst
Good is scattered.
（4）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 50wt% ethanol waters, mass space velocity
6h-1, 340 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and opens
Begin after reacting 2 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 2.
Embodiment 2
（1）The preparation of carrier：
4.8g citric acids and 15.0g Macrogol 600s are added in deionized water, mixed solution is made into, then adds
37.8mL tetraethyl orthosilicates, after stirring, it is in 0.5mm ball-aluminium oxides, at 60 DEG C to be added to the 73.0g particle diameters prepared
2 h of lower stirring, then stirring is into gel at 80 DEG C, the lower h of aging 8 at 40 DEG C, then in 110 DEG C of dry 8 h,
550 DEG C of 3 h of roasting, obtain the alumina support of coated with silica, and wherein silica accounts for the 12% of vehicle weight, citric acid with
The mol ratio of silica is 0.15, and the mol ratio of Macrogol 600 and silica is 0.15.
（2）The preparation of catalyst：Catalyst is prepared using supersaturated infusion process, and step is as follows：
8.9g boric acid and 12.5g phosphotungstic acids are added in deionized water, are configured to mixed solution；The carrier that will be prepared
It is added in mixed solution, stirring to solution is evaporated at 60 DEG C；Then obtained solid is dried into 8 h at 110 DEG C,
3 h are calcined at 350 DEG C, H is made3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 5wt%, H3PW12O40Content
For 12wt%, SiO2Content is the 12wt% of the alumina support of coated with silica.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 50wt% ethanol waters, mass space velocity
8h-1, 340 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and opens
Begin after reacting 2 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 2.
Embodiment 3
（1）The preparation of carrier：
7.6g citric acids and 14.3g polyethylene glycol 400s are added in deionized water, mixed solution is made into, then adds
44.9mL tetraethyl orthosilicates, after stirring, it is in 0.3mm ball-aluminium oxides, at 60 DEG C to be added to the 67.2g particle diameters prepared
2 h of lower stirring, then stirring is into gel at 80 DEG C, the aging 8h at 40 DEG C, then in 110 DEG C of dry 8 h, 550
DEG C 3 h of roasting, obtain the alumina support of coated with silica, and wherein silica accounts for the 15% of vehicle weight, citric acid and oxidation
The mol ratio of silicon is 0.2, and the mol ratio of polyethylene glycol 400 and silica is 0.18.
（2）The preparation of catalyst：Catalyst is prepared using supersaturated infusion process, and step is as follows：
10.6g boric acid and 15.6g phosphotungstic acids are added in deionized water, are configured to mixed solution；The load that will be prepared
Body is added in mixed solution, 60oStirring to solution is evaporated under C；Then by obtained solid 110o8 h are dried under C,
350o3 h are calcined under C, H is made3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 6wt%, H3PW12O40
Content is 15wt%, SiO2Content is the 15wt% of the alumina support of coated with silica, and catalyst property is listed in table 1.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 50wt% ethanol waters, mass space velocity
8h-1, 330 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and opens
Begin after reacting 2 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 2.
Embodiment 4
In embodiment 3, citric acid is changed to 5.8g tartaric acid, phosphotungstic acid is changed to silico-tungstic acid, and remaining is the same as embodiment 3, institute
It is H to obtain catalyst4SiW12O40-B2O3/Al2O3-SiO2, wherein B2O3Content is 6wt%, H4SiW12O40Content is 15wt%, SiO2
Content is the 15wt% of the alumina support of coated with silica.
The evaluation of catalyst the results are shown in Table 2 with embodiment 3, ethanol conversion and ethylene selectivity.
Embodiment 5
（1）Carrier prepared by selection example 3；
（2）The preparation of catalyst：Catalyst is prepared using supersaturated infusion process, and step is as follows：
12.4g boric acid and 18.7g phosphotungstic acids are added in deionized water, are configured to mixed solution；The load that will be prepared
Body is added in mixed solution, 60oStirring to solution is evaporated under C；Then by obtained solid 110o8 h are dried under C,
350o3 h are calcined under C, H is made3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 7wt%, H3PW12O40
Content is 18wt%, SiO2Content is the 15wt% of the alumina support of coated with silica.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 50% ethanol water, mass space velocity
10h-1, 340 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and opens
Begin after reacting 2 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 2.
Comparative example 1
Tetraethyl orthosilicate is added during alumina support extruded moulding, Al is made2O3-SiO2Carrier, wherein SiO2Contain
Measure the 15wt% for carrier., with embodiment 3, gained catalyst is H for remaining3PW12O40-B2O3/Al2O3-SiO2, wherein B2O3Content
For 6wt%, H3PW12O40Content is 15wt%, SiO2Content is Al2O3-SiO2The 15wt% of carrier.
The evaluation of catalyst the results are shown in Table 2 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 2
In embodiment 3, carrier is changed to aluminum oxide, with embodiment 3, gained catalyst is H for remaining3PW12O40-B2O3/
Al2O3, wherein B2O3Content is 6wt%, H3PW12O40Content is 15wt%, and catalyst property is listed in table 1.
The evaluation of catalyst the results are shown in Table 2 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 3
In embodiment 3, citric acid is changed to 1.5g, polyethylene glycol 200 is changed to 2.9g, tetraethyl orthosilicate is changed to 9.1mL,
Aluminum oxide is changed to 76.6g, and, with embodiment 3, gained catalyst is H for remaining3PW12O40-B2O3/Al2O3-SiO2, wherein B2O3Content
For 6wt%, H3PW12O40Content is 15wt%, SiO2Content is the 3wt% of the alumina support of coated with silica.
The evaluation of catalyst the results are shown in Table 2 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 4
In embodiment 3, tetraethyl orthosilicate is changed to 75mL, aluminum oxide is changed to 59.2g, and, with embodiment 3, gained is urged for remaining
Agent 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 the results are shown in Table 2 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 5
In embodiment 3, auxiliary agent boron oxide is not added, and, with embodiment 3, gained catalyst is H for remaining3PW12O40/Al2O3-
SiO2, H3PW12O40Content is 15wt%, SiO2Content is the 15wt% of the alumina support of coated with silica.
The evaluation of catalyst the results are shown in Table 2 with embodiment 3, ethanol conversion and ethylene selectivity.
The catalyst property of table 1
| 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 and selectivity of 2 each catalyst of table
| 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 the result of table 2, activity, the selectivity of catalyst of the present invention are significantly better than comparative example catalyst.
Claims (14)
1. a kind of heteropoly acid catalyst, using alumina support, using heteropoly acid as active component, auxiliary agent is boron oxide, wherein
Alumina carrier surface coated silica, the weight of silica account for the carrying alumina body weight of coated with silica 5% ~
20%, on the basis of the weight of catalyst, the content of heteropoly acid is 3% ~ 25%, the content of the alumina support of coated with silica
For 67% ~ 95%, auxiliary agent is using the content that oxide is counted as 2% ~ 8%.
2. according to the catalyst described in claim 1, it is characterised in that the weight of the silica accounts for coated with silica
The 8% ~ 18% of carrying alumina body weight.
3. according to the catalyst described in claim 1, it is characterised in that on the basis of the weight of catalyst, the content of heteropoly acid
For 8% ~ 20%, the content of the alumina support of coated with silica is 72% ~ 90%, and auxiliary agent is using the content that oxide is counted as 2% ~ 8%.
4. according to the catalyst described in claim 1, it is characterised in that on the basis of the weight of catalyst, the content of heteropoly acid
For 12% ~ 20%, the content of the alumina support of coated with silica is 72% ~ 86%, auxiliary agent using the content that oxide is counted as 2% ~
8%。
5. according to the catalyst described in claim 1, it is characterised in that being shaped as catalyst is spherical, its particle diameter 0.1 mm ~
0.5 mm。
6. the preparation method of any catalyst of claim 1 ~ 5, including：
（1）Prepare alumina support；
（2）Prepare the alumina support of coated with silica；
（3）By step（2）Obtained carrier is added in the mixed solution of heteropoly acid and auxiliary agent presoma, at 50 DEG C ~ 90 DEG C
Stirring to solution is evaporated；
（4）By step（3）Obtained solid, through drying and being calcined, produce catalyst.
7. in accordance with the method for claim 6, it is characterised in that step（1）In, described alumina support is by intending thin water
Aluminium stone through being molded, dry and roasting and obtain；Described roasting condition：Sintering temperature is 400 DEG C ~ 700 DEG C, roasting time 2
h ~10 h。
8. in accordance with the method for claim 6, it is characterised in that step（2）In, prepare the carrying alumina of coated with silica
The method of body is as follows：Organic acid, dispersion aids are mixed with water and are made into mixed solution, silicon source is added in mixed solution, is mixed
After closing uniformly, add alumina support, the h of 2 h ~ 6 stirred at 50 DEG C ~ 90 DEG C, then at 50 DEG C ~ 90 DEG C stirring to Cheng Ning
Glue, the h of the h of aging 5 ~ 12 at 20 DEG C ~ 50 DEG C, in the h of 90 DEG C ~ 120 DEG C 5 h of drying ~ 12,2 h ~ 6 are calcined at 300 DEG C ~ 600 DEG C
H, obtain the alumina support of coated with silica.
9. in accordance with the method for claim 8, it is characterised in that described organic acid is in citric acid, tartaric acid and malic acid
One or more, organic acid and silicon source are using the mol ratio that silica is counted as 0.05 ~ 0.25；Dispersion aids is that molecular weight is
One or more in 200 ~ 2000 polyethylene glycol, polyethylene glycol and silicon source using the mol ratio that silica is counted as 0.05 ~
0.20。
10. in accordance with the method for claim 8, it is characterised in that the silicon source is one kind in tetraethyl orthosilicate, Ludox
It is or a variety of.
11. in accordance with the method for claim 6, it is characterised in that in step（3）In, described heteropoly acid is phosphotungstic acid, silicon
One or more in wolframic 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）In, described drying is 90 DEG C ~ 120
DEG C dry the h of 5 h ~ 12, roasting is that the h of 2 h ~ 6 is calcined at 300 DEG C ~ 450 DEG C.
A kind of 13. method of preparing ethylene by dehydrating ethanol, it is characterised in that using any 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
The ethanol water that concentration is 5wt% ~ 100wt% is raw material, the h of mass space velocity 0.5-1~15 h-1, reaction temperature 280 DEG C ~ 400
℃。
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| CN105709829A (en) | 2016-06-29 |
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