CN104588106B - Catalyst used for producing dimethyl ether through methanol dehydration, and preparation method thereof - Google Patents
Catalyst used for producing dimethyl ether through methanol dehydration, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst used for producing dimethyl ether through methanol dehydration, and a preparation method thereof. The catalyst comprises an active component, an auxiliary agent and a carrier. The active component is heteropoly acid ammonium salt. The auxiliary agent is lanthanum oxide and/or cerium oxide. The carrier is silicon oxide. The preparation method comprises the following steps: alkane, an organic acid, and an ammonium-containing alkaline solution or ammonia gas are sequentially loaded on the silicon oxide carrier; heteropoly acid and the auxiliary agent are loaded on the carrier; and drying and roasting are carried out, such that the catalyst is obtained. The catalyst provided by the invention has relatively high low-temperature activity, selectivity and coking resistance. Also, the stability of the catalyst is improved. The catalyst provided by the invention is especially suitable for a reaction for producing dimethyl ether with a methanol raw material with relatively high water content.
Description
Technical field
The present invention relates to a kind of producing dimethyl ether by dehydrating methanol catalyst and preparation method thereof, more particularly to one kind is used for
Carried heteropoly acid ammonium salt in catalysis agent of producing dimethyl ether by dehydrating methanol and preparation method thereof.
Background technology
Dimethyl ether (dimethy ether, abridge dme) is a kind of colourless, non-toxic gas under normal temperature and pressure state, can be through
Boil down to liquid.Dimethyl ether is important Organic Chemicals and chemical intermediate, can be used for aerosol, cold-producing medium, alkylation
The industries such as agent, pharmacy, cosmetics, fuel.
Dimethyl ether is obtained by after the side-product rectification in high-pressure process methanol production earliest, develops into methanol dehydration and conjunction quickly
Gas is become to be directly synthesized two kinds of techniques.Liquid phase methanol dewatering preparing dimethy ether, reaction is carried out in the liquid phase, and major defect is that equipment is rotten
Erosion is serious, operating condition is severe, and environmental pollution is serious, and product post processing is relatively difficult gradually to be eliminated.And synthesis gas is straight
It is bonded into dimethyl ether and remains in the experimentation stage, the dominating process route producing dimethyl ether at present in the world remains gas
Phase method methanol dehydration.
At present, the catalyst that methanol dehydration adopts is usually al2o3Or molecular sieve, wherein conventional molecular sieve have aluminum phosphate,
Hzsm-5, hy, sapo etc., they have respective shortcoming: although as aluminium oxide stability is high, reaction temperature is high, to anti-
The equipment requirements answered are very high, lead to high expensive；Molecular sieve catalysts acidity is stronger, and initial temperature is low, but there is also by-product
Thing is many, the shortcoming of easy carbon distribution, easy in inactivation.Because above catalyst has the shortcoming of itself so that the preparation of dimethyl ether, invest
Greatly, high cost, leads to the production of dimethyl ether and use to be restricted.
Cn101214451a discloses heteropoly acid and transition metal oxide are supported on nanometer hzsm-5 zeolite and is formed
A kind of composite solid-acid catalyst.In the reaction of methanol gas phase dewatering preparing dimethy ether, when reaction temperature is 200oDuring c, methanol
High conversion rate in 85%, dimethyl ether selectivity is higher than 99.5%.But due to the specific surface of carrier relatively small it is impossible to load more
Many heteropoly acids are so as to relatively low in the catalysis activity of low temperature.
Cn00102506.6 discloses a kind of catalyst of preparing dimethyl ether by dewatering methanol.This catalyst is with aluminium oxide for carrying
Body, the active component of load is heteropoly acid, and anti-carbon deposit group is divided into titanium dioxide and lanthanum sesquioxide, using infusion process preparation.King
Keep state etc. [molecular science journal 2001,2 (17): 99-104] and report entitled h4siw12o40-la2o3/γ-al2o3Catalysis first
Dehydration of alcohols prepares the article of dimethyl ether.Above-mentioned catalyst has higher catalysis activity and selectivity in the reaction, silico-tungstic acid
Optimum load amount is 10wt% ~ 16wt%, and at ambient pressure, during for processing pure methanol feedstock, its selectivity is higher, but its low temperature is lived
Property bad, and during for aqueous methanol feedstock, its stability is bad, and selectivity and activity also decline therewith.
Content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of catalysis of producing dimethyl ether by dehydrating methanol
Agent and preparation method thereof.This catalyst not only has the characteristics that low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, Er Qiewen
Qualitative good.
Producing dimethyl ether by dehydrating methanol catalyst of the present invention, including active component, auxiliary agent and carrier, active component is miscellaneous many
Acid ammonium salt is shown in formula (1), and auxiliary agent is lanthana and/or cerium oxide, and carrier is silicon oxide；On the basis of the weight of catalyst, miscellaneous many
The content of acid ammonium salt is 1 % ~ 40 %, preferably 5% ~ 30%, the content that auxiliary agent is counted with oxide is for 1 % ~ 15 %, the content of carrier
For 45 % ~ 98 %, preferably 55 % ~ 94 %；
hm(nh4)nyx12o40(1)
Wherein x represents w or mo, and y represents si or p；When y represents si, m+n=4, n value is 0.1 ~ 1.0；When y represents p
When, m+n=3, n value is 0.1 ~ 1.0.
The property of described silica support is as follows: specific surface area is 480 ~ 800 m2/ g, pore volume is 0.60 ~ 0.90 ml/g,
Average pore diameter is 4.5 ~ 6.5 nm.
The preparation method of described producing dimethyl ether by dehydrating methanol catalyst, comprising:
(1) silica support is added in alkane solvent, then filters, be dried at room temperature for carrier surface aneroid
Phase；
(2) material obtaining step (1) is added in aqueous solutions of organic acids, stirs and steam to solution at 50 DEG C ~ 90 DEG C
Dry；
(3) material obtaining step (2) is added in the alkaline solution containing ammonium, through filtering, dry at 40 DEG C ~ 100 DEG C
Dry, or the material that step (2) is obtained adsorbs ammonia at 40 DEG C ~ 100 DEG C；
(4) mixed aqueous solution of auxiliary agent presoma and heteropoly acid is added in the material that step (3) obtains, 60 DEG C ~
Stir at 90 DEG C and be evaporated to solution；
(5) solid obtaining step (4) is in 90 DEG C ~ 120 DEG C drying 3 h ~ 12 h, then in 300 DEG C ~ 550 DEG C roastings 2
H ~ 6 h, obtains final product catalyst.
Silica support described in step (1) is adopted and is prepared with the following method:
A, template is added to containing in organic aqueous acid, obtains solutions i；
B, silicon source is added in solutions i, obtains solutions i i, then stir at 50 DEG C ~ 90 DEG C to becoming gel；
C, by gel in aged at room temperature 8 h ~ 24 h, then in 90 DEG C ~ 120 DEG C drying 3 h ~ 12 h, 300 DEG C ~
700 DEG C of roasting 2 h ~ 6 h, obtain silica support.
In step a, described template is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecane
Base sodium sulfate, triblock polymer p123, triblock polymer f127, triblock polymer f108, molecular weight be 1000 ~
One or more of 10000 Polyethylene Glycol, described template and sio in carrier2Mol ratio be 0.01 ~ 1.0；Described
Organic acid is one or more of citric acid, tartaric acid, malic acid, sio in described organic acid and carrier2Mol ratio be
0.1~1.0.
In step b, described silicon source is one or more of tetraethyl orthosilicate, Ludox.
In step (1), described alkane solvent is c5~c10One or more of liquid n-alkane.Alkane solvent with
The volume ratio of silica support is 1 ~ 3, and silica support adds the time being impregnated in alkane solvent to be generally 5 min ~ 20
min.
In step (2), described organic acid is one or more of citric acid, tartaric acid, malic acid.Described organic acid
With sio in carrier2Mol ratio be 0.05 ~ 0.5.
In step (3), the material that step (2) is obtained is added in the alkaline solution containing ammonium and is impregnated, dip time
Generally 5 min ~ 30 min.The solid absorption ammonia that step (2) is obtained, adsorption time is generally 5 min ~ 30 min.Step
Suddenly, in (3), the described alkaline solution containing ammonium is one or more of ammonia, sal volatile, ammonium bicarbonate soln.
In step (3), described ammonia can adopt pure ammonia, it would however also be possible to employ the gaseous mixture containing ammonia, in mixed gas
In addition to ammonia, other is noble gases such as one or more of nitrogen, argon etc..
In step (4), auxiliary agent presoma can be one or more of Lanthanum (III) nitrate, cerous nitrate；Described heteropoly acid is phosphorus
One or more of wolframic acid, silico-tungstic acid, phosphomolybdic acid.
Mesopore molecular sieve can also be added, in such as sba-15, sba-3, mcm-41 etc. in described silica support
One or more, molecular sieve weight content in the carrier below 10%, generally 1% ~ 8%.
Present invention also offers a kind of method of methanol dehydration dimethyl ether-preparing, wherein adopt the catalyst of the present invention.This
Invention preparing dimethyl ether by dewatering methanol catalyst is particularly well-suited to the higher methanol feedstock dewatering preparing dimethy ether reaction of water content.Described
Methanol feedstock water content be 10wt% ~ 20wt%, can from synthesis gas be obtained methanol.In the present invention, methanol dewatered
The reaction condition of standby dimethyl ether is as follows: reaction pressure 0 ~ 4.0 mpa, mass space velocity 1.0 h-1~4.0 h-1, reaction temperature 160
℃~240℃.
Catalyst of the present invention adopts the silica support of bigger serface, by specific method carried heteropoly acid and auxiliary agent
Component, makes heteropoly acid in catalyst exist with ammonium salts, and makes ammonium heteropoly acidses and the auxiliary agent can be equal in carrier surface
Even dispersion, catalyst not only has the characteristics that low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and good stability.
Specific embodiment
With reference to embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
(1) preparation of carrier:
Weigh 145.8g cetyl trimethylammonium bromide and 205g citric acid is made into mixed solution, by positive for 302ml silicic acid
Tetra-ethyl ester is added in mixed solution, stirs 2 h, then stirs at 70 DEG C to becoming gel, by gel in aged at room temperature 12 h,
Then 8 hs are dried at 110 DEG C, in 600 DEG C of roasting 3 h, obtain silica support, wherein cetyl trimethylammonium bromide
Mol ratio with silicon oxide is 0.3, and citric acid is 0.8 with the mol ratio of silicon oxide.Support is: specific surface area is 533
m2/ g, pore volume is 0.65 ml/g, and average pore diameter is 4.9 nm.
(2) preparation of catalyst:
The silica support of preparation is added in c6 alkane solvent, impregnates 10min, then filter, be dried at room temperature for
To carrier surface no liquid phase；It is then added to, containing in 25.6g Fructus Citri Limoniae aqueous acid, stir at 70 DEG C and be evaporated to solution；
The material obtaining is added to dipping 10min in sal volatile, is dried after filtration at 60 DEG C；It is then added to containing 13.3g
In the mixed aqueous solution of Lanthanum (III) nitrate and 15.6g phosphotungstic acid, stir at 70 DEG C and be evaporated to solution；By the solid obtaining at 110 DEG C
8.0 hs are dried, then in 500 DEG C of roasting 3.0 h, (nh are obtained4)0.5h2.5pw12o40-la2o3/sio2Catalyst, wherein la2o3
Content is 5wt%, (nh4)0.5h2.5pw12o40Content is 15wt%.
(3) catalyst characterization:
Surrounding in catalyst granules section and centre take a little, carry out elementary analysiss by sem to each point, result shows:
Promoter metal at surrounding each point and heteropoly acid ammonium salt content are substantially suitable, and middle each point is not detected by promoter metal and miscellaneous many
Acid ammonium salt, illustrates the catalyst using the method preparation, and its promoter metal and ammonium heteropoly acidses have on catalyst surface
Dispersion, and be not impregnated with duct.
(4) evaluation of catalyst:
The reaction of methanol (technical grade, >=98.5wt%) dewatering preparing dimethy ether is carried out in fixed-bed tube reactor, normal pressure,
Mass space velocity 2.0h-1, 180 DEG C of reaction temperature.Before reaction, catalyst is in n2Activate 2 h in 400 DEG C under protection, be then down to
After reaction temperature starts to react 4 hours, product is analyzed by gas chromatogram, calculates selectivity and conversion ratio, the results are shown in Table 1.
Embodiment 2
(1) preparation of carrier:
Weigh 200g cetyl trimethylammonium bromide and 105.7g citric acid is made into mixed solution, by positive for 250ml silicic acid
Tetra-ethyl ester is added in mixed solution, stirs 2 h, then stirs at 70 DEG C to becoming gel, by gel in aged at room temperature 12 h,
Then 8 hs are dried at 110 DEG C, in 600 DEG C of roasting 3 h, obtain silica support, wherein cetyl trimethylammonium bromide
Mol ratio with silicon oxide is 0.5, and citric acid is 0.5 with the mol ratio of silicon oxide.Support is: specific surface area is 570
m2/ g, pore volume is 0.72 ml/g, and average pore diameter is 5.1 nm.
(2) preparation of catalyst:
The silica support of preparation is added in c6 alkane solvent, impregnates 10min, then filter, be dried at room temperature for
To carrier surface no liquid phase；It is then added to, containing in 42.3g Fructus Citri Limoniae aqueous acid, stir at 70 DEG C and be evaporated to solution；
The material obtaining is added to dipping 10min in sal volatile, is dried after filtration at 60 DEG C；It is then added to containing 37.2g
In the mixed aqueous solution of Lanthanum (III) nitrate and 20.8g phosphotungstic acid, stir at 70 DEG C and be evaporated to solution；By the solid obtaining at 110 DEG C
8.0 hs are dried, then in 470 DEG C of roasting 3.0 h, (nh are obtained4)0.7h2.3pw12o40-la2o3/sio2Catalyst, wherein la2o3
Content is 14wt%, (nh4)0.7h2.3pw12o40Content is 20wt%.
With embodiment 1, the selectivity of conversion ratio and crackate the results are shown in Table 1 for the evaluation of catalyst.
Embodiment 3
(1) preparation of carrier:
Weigh 316g cetyl trimethylammonium bromide and 62.4g citric acid is made into mixed solution, by positive for 246ml silicic acid four
Ethyl ester is added in mixed solution, stirs 2 h, then stirs at 70 DEG C to becoming gel, by gel in aged at room temperature 12 h, so
8 hs are dried at 110 DEG C afterwards, in 600 DEG C of roasting 3 h, obtain silica support, wherein cetyl trimethylammonium bromide with
The mol ratio of silicon oxide is 0.8, and citric acid is 0.3 with the mol ratio of silicon oxide.Support is: specific surface area is 612 m2/
G, pore volume is 0.76 ml/g, and average pore diameter is 5.0 nm.
(2) preparation of catalyst:
The silica support of preparation is added in c6 alkane solvent, impregnates 10min, then filter, be dried at room temperature for
To carrier surface no liquid phase；It is then added to, containing in 62.4g Fructus Citri Limoniae aqueous acid, stir at 70 DEG C and be evaporated to solution；
The material obtaining is added to dipping 10min in sal volatile, is dried after filtration at 60 DEG C；It is then added to containing 26.6g
In the mixed aqueous solution of Lanthanum (III) nitrate and 25.9g phosphotungstic acid, stir at 70 DEG C and be evaporated to solution；By the solid obtaining at 110 DEG C
8.0 hs are dried, then in 520 DEG C of roasting 3.0 h, (nh are obtained4)0.2h2.8pw12o40-la2o3/sio2Catalyst, wherein la2o3
Content is 10wt%, (nh4)0.2h2.8pw12o40Content is 25wt%.
With embodiment 1, the selectivity of conversion ratio and crackate the results are shown in Table 1 for the evaluation of catalyst.
Embodiment 4
In embodiment 3, cetyl trimethylammonium bromide is changed to 628g p123, Lanthanum (III) nitrate is changed to 25.2g
Cerous nitrate,, with embodiment 3, gained catalyst is (nh for remaining4)0.2h2.8pw12o40-ceo2/sio2, wherein ceo2Contain
Measure as 10wt%, (nh4)0.2h2.8pw12o40Content is 25wt%, p123 and sio2Mol ratio be 0.1.Support is: compares table
Area is 575 m2/ g, pore volume is 0.81 ml/g, and average pore diameter is 5.6 nm.
With embodiment 1, the selectivity of conversion ratio and crackate the results are shown in Table 1 for the evaluation of catalyst.
Embodiment 5
In embodiment 3, phosphotungstic acid is changed to silico-tungstic acid, dipping 10min is changed to inhale in sal volatile
Attached 10v% nh3/ ar gaseous mixture 10min,, with embodiment 3, gained catalyst is (nh for remaining4)0.2h3.8siw12o40-
la2o3/sio2, wherein la2o3Content is 10wt%, (nh4)0.2h3.8siw12o40Content is 25wt%.
With embodiment 1, the selectivity of conversion ratio and crackate the results are shown in Table 1 for the evaluation of catalyst.
Embodiment 6
Compared with Example 3, difference is: in evaluating catalyst, methanol feedstock is changed into and is changed to purity and is
The methanol of 80wt%, wherein aqueous 20wt%, remaining is with embodiment 3.
Embodiment 7
Catalyst is obtained according to embodiment 3, the appreciation condition according to embodiment 3 has carried out 100 h to catalyst and stablized
Property evaluation experimental, the selectivity of conversion ratio and crackate the results are shown in Table 2.
Comparative example 1
In embodiment 3, carrier is added directly into the mixed aqueous solution containing 26.6g Lanthanum (III) nitrate and 25.5g phosphotungstic acid
In, stir at 70 DEG C and be evaporated to solution；By the solid obtaining in 110 DEG C of drying 8.0 h, then in 350 DEG C of roasting 3.0 h,
Prepared h3pw12o40-la2o3/sio2Catalyst, wherein la2o3Content is 10wt%, h3pw12o40Content is 25wt%.
With embodiment 1, the selectivity of conversion ratio and crackate the results are shown in Table 1 for the evaluation of catalyst.
Comparative example 2
Compared with comparative example 1, difference is: in evaluating catalyst, methanol feedstock is changed into and is changed to purity and is
The methanol of 80wt%, wherein aqueous 20wt%, remaining is with comparative example 1.
Comparative example 3
Catalyst is obtained according to comparative example 1, the appreciation condition according to comparative example 1 has carried out 100 h to catalyst and stablized
Property evaluation experimental, the selectivity of conversion ratio and crackate the results are shown in Table 2.
The conversion ratio of 1 each catalyst of table and selectivity
Table 2 stability test evaluation result
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 7 | 86.8 | 99.2 |
| Comparative example 3 | 83.8 | 84.5 |
Claims (18)
1. a kind of producing dimethyl ether by dehydrating methanol catalyst, including active component, auxiliary agent and carrier, active component is heteropoly acid ammonium
Formula (1) is shown in by salt, and auxiliary agent is lanthana and/or cerium oxide, and carrier is silicon oxide；On the basis of the weight of catalyst, heteropoly acid ammonium
The content of salt is 1% ~ 40%, and for 1 % ~ 15 %, the content of carrier is 45 % ~ 98 % to the content that auxiliary agent is counted with oxide；
hm(nh4)nyx12o40(1)
Wherein x represents w or mo, and y represents si or p；When y represents si, m+n=4, n value is 0.1 ~ 1.0；When y represents p, m
+ n=3, n value is 0.1 ~ 1.0.
2. according to the catalyst described in claim 1 it is characterised in that: on the basis of the weight of catalyst, ammonium heteropoly acidses
Content is 5% ~ 30%, and for 1 % ~ 15 %, the content of carrier is 55 % ~ 94 % to the content that auxiliary agent is counted with oxide.
3. according to the catalyst described in claim 1 or 2 it is characterised in that: the property of described silica support is as follows: specific surface
Amass as 480 ~ 800 m2/ g, pore volume is 0.60 ~ 0.90 ml/g, and average pore diameter is 4.5 ~ 6.5 nm.
4. the preparation method of catalyst described in claim 1, comprising:
(1) silica support is added in alkane solvent, then filters, be dried at room temperature for carrier surface no liquid phase；
(2) material obtaining step (1) is added in aqueous solutions of organic acids, stirs and be evaporated to solution at 50 DEG C ~ 90 DEG C；
(3) material obtaining step (2) is added in the alkaline solution containing ammonium, through filtering, is dried at 40 DEG C ~ 100 DEG C, or
The material that step (2) obtains is adsorbed ammonia at 40 DEG C ~ 100 DEG C by person；
(4) mixed aqueous solution of auxiliary agent presoma and heteropoly acid is added in the material that step (3) obtains, at 50 DEG C ~ 90 DEG C
Under stir and be evaporated to solution；
(5) solid obtaining step (4) is in 90 DEG C ~ 120 DEG C drying 3 h ~ 12 h, then 300 DEG C ~ 550 DEG C roasting 2 h ~ 6
H, obtains final product catalyst.
5. in accordance with the method for claim 4 it is characterised in that: the silica support described in step (1) is adopted with the following method
Preparation:
A, template is added to containing in organic aqueous acid, obtains solutions i；
B, silicon source is added in solutions i, obtains solutions i i, then stir at 50 DEG C ~ 90 DEG C to becoming gel；
C, by gel in aged at room temperature 8 h ~ 24 h, then in 90 DEG C ~ 120 DEG C drying 3 h ~ 12 h, at 300 DEG C ~ 700 DEG C
Roasting 2 h ~ 6 h, obtains silica support.
6. in accordance with the method for claim 5 it is characterised in that: in step a, described template be cetyl trimethyl bromine
Change ammonium, hexadecyltrimethylammonium chloride, sodium lauryl sulphate, triblock polymer p123, triblock polymer f127, three
Block polymer f108, molecular weight are one or more of 1000 ~ 10000 Polyethylene Glycol.
7. in accordance with the method for claim 5 it is characterised in that: described template and sio in carrier2Mol ratio be
0.01~1.0.
8. in accordance with the method for claim 5 it is characterised in that: organic acid described in step a be citric acid, tartaric acid, Herba Marsileae Quadrifoliae
One or more of fruit acid, described organic acid and sio in carrier2Mol ratio be 0.1 ~ 1.0.
9. in accordance with the method for claim 5 it is characterised in that: in step b, described silicon source is tetraethyl orthosilicate, silicon is molten
One or more of glue.
10. in accordance with the method for claim 4 it is characterised in that: in step (1), described alkane solvent is c5~c10Liquid
One or more of n-alkane, alkane solvent is 1 ~ 3 with the volume ratio of silica support.
11. in accordance with the method for claim 4 it is characterised in that: in step (2), described organic acid be citric acid, winestone
One or more of acid, malic acid；Described organic acid and sio in carrier2Mol ratio be 0.05 ~ 0.5.
12. in accordance with the method for claim 4 it is characterised in that: in step (3), the described alkaline solution containing ammonium is ammonia
One or more of water, sal volatile, ammonium bicarbonate soln.
13. in accordance with the method for claim 4 it is characterised in that: in step (3), described ammonia adopts pure ammonia, or
Using the gaseous mixture containing ammonia, in mixed gas in addition to ammonia, other is noble gases.
14. in accordance with the method for claim 4 it is characterised in that: in step (4), auxiliary agent presoma be Lanthanum (III) nitrate, cerous nitrate
One or more of；Described heteropoly acid is one or more of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
15. in accordance with the method for claim 4 it is characterised in that: in described silica support add mesopore molecular sieve
One or more of sba-15, sba-3, mcm-41, mesopore molecular sieve weight content in the carrier is below 10%.
A kind of 16. methods of methanol dehydration dimethyl ether-preparing are it is characterised in that adopt the arbitrary described catalysis of claim 1 ~ 3
Agent.
17. in accordance with the method for claim 16 it is characterised in that: in described methanol feedstock water content be 10wt% ~
20wt%.
18. according to the method described in claim 16 or 17 it is characterised in that: the reaction condition of methanol dehydration dimethyl ether-preparing is such as
Under: reaction pressure 0 ~ 4.0mpa, mass space velocity 1.0h-1~4.0 h-1, 160 DEG C ~ 240 DEG C of reaction temperature.
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| CN106944114B (en) * | 2016-01-07 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of utilization method of useless hydrotreating catalyst |
| CN106944138B (en) * | 2016-01-07 | 2019-07-12 | 中国石油化工股份有限公司 | A kind of utilization method of useless hydrogenation catalyst |
| CN109926074B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | 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 |
| 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 |
| CN109926094B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308987A (en) * | 2000-02-17 | 2001-08-22 | 东北师范大学 | Supported heteropolyacid catalyst for preparing dimethyl ether by methanol dehydration and production method thereof |
| JP2006088061A (en) * | 2004-09-24 | 2006-04-06 | Hokkaido Univ | Composition composed of salt of heteropoly acid and inorganic oxide, and method for producing the same |
| CN1837170A (en) * | 2006-02-21 | 2006-09-27 | 汪荣华 | Process for preparing dimethyl enther by vapour catalytic dehydration of methanol with high-activity dipping-type heteropoly acid as catalyst |
| CN101380585A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Wide temperature type methanol dehydration catalyst for producing dimethyl ether and preparation method thereof |
| CN101722001A (en) * | 2008-10-10 | 2010-06-09 | 北京石油化工学院 | Composite catalyst for dimethyl ether synthesis and preparation method and application thereof |
-
2013
- 2013-11-03 CN CN201310532077.9A patent/CN104588106B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308987A (en) * | 2000-02-17 | 2001-08-22 | 东北师范大学 | Supported heteropolyacid catalyst for preparing dimethyl ether by methanol dehydration and production method thereof |
| JP2006088061A (en) * | 2004-09-24 | 2006-04-06 | Hokkaido Univ | Composition composed of salt of heteropoly acid and inorganic oxide, and method for producing the same |
| CN1837170A (en) * | 2006-02-21 | 2006-09-27 | 汪荣华 | Process for preparing dimethyl enther by vapour catalytic dehydration of methanol with high-activity dipping-type heteropoly acid as catalyst |
| CN101380585A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Wide temperature type methanol dehydration catalyst for producing dimethyl ether and preparation method thereof |
| CN101722001A (en) * | 2008-10-10 | 2010-06-09 | 北京石油化工学院 | Composite catalyst for dimethyl ether synthesis and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| B.Y. Giri,et al.Esterification of palmitic acid on the ammonium salt of 12-tungstophosphoric acid: The infl * |
| H4SiW12O40-La2O3/γ-Al2O3催化甲醇脱水制备二甲醚;王守国等;《分子科学学报》;20010630;第17卷(第2期);第788-792页 * |
| uence of partial proton exchange on the activity of the catalyst，.《Catalysis Communications》.2005,第6卷(第12期),第788-792页. * |
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