CN101823005A - Catalyst for preparing dimethyl ether from low-temperature methanol by gas phase de-hydration, preparation method and application - Google Patents
Catalyst for preparing dimethyl ether from low-temperature methanol by gas phase de-hydration, preparation method and application Download PDFInfo
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Abstract
The invention provides a catalyst for preparing dimethyl ether from low-temperature methanol by gas phase de-hydration, a preparation method and application thereof. The catalyst is a metal oxide inclusive perfluorosulfonic acid ion-exchange resin and has a specific surface of 570 to 1,000 m<2>/g. The preparation method comprises the following steps of: preparing perfluorosulfonic acid ion-exchange resin aqueous solution; preparing a metal oxide sol; preparing a gel; aging the gel; drying the gel; acidifying and washing the dried gel; and drying again and the like to obtain the target catalyst. The preparation method is characterized in that: the pH value of the solution is regulated to be 3.5 to 5.8 when the gel is prepared. The catalyst has high specific surface, high low-temperature activity for preparing the dimethyl ether from the methanol by a gas phase de-hydration reaction, and high dimethyl ether yield.
Description
Technical field
The present invention relates to dimethyl ether catalyst for synthesizing field, be specifically related to be used for the metal oxide containing perfluorinated sulfonic acid ion-exchange resin catalyst and the preparation method and the application that utilize the sol-gel process preparation of low-temp methanol gas-phase dehydration.
Background technology
Dimethyl ether is broad-spectrum a kind of ether in the chemical industry, has characteristics such as nontoxic, safety, calorific value height, can be used as propellant, diesel fuel, domestic fuel, also is the intermediate of coal preparing liquid fuel simultaneously.It also is important basic chemical industry intermediate simultaneously, the relevant purposes [CN100379491C] widely at aspects such as pharmacy, agricultural chemicals, dyestuff, daily-use chemical industries.
The production of initial dimethyl ether be with the concentrated sulfuric acid as dehydration catalyst, this method has bigger environmental pollution and to the seriously corroded of equipment.The traditional production method of dimethyl ether is to use methanol steam at 350～400 ℃, under the pressure of 1.5MPa, makees catalyst with aluminum phosphate and makes.Improve it nearly decades, substituted the concentrated sulfuric acid with solid acid, be representative wherein, on active component, can simply be divided into alumina series catalyst and molecular sieve series catalysts [CN101380585A] again with alundum (Al, modification alundum (Al, molecular sieve, aluminum phosphate.Japan Patent JP20010261933 zirconia, tripoli and/or titanium oxide modified aluminas are done methanol dehydration catalyst; U.S. Pat 4595785 is with the γ-Al of aluminium titanates modification
2O
3For catalyst can improve reaction rate and prevent carbon distribution; U.S. Pat 6740783B1 is with the sieve peg-raking catalyst of containing metal or amine; Chinese patent CN101204669A is catalyst with the molecular sieve, and it contains a kind of zeolite-type molecular sieves and at least a non-zeolitic molecular sieves at least.
In the prior art, methanol dehydration needs still to carry out that (temperature is all more than 240 ℃ under higher temperature, and optimum operating temperature is many at 270～300 ℃), this just causes investment of production equipment and operating cost higher, and methanol conversion and selectivity low [Zhang Liwei. the preparation of solid acid catalyst and application [D] in the Dehydration of methanol, Zhejiang University, 2008].Therefore, new catalyst is significant preferably to develop a kind of low temperature active.
Theoretically, for reaction of preparing dimethyl ether from methanol by dehydration, strong more its activity of the acidity of catalyst is just high more, but acidity easily makes catalyst junction charcoal and generation accessory substance too by force, and rapid inactivation.If acidity too a little less than, just may cause the reaction temperature height, the pressure height, reactivity is low or do not have an activity.
Chinese patent CN1170373A discloses " obtained by sol-gel process, be used for the perfluorinate ion-exchange polymer of isomerisation of olefin and the porous compound particles of metal oxide ".The required pH value of this technology is by adding alkali at PFIEP solution or add PFIEP solution in alkali, or replaces regulating with acid or alkali by add metal oxide in solution.The acid amount is few even not to add acid owing to add when this patent prepares gel, and pH is higher during gel, and it is not very big causing the xerogel specific area, not obvious as the advantage of solid acid catalyst, particularly, can not satisfy the requirement of methanol gas phase dewatering preparing dimethy ether.
Summary of the invention
At the characteristics and the deficiency of existing dimethyl ether production method, the present invention utilizes metal oxide containing perfluorinated sulfonic resin to be methanol dehydration catalyst first, and reaction temperature is low, methanol conversion and dimethyl ether selectivity height.
Perfluorinated sulfonic acid ion exchange resin is tetrafluoroethene and the copolymer that has the perfluoroalkyl vinyl ether of sulfonic acid group, in perfluorinated sulfonic acid ion exchange resin molecule, what sulfonic acid group connected is perfluoroalkyl, and the F electronegativity is very strong, makes perfluorinated sulfonic acid ion exchange resin acid strength and 100%H
2SO
4Quite, and because the F atomic radius is relatively large, carbochain is played a very good protection, therefore, perfluorinated sulfonic acid ion exchange resin has the high and good characteristics of high-temperature stability of acid strength, can be used as solid acid catalyst.But perfluorinated sulfonic acid ion exchange resin specific area is very little, pact≤0.02m
2/ g, the sulfonic group utilization rate is low, and its advantage as solid acid catalyst is difficult to embody.Comprehensive above characteristics, the present invention adopts sol-gel process to prepare the perfluorinated sulfonic acid ion exchange resin complexes that metal oxide contains, and is the catalyst methanol gas phase dewatering preparing dimethy ether with it.
The present invention realizes by following process:
1. prepare perfluorinated sulfonic acid amberlite lipoprotein solution.The preparation method of perfluorinated sulfonic acid amberlite lipoprotein solution of the present invention itself is known, can be referring to Wang Hai etc., perfluorinated sulfonic resin Nafion to this
The preparation of NR50 solution. applied chemistry, 2001,18 (10): 798-801.The present invention is put into perfluorinated sulfonic acid ion exchange resin and is heated to 180 ℃～250 ℃ in the reactor with alcohol solution, preferred 190 ℃～200 ℃, obtain containing perfluorinated sulfonic acid ion exchange resin weight percentage and be 2%～7% solution.
Described perfluorinated sulfonic acid amberlite lipoprotein solution is the alcohol solution of perfluorinated sulfonic acid ion exchange resin, the preferred bi-component solvent of alcohol solution or multicomponent solvent, more preferably multicomponent solvent.Alcohols can be used methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol etc., particular methanol, normal propyl alcohol and isopropyl alcohol.And it is 10～70 ︰ 90～30 that alcohol solution volume ratio composition is preferably: Shui ︰ alcohols; The alcohol solution volume ratio is formed more preferably, and: Shui ︰ Yi Bing Chun ︰ methyl alcohol is 30～70 ︰, 65～15 ︰ 5～15; Shui ︰ Yi Bing Chun ︰ methyl alcohol=45 ︰, 45 ︰ 10(volume ratios most preferably).
Described perfluorinated sulfonic acid amberlite lipoprotein solution prepares in reactor in 4～8MPa, and temperature is 180 ℃～250 ℃, is preferably 190 ℃～200 ℃.
2. preparation metal oxide sol.Described " metal oxide " is meant the oxide of metallicity or semimetal, comprising: the oxide of alundum (Al, silica, titanium dioxide, germanium oxide, zirconia, alumina silicate, silicic acid oxygen zirconium or iron etc.Metal oxide is preferred: silica, titanium dioxide or alundum (Al; Most preferably be silica.Silica can be obtained by alkoxyl silicone or silicate (as potassium silicate, sodium metasilicate etc.).The present invention is the example explanation with the positive tetraethyl orthosilicate of alkoxyl silicone.
At 20～60 ℃, under preferred 40 ℃ of conditions, the positive tetraethyl orthosilicate of 50～150mL, 15～100mL absolute ethyl alcohol, 5～80mL deionized water joined stir 5～20 minutes in the flask, so that it fully mixes, use watery hydrochloric acid regulator solution pH to 0.5～2.5 then, stirred 30～90 minutes.
3. preparation gel: add 15～150mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, with NaOH solution regulator solution pH to 3.5～5.8 of 0.05～2mol/L, treat solution gel, gel time can change by several hours from moment;
4. gel ageing:, placed 20～30 hours under preferred 40 ℃ of conditions at 20～60 ℃;
5. gel drying made xerogel: 80～110 ℃ of following freeze-day with constant temperature 40～60 hours;
6. xerogel acidifying, washing: xerogel is with 1～5mol/L sulfuric acid, hydrochloric acid or nitric acid acidifying, and then with the unnecessary acid of deionized water flush away;
7. made the target catalyst in 20～30 hours at 80～110 ℃ of following freeze-day with constant temperature again.
Described catalyst adopts above-mentioned sol-gel process, perfluorinated sulfonic acid amberlite lipoprotein solution is included in the metal oxide network, it is 1%～30% that the perfluorinated sulfonic acid ion exchange resin that contains accounts for target catalyst weight percentage composition, preferred 5%～20%, more preferably 5%～15%.
The specific surface of described catalyst is 570～1000m
2/ g, pore volume are 0.2～1.0mL/g, average pore size 1.9～3.3nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.
The present invention has added absolute ethyl alcohol during the preparation metal oxide sol in catalyst preparation process, be convenient to positive tetraethyl orthosilicate and contact with water, shortened the colloidal sol preparation time, and catalyst activity component branch is more even.
The present invention is in catalyst preparation process, and the pH lower (3.5～5.8) during the preparation gel makes the bigger (570～1000m of target specific surface area of catalyst
2/ g), the reaction efficiency of perfluorinated sulfonic resin is higher, has reduced the catalyst cost; Simultaneously, catalyst low temperature (170～200 ℃) activity and selectivity can make the operating cost of producing dimethyl ether reduce greatly apparently higher than existing catalyst.
The physical and chemical performance assay method of catalyst is as follows:
1. specific area, pore volume and average pore-size distribution adopt the ASAP of U.S. Micromerities company
TM2020 type gas absorption instrument low-temperature nitrogen adsorption methods, specific area is the BET specific area;
2. adopt Japanese D/max2000X-x ray diffractometer x analysis of catalyst thing phase of science;
3. thermogravimetric: the SDTQ600 thermogravimetric differential thermal analyzer that adopts U.S. TA company to produce carries out thermogravimetric-differential thermal analysis, and represents the weight percentage of active component perfluorinated sulfonic acid ion exchange resin in the catalyst with the thermal weight loss between 365 ℃～570 ℃.
The activity of such catalysts evaluation method is as follows:
Methanol gas phase dehydration is reflected in the high-pressure micro-device and carries out, and catalyst is positioned at the reaction flat-temperature zone.In fixed bed reactors, pack into 20～40 purpose catalyst of 5～15mL, two ends filling 60～80 purpose quartz sands.Enter beds by the methyl alcohol of micro-sampling pump continuous sample introduction after via the vaporizer gasification, the Application of Catalyst condition is: pressure 0.15～0.4MPa; 160～240 ℃ of temperature; The methanol liquid air speed is 0.5～3h
-1Reaction condition is preferably: 170～200 ℃ of temperature, more preferably 175～180 ℃; Pressure 0.2MPa; Methanol liquid air speed 1h
-1Product Agilent6890N type gas chromatograph on-line determination.
The catalyst of the present invention's preparation has high-specific surface area, and is good to the reaction of preparing dimethyl ether from methanol by dehydration low temperature active, the yield height of dimethyl ether.
The specific embodiment
Below only be preferred embodiment of the present invention, can not limit scope of the present invention with this.Promptly the equalization of being done according to the present patent application claim generally changes and modifies, and all should still belong in the scope that patent of the present invention contains.
Perfluorinated sulfonic acid ion exchange resin is tetrafluoroethene and the copolymer that has the perfluoroalkyl vinyl ether of sulfonic acid group, new material Science and Technology Ltd. buys from Divine Land, Eastern Mountain, Shandong, outward appearance is a translucent particle, average grain diameter is 5～7mm, exchange capacity is 1.13～1.17mmol/g, and density is 1.93～2.03g/cm
3
Embodiment 1
Perfluorinated sulfonic acid ion exchange resin is put into and is heated to 190 ℃～200 ℃ in the reactor with volume ratio Wei Shui ︰ Yi Bing Chun ︰ methyl alcohol=alcohol solution of 45 ︰, 45 ︰ 10, about pressure 6MPa, obtain containing perfluorinated sulfonic acid ion exchange resin weight percentage and be 5% solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 19.52mL absolute ethyl alcohol, 8mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Use watery hydrochloric acid regulator solution pH to 0.5 then, stir 60min.In metal oxide sol, add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution, equal 4, solution 130min gel with the NaOH solution regulator solution pH of 0.2mol/L.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific surface area of catalyst (being determined by the BET method), pore volume and aperture are respectively: 669m
2/ g, 0.344mL/g, 2.06nm.Measure as can be known by crystalline phase that catalyst is an amorphous form, by thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is carried out in fixed bed reactors, and catalyst is positioned at the reaction flat-temperature zone, and quartz sand is filled at two ends.The Application of Catalyst condition is: catalyst 10mL, 175～180 ℃ of reaction temperatures, pressure 0.2MPa, methanol liquid volume space velocity 1h
-1
After measured, methanol conversion is 54.49%, and the dimethyl ether selectivity is 99.97%.
Embodiment 2
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 32.53mL absolute ethyl alcohol, 8mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.In metal oxide sol, add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution, equal 5, solution 180min gel with the NaOH solution regulator solution pH of 1mol/L.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 100 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 823m
2/ g, 0.441mL/g, 2.14nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 45.78%, and the dimethyl ether selectivity is 99.98%.
Embodiment 3
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 32.53mL absolute ethyl alcohol, 19mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.In metal oxide sol, add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution, equal 3.5, solution 210min gel with the NaOH solution regulator solution pH of 1mol/L.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 100 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 862m
2/ g, 0.433mL/g, 2.01nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 56.21%, and the dimethyl ether selectivity is 99.96%.
Embodiment 4
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 45.55mL absolute ethyl alcohol, 8mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 2.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.In metal oxide sol, add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution, equal 5.8, solution 18min gel with the NaOH solution regulator solution pH of 2mol/L.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L sulfuric acid acidation, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 100 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 985m
2/ g, 0.881mL/g, 3.29nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 32.48%, and the dimethyl ether selectivity is 99.99%.
Embodiment 5
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 19.52mL absolute ethyl alcohol, 16mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 5.8 with the NaOH solution regulator solution pH of 2mol/L, solution is supergrip very.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel is with the acidifying of 2mol/L nitric acid, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 100 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 681m
2/ g, 0.465mL/g, 2.728nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 42.04%, and the dimethyl ether selectivity is 99.99%.
Embodiment 6
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 45.55mL absolute ethyl alcohol, 16mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 0.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 5 with the NaOH solution regulator solution pH of 1mol/L, solution is supergrip very.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 747m
2/ g, 0.48mL/g, 2.57nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 50.98%, and the dimethyl ether selectivity is 99.98%.
Embodiment 7
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 19.52mL absolute ethyl alcohol, 24mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 2.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 5 with the NaOH solution regulator solution pH of 1mol/L, solution is supergrip very.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 648m
2/ g, 0.33mL/g, 2.05nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 52.51%, and the dimethyl ether selectivity is 99.98%.
Embodiment 8
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 32.53mL absolute ethyl alcohol, 24mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 0.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 5.8 with the NaOH solution regulator solution pH of 1mol/L, solution is supergrip very.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 598m
2/ g, 0.30mL/g, 2.0nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 51.25%, and the dimethyl ether selectivity is 99.98%.
Embodiment 9
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 50mL, 45.55mL absolute ethyl alcohol, 24mL deionized water be added in the 250mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 17mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 4 with the NaOH solution regulator solution pH of 0.5mol/L, solution is supergrip very.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 711m
2/ g, 0.37mL/g, 2.08nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 51.79%, and the dimethyl ether selectivity is 99.98%.
Embodiment 10
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 150mL, 97.5mL absolute ethyl alcohol, 72mL deionized water be added in the 500mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 51mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 4 with the NaOH solution regulator solution pH of 0.5mol/L, solution is supergrip very.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 655m
2/ g, 0.324mL/g, 1.978nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 5%.
Application of Catalyst is with example 1.After measured, methanol conversion is 55.45%, and the dimethyl ether selectivity is 99.98%.
Embodiment 11
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 100mL, 65mL absolute ethyl alcohol, 48mL deionized water be added in the 500mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 69.6mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 4 with the NaOH solution regulator solution pH of 0.5mol/L, solution is through the 135min gel.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 640m
2/ g, 0.318mL/g, 1.987nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 10%.
Application of Catalyst is with example 1.After measured, methanol conversion is 82.74%, and the dimethyl ether selectivity is 99.94%.
Embodiment 12
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 100mL, 65mL absolute ethyl alcohol, 48mL deionized water be added in the 500mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 100.4mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 4 with the NaOH solution regulator solution pH of 0.5mol/L, solution is through the 140min gel.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 598m
2/ g, 0.305mL/g, 2.04nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 15%.
Application of Catalyst is with example 1.After measured, methanol conversion is 89.04%, and the dimethyl ether selectivity is 99.93%.
Embodiment 13
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 100mL, 65mL absolute ethyl alcohol, 48mL deionized water be added in the 500mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 134mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 4 with the NaOH solution regulator solution pH of 0.5mol/L, solution is through the 210min gel.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 588m
2/ g, 0.302mL/g, 2.05nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 20%.
Application of Catalyst is with example 1.After measured, methanol conversion is 90.62%, and the dimethyl ether selectivity is 99.90%.
Embodiment 14
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, the positive tetraethyl orthosilicate of 100mL, 65mL absolute ethyl alcohol, 48mL deionized water be added in the 500mL flask stir 10min, so that it fully mixes.Equal 1.5 with watery hydrochloric acid regulator solution pH value then, stir 60min.Add 209mL perfluorinated sulfonic acid amberlite lipoprotein solution in metal oxide sol, equal 4 with the NaOH solution regulator solution pH of 0.5mol/L, solution is through the 210min gel.At 40 ℃ of following ageing 24h, then at 95 ℃ of following freeze-day with constant temperature 48h.Xerogel 2mol/L hcl acidifying, and then with the unnecessary acid of deionized water flush away; Made the target catalyst in 20 hours at 110 ℃ of following freeze-day with constant temperature again.Specific area (being determined by the BET method), pore volume and aperture are respectively: 570m
2/ g, 0.297mL/g, 2.08nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 30%.
Application of Catalyst is with example 1.After measured, methanol conversion is 90.96%, and the dimethyl ether selectivity is 99.92%.
Embodiment 15
Get 11 controlling catalysts of embodiment, its application is carried out in fixed bed reactors, and catalyst is positioned at the reaction flat-temperature zone, and quartz sand is filled at two ends.The Application of Catalyst condition is: catalyst 10mL, 183 ℃ of reaction temperatures, pressure 0.2MPa, methanol liquid volume space velocity 1h
-1
Through 180h, conversion of methanol maintains 90.1%, and the dimethyl ether selectivity maintains 99.98%.
Embodiment 16
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, 75mL butyl titanate, 58mL absolute ethyl alcohol joined in the 250mL flask stir 10min, 38mL perfluor sulfoacid resin solution and 24mL deionized water slowly are added drop-wise in the alcoholic solution of butyl titanate, with watery hydrochloric acid regulator solution pH to 3.5, and stirring 30min, gel after about 1.5 hours.Ageing, drying, acidifying, washing, drying steps make the target catalyst with embodiment 1.Specific area (being determined by the BET method), pore volume and aperture are respectively: 632m
2/ g, 0.33mL/g, 2.09nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 10%.
Application of Catalyst is with example 1.After measured, methanol conversion is 80.35%, and the dimethyl ether selectivity is 99.96%.
Embodiment 17
Adopt the mode of embodiment 1 to prepare perfluorinated sulfonic acid amberlite lipoprotein solution.
Under 40 ℃, 57mL tri sec-butoxy aluminum, 58mL absolute ethyl alcohol and 24mL deionized water joined in the 250mL flask stir 10min, so that it fully mixes.Be 1.5 with watery hydrochloric acid regulator solution pH then, stirred 60 minutes, in metal oxide, drip the 23mL perfluor sulfoacid resin solution, equal 3.5, gel after about 3 hours with the NaOH solution regulator solution pH of 0.5mol/L.Ageing, drying, acidifying, washing, drying steps make the target catalyst with embodiment 1.Specific area (being determined by the BET method), pore volume and aperture are respectively: 613m
2/ g, 0.32mL/g, 2.09nm.Measuring as can be known by crystalline phase, catalyst is an amorphous form.By thermogravimetric analysis as can be known perfluorinated sulfonic acid ion exchange resin mass content be 10%.
Application of Catalyst is with example 1.After measured, methanol conversion is 79.43%, and the dimethyl ether selectivity is 99.97%.
Comparative Examples 1
The method that adopts the disclosed sol-gel process of Chinese patent CN1170373A to prepare the porous compound particles of perfluorinate ion-exchange polymer and metal oxide prepares catalyst, stir the positive tetraethyl orthosilicate of 108g, 28g distilled water and 2.4g0.04M hydrochloric acid solution 2.5 hours get settled solution.The NaOH solution that adds 55mL0.4M in the perfluor sulfoacid resin solution (5%) that 75mL is stirring continues to stir 15 minutes.Silica containing solution is joined the solution of the perfluorinated sulfonic resin that is stirring fast, moment system form gel.With gel 95 ℃ of dryings 2 days, then in a vacuum in 125 ℃ of dried overnight.Abrasive gel, and by 10 purpose sieves, then with 3.5MHCl(250mL acid) reacidizing is 1 hour, washs solid collected by filtration again with the 250mL deionized water.Acidifying, washing and filtration repeat 5 times altogether, after the washing, solid are made the target catalyst in 24 hours in 100 ℃ of dryings in a vacuum the last time.Specific area (being determined by the BET method), pore volume and aperture are respectively: 350m
2/ g, 0.74mL/g and 8.3nm.Resin content is 10%.
Application of Catalyst is with embodiment 1.After measured, methanol conversion is 60.5%, and the dimethyl ether selectivity is 99.98%.Comparative Examples is identical therewith for embodiment 11 gained catalyst activity constituent contents, and methanol conversion exceeds 22%.
Claims (10)
1. low-temp methanol gas phase dewatering preparing dimethy ether catalyst is characterized in that: be that metal oxide contains perfluorinated sulfonic acid ion exchange resin, the specific area of catalyst is 570～1000m
2/ g.
2. the described Preparation of catalysts method of claim 1 comprises: preparation perfluorinated sulfonic acid ion exchange resin alcohol solution; The preparation metal oxide sol; The preparation gel; The gel ageing; Gel drying; Acidifying, washing; Drying makes the target catalyst again.
3. according to the described Preparation of catalysts method of claim 2, it is characterized in that: regulator solution pH is 3.5～5.8 during the preparation gel.
4. according to claim 2 or 3 described Preparation of catalysts methods, it is characterized in that: add ethanol during the preparation metal oxide sol.
5. according to the described Preparation of catalysts method of claim 2, it is characterized in that: perfluorinated sulfonic acid ion exchange resin formulations prepared from solutions temperature is 180 ℃～250 ℃, preferred 190 ℃～200 ℃.
6. according to the described any Preparation of catalysts method of claim 2～5, it is characterized in that: it is 1%～30% that perfluorinated sulfonic acid ion exchange resin accounts for target catalyst weight percentage composition, preferred 5%～20%, more preferably 5%～15%.
7. a metal oxide contains the application of perfluorinated sulfonic acid ion-exchange resin catalyst in methanol gas phase dewatering preparing dimethy ether.
8. according to the described application of claim 7, it is characterized in that: specific surface area of catalyst is 570～1000m
2/ g.
9. according to claim 7 or 8 described application, it is characterized in that: reaction temperature is 160～240 ℃; Preferred 170～200 ℃; More preferably 175～180 ℃.
10. according to the described any application of claim 7～9, it is characterized in that: applying pressure is 0.15～0.4MPa; Preferred pressure 0.2MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962100A (en) * | 2012-12-05 | 2013-03-13 | 新奥新能(北京)科技有限公司 | Catalyst for dimethyl ether preparation through low-temperature methanol dehydration and preparation method as well as applications thereof |
| CN106925347A (en) * | 2015-12-29 | 2017-07-07 | 山东华夏神舟新材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962100A (en) * | 2012-12-05 | 2013-03-13 | 新奥新能(北京)科技有限公司 | Catalyst for dimethyl ether preparation through low-temperature methanol dehydration and preparation method as well as applications thereof |
| CN102962100B (en) * | 2012-12-05 | 2016-03-23 | 新奥新能(北京)科技有限公司 | A kind of low-temp methanol dehydration catalyst for producing dimethyl ether and preparation method and application |
| CN106925347A (en) * | 2015-12-29 | 2017-07-07 | 山东华夏神舟新材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
| CN106925347B (en) * | 2015-12-29 | 2019-10-29 | 山东东岳未来氢能材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
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Assignee: Newly can (Zhangjiagang) limited energy company Assignor: Xinao Xinneng (Beijing) Technology Co., Ltd. Contract record no.: 2012320010131 Denomination of invention: Catalyst for preparing dimethyl ether from low-temperature methanol by gas phase de-hydration, preparation method and application Granted publication date: 20110907 License type: Exclusive License Open date: 20100908 Record date: 20120611 |