CN102698814B - Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof - Google Patents

Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof Download PDF

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CN102698814B
CN102698814B CN201210197359.3A CN201210197359A CN102698814B CN 102698814 B CN102698814 B CN 102698814B CN 201210197359 A CN201210197359 A CN 201210197359A CN 102698814 B CN102698814 B CN 102698814B
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preparation
catalyst
mesoporous material
salt
solution
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CN102698814A (en
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房德仁
任万忠
刘波
王涛
张慧敏
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Yantai University
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a mesoporous material and a preparation method thereof. The mesoporous material comprises the following raw materials by weight percent: 1-40% of Cr2O3 and 60-99% of Al2O3. The mesoporous material prepared by the preparation method has excellent thermal stability and larger specific surface area, the specific surface area of the mesoporous material after the mesoporous material is roasted at the temperature of 550 DEG C is more than 400 m<2>/g, and the mesoporous material has a regular structure and multiple active points. The invention further relates to a catalyst with the mesoporous material as a carrier and a preparation method of the catalyst. The catalyst comprises the following raw materials by weight percent: 5-39% of Cr2O3, 55-92% of Al2O3 and 0.1-10% of MxO, wherein M is alkali metal or alkaline-earth metal. The specific surface area of the catalyst prepared by the preparation method is more than 150 m<2>/g, and the catalyst has a stable structure and excellent catalytic activity.

Description

A kind of mesoporous material and preparation method thereof and Catalysts and its preparation method
Technical field
The present invention relates to a kind of mesoporous material and preparation method thereof and Catalysts and its preparation method, especially a kind of mesoporous material Cr-Al-O and preparation method thereof and catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, belong to organic chemical synthesis technical field.
Background technology
It is important industrial processes that dehydrating alkanes prepares alkene, and such as dehydrogenating propane produces propylene, butylene etc. is produced in butane dehydrogenation.The alkane dehydrogenating catalyst of general industry is divided into precious metal, as Pt/Al 2o 3catalyst, and Cr 2o 3/ Al 2o 3catalyst etc.Catalyst adopts infusion process and kneading method preparation.Patent CN101898130A discloses a kind of preparation method of catalyst for preparing propylene with propane dehydrogenation, take aluminium oxide as carrier, take Sn as auxiliary agent, be dehydrogenation activity group with one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium, wherein auxiliary agent Sn substep is incorporated in alumina support, part Sn introduces the material containing Sn when aluminium oxide plastic, then make carrier; Rest Sn is introduced by infusion process.Patent CN101940922A discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof.This catalyst is active metal component with chromium, take alkali metal as co catalysis component, and to contain chromium aluminium oxide for carrier, wherein chromium oxide weight content is in the carrier 2.0% ~ 15.0%.In the present invention, the active metal component chromium method introduced in alumina support is that part adopts kneading method, and part adopts infusion process.In order to the restriction that the catalyst that top legal system is standby amasss due to stand under load surface area per unit volume, catalytic activity during high-speed is lower, and because operating temperature is higher, accessory substance is more.
Mesopore molecular sieve is the new function material that a class has regular pore passage structure, and its specific area is generally at 300m 2/ more than g, and there is uniform pore passage structure, be the extremely promising catalysis material of a class.How improving thermal stability and the content of heteroatoms thereof of mesoporous material, is the key point being applied to catalytic field.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of high stability mesoporous material and preparation method thereof and catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of mesoporous material, is made up of the raw material of following percentage by weight: Cr 2o 31 ~ 40% and Al 2o 360 ~ 99%.
The invention has the beneficial effects as follows, mesoporous Cr-Al-O prepared by the present invention has fabulous heat endurance and larger specific area, and the specific area after 550 DEG C of roastings is greater than 400m 2/ g, and its compound with regular structure, active site is many.
Another technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of mesoporous material, comprises the following steps:
1) the solubility salt of chromium and the solubility salt of aluminium are dissolved in deionized water together, obtain solution A; Again template is dissolved in deionized water in another container, obtains B solution; Then solution A is joined B solution, and be constantly stirred to abundant mixing, obtain a kind of uniform mixed solution;
Wherein, the parts by weight of total solubility salt of the solubility salt of described chromium and the solubility salt of aluminium and the ratio of weight and number of deionized water are 1:1.0 ~ 3.0; The ratio of weight and number of described template and deionized water is 1:50 ~ 100;
2) adjust the pH value of above-mentioned mixed solution with alkaline solution, then continue stirring 0.5 ~ 1 hour, make described mixed solution carry out synthetic reaction, after reaction terminates, be cooled to room temperature, obtain floccule and taken out, described floccule is blue;
3) floccule of taking-up is carried out wash, filter, obtain filter cake, more described filter cake is carried out drying, roasting and get final product.
Described room temperature room temperature, also referred to as normal temperature or general temperature, is commonly defined as 25 degrees Celsius.Be set to 300K (about 27 DEG C) sometimes, be beneficial to the calculating using absolute temperature.In general, room temperature has the definition of 3 kinds of scopes: 1.23 DEG C ± 2 DEG C; 2.25 ± 5 DEG C; 3.20 ± 5 DEG C.Optimum temperature winter 16 ~ 18 degrees Celsius in room, summer 24 ~ 26 degrees Celsius.
On the basis of technique scheme, the present invention can also do following improvement.
Further, in step 1), the solubility salt of described chromium, the solubility salt of aluminium comprise nitrate, sulfate, chloride, acetate, and the solubility salt of aluminium also comprises the polymeric aluminum colloidal sol of aluminium polychloride, polyaluminium sulfate and polymerization aluminum nitrate.
Further, in step 1), described template is a kind of or several arbitrarily mixture in cationic surfactant, anion surfactant, non-ionic surface active agent and amphoteric surfactant.
Further, in step 2) in, described alkaline solution is NaOH, NaHCO 3, Na 2cO 3, KOH, KHCO 3or K 2cO 3the aqueous solution.
Further, in step 2) in, the pH value of described adjustment is 6 ~ 14, is preferably 7 ~ 12.
Further, in step 2) in, the temperature of described synthetic reaction is 5 DEG C ~ 200 DEG C, and the time is 2 ~ 720 hours.Synthesis reaction temperature is preferably 15 DEG C ~ 150 DEG C, and the reaction time is preferably 10 ~ 300 hours.
Further, in step 3), described filter cake carries out drying at the temperature of 10 DEG C ~ 200 DEG C, is preferable over 20 DEG C ~ 150 DEG C and carries out drying; Dried filter cake is at the roasting temperature 2 ~ 100 hours of 250 DEG C ~ 650 DEG C, and temperature is preferable over 300 DEG C ~ 550 DEG C, and roasting time is preferable over 3 ~ 30 hours.
The another technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, comprise the following steps: the mesoporous material obtained with above-mentioned preparation method is carrier, the salt of alkali-metal salt or alkaline-earth metal is mixed with described mesoporous material, more successively through super-dry, granulation, roasting, shaping, to obtain final product.
Described prilling is by levigate powder, through adding water, roll, dry, pulverize, the operation such as to sieve, make good fluidity, particle that particle diameter is about 0.05 ~ 0.5mm.
Described roasting refers to, the course of reaction that solid material carries out under the condition of melting does not occur high temperature, and Main Function is decomposed by catalyst Precursors to generate corresponding metal oxide etc.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described mixing is the method mixing by being dry mixed or flood.
Described dry pigmentation refers to, is at room temperature mixed by the mesoporous material after roasting, then mixed with ball mill etc. with the salt of active component Me and the salt of alkali-metal salt or alkaline-earth metal, and then successively through roasting, shaping, to obtain final product.
Described dipping refers to, fills the method for sintered body hole with nonmetal fluid (paraffin of such as lubricating oil, melting or resin).
Further, the salt of described alkali-metal salt or alkaline-earth metal is a kind of or several arbitrarily mixture in hydroxide, carbonate, oxalates or nitrate.
The another technical scheme that the present invention solves the problems of the technologies described above is as follows:
According to the catalyst for dehydrogenation of low-carbon paraffin that above-mentioned preparation method obtains, be made up of the raw material of following percentage by weight: Cr 2o 35 ~ 39%, Al 2o 355 ~ 92%, M xo 0.1 ~ 10%; Wherein, described M is alkali metal or alkaline-earth metal.
The beneficial effect of the catalyst of the technical program synthesis of low-carbon alcohol and mixture of light hydrocarbons is: based on this mesoporous material, further by auxiliary agent M xo load on it, has obtained a kind of specific area and has been greater than 150m 2/ g, and constitutionally stable Cr-M x-Al 2o 3catalyst for dehydrogenation of low-carbon paraffin, this catalyst has fabulous catalytic activity.
Detailed description of the invention
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Take Cr (NO respectively 3) 3● 6H 2o 3g, Al (NO 3) 3● 9H 2o 70g, miscible in 110ml deionized water; Taking 1g trimethyl cetyl ammonium bromide is dissolved in 100ml deionized water, then with vigorous stirring by two kinds of solution mixing, with the 1M NaOH aqueous solution, pH value is adjusted to 8.5, continues stirring 60 minutes.The pasty material of generation to be transferred in the stainless steel synthesis reactor of 300ml and be warmed up to 120 DEG C and continue reaction 100h, reaction end is cooled to room temperature, material is drawn off and repeatedly washs with centrifuge, filter cake at room temperature dries, then in tube furnace under air atmosphere at 550 DEG C of roasting 20h, obtain a kind of solid matter, measuring its specific area with nitrogen adsorption method (BET method) is 450m 2/ g, XRD method measures it and has meso-hole structure, and the material prepared by explanation is high stability mesoporous material Cr-Al-O of the present invention.Take K 2cO 30.5g deionized water 10ml dissolves, and above-mentioned mesoporous material is added mixing, and then material is in an oven in 120 DEG C of dry 10h, be crushed to 10-20 order, in 350 DEG C of roasting 5h in Muffle furnace, be finally pressed into sheet with tablet press machine, namely obtain a kind of catalyst for dehydrogenation of low-carbon paraffin A.
Embodiment 2
Take Cr (NO respectively 3) 3● 6H 2o 18g, aluminium polychloride is (containing Al 2o 320%) 33g, miscible in 100ml deionized water; Taking 2g dodecyl sodium sulfate is dissolved in 100ml deionized water, then with vigorous stirring by two kinds of solution mixing, with the 1M KOH aqueous solution, pH value is adjusted to 7.5, continues stirring 60 minutes.The pasty material of generation to be transferred in the stainless steel synthesis reactor of 300ml and be warmed up to 20 DEG C and continue reaction 100h, reaction end is cooled to room temperature, material is drawn off and repeatedly washs with centrifuge, filter cake at room temperature dries, then in tube furnace under air atmosphere at 550 DEG C of roasting 20h, obtain a kind of solid matter, measuring its specific area with nitrogen adsorption method (BET method) is 420m 2/ g, XRD method measures it and has meso-hole structure, and the material prepared by explanation is high stability mesoporous material Cr-Al-O of the present invention.Take K 2cO 31.0g deionized water 10ml dissolves, and above-mentioned mesoporous material is added mixing, and then material is in an oven in 120 DEG C of dry 10h, be crushed to 10-20 order, in 400 DEG C of roasting 3h in Muffle furnace, be finally pressed into sheet with tablet press machine, namely obtain a kind of catalyst for dehydrogenation of low-carbon paraffin B.
Embodiment 3
Take Cr (NO respectively 3) 2● 6H 2o 10g, aluminium polychloride is (containing Al 2o 320%) 30g, miscible in 120ml deionized water; Taking 2g betaine is dissolved in 150ml deionized water, then with vigorous stirring by two kinds of solution mixing, with the 1M KOH aqueous solution, pH value is adjusted to 10.5, continues stirring 60 minutes.The pasty material of generation to be transferred in the stainless steel synthesis reactor of 300ml and be warmed up to 50 DEG C and continue reaction 200h, reaction end is cooled to room temperature, material is drawn off and repeatedly washs with centrifuge, filter cake at room temperature dries, then in tube furnace under air atmosphere at 550 DEG C of roasting 20h, obtain a kind of solid matter, measuring its specific area with nitrogen adsorption method (BET method) is 425m 2/ g, XRD method measures it and has meso-hole structure, and the material prepared by explanation is high stability mesoporous material Cr-Al-O of the present invention.Take Li 2cO 31.0g deionized water 10ml dissolves, and above-mentioned mesoporous material is added mixing, and then material is in an oven in 120 DEG C of dry 10h, be crushed to 10-20 order, in 400 DEG C of roasting 3h in Muffle furnace, be finally pressed into sheet with tablet press machine, namely obtain a kind of catalyst for dehydrogenation of low-carbon paraffin C.
In order to prove that catalyst for dehydrogenation of low-carbon paraffin prepared by above-mentioned mesoporous material has higher catalytic activity, spy has done the catalyst for dehydrogenation of low-carbon paraffin prepared by traditional infusion process, and carrying out energy can comparative determination.
Comparative example 1
Take Cr (NO 3) 26H 2o 3g, K 2cO 30.5g is dissolved in altogether in 10ml deionized water and is made into maceration extract; Take 9.5g Al 2o 3impregnated in above-mentioned solution, then in an oven in 150 DEG C of dryings 4 hours, be crushed to below 10 orders, in 350 DEG C of roastings 4 hours in Muffle furnace, beat sheet after cooling shaping, gained catalyst is called sample D.
Comparative example 2
Take Cr (NO 3) 26H 2o 18g, K 2cO 31.0g is dissolved in altogether in 30ml deionized water and is made into maceration extract; Take 6.6g Al 2o 3impregnated in above-mentioned solution, be then evaporated to dry in water-bath, in an oven in 120 DEG C of dryings 6 hours, be crushed to below 10 orders, in 400 DEG C of roastings 4 hours in Muffle furnace, beat sheet after cooling shaping, gained catalyst is called sample E.
Above sample micro anti-evaluation device evaluates its reactivity and selective.Evaluation method is: first catalyst sample is crushed to 40-60 order, measures 5ml quartz sand and dilutes by 1:1.Then reaction temperature 550 DEG C, pressure 0.1MPa, air speed is 3000h -1condition under carry out activity rating.Reactor feed gas is iso-butane, the on-line analysis of product composition.
Active appraisal experiment result
Above data illustrate, the reactivity of catalyst of the present invention and selectivity of product are obviously better than catalyst prepared by existing patented method.
Above experimental result illustrates, of the present invention take mesoporous material as the Cr-M of skeleton structure x-Al 2o 3catalyst has larger specific area, compared with traditional infusion process catalyst, for the reactivity of catalyst for dehydrogenation of low-carbon paraffin and selectivity of product better.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (9)

1. a preparation method for catalyst for dehydrogenation of low-carbon paraffin, is characterized in that, comprises the following steps:
1) the solubility salt of chromium and the solubility salt of aluminium are dissolved in deionized water together, obtain solution A; Again template is dissolved in deionized water in another container, obtains B solution; Then solution A is joined in B solution, and be constantly stirred to abundant mixing, obtain a kind of uniform mixed solution;
Wherein, the parts by weight of total solubility salt of the solubility salt of described chromium and the solubility salt of aluminium and the ratio of weight and number of deionized water are 1:1.0 ~ 3.0; The ratio of weight and number of described template and deionized water is 1:50 ~ 100; Described template is a kind of or several arbitrarily mixture in cationic surfactant, anion surfactant, non-ionic surface active agent and amphoteric surfactant;
2) adjust the pH value of above-mentioned mixed solution with alkaline solution, then continue stirring 0.5 ~ 1 hour, make described mixed solution carry out synthetic reaction, after reaction terminates, be cooled to room temperature, obtain floccule and taken out;
3) floccule of taking-up is carried out wash, filter, obtains filter cake, more described filter cake is carried out drying, namely roasting obtain mesoporous material, described mesoporous material is made up of the raw material of following percentage by weight: Cr 2o 31 ~ 40% and Al 2o 360 ~ 99%;
4) using obtained mesoporous material as carrier, the salt of alkali-metal salt or alkaline-earth metal is mixed with described mesoporous material, more successively through super-dry, granulation, roasting, shaping, obtain described catalyst for dehydrogenation of low-carbon paraffin.
2. preparation method according to claim 1, is characterized in that, in step 1) in, the solubility salt of described chromium, the solubility salt of aluminium be in nitrate, sulfate, chloride or acetate any one.
3. preparation method according to claim 1, is characterized in that, in step 2) in, described pH value is 6 ~ 14.
4. preparation method according to claim 1, is characterized in that, in step 2) in, described alkaline solution is NaOH, NaHCO 3, Na 2cO 3, KOH, KHCO 3or K 2cO 3in any one.
5. preparation method according to claim 1, is characterized in that, in step 2) in, the temperature of described synthetic reaction is 5 DEG C ~ 200 DEG C, and the time is 2 ~ 720 hours.
6. preparation method according to claim 1, is characterized in that, in step 3) in, described filter cake carries out drying at the temperature of 10 DEG C ~ 200 DEG C; Dried filter cake is at the roasting temperature 2 ~ 100 hours of 250 DEG C ~ 650 DEG C.
7. preparation method according to claim 1, is characterized in that, in step 4) in, described mixing is the method mixing by being dry mixed or flood.
8. preparation method according to claim 1, is characterized in that, in step 4) in, the salt of described alkali-metal salt or alkaline-earth metal is a kind of or several arbitrarily mixture in hydroxide, carbonate, oxalates or nitrate.
9. the catalyst for dehydrogenation of low-carbon paraffin that the preparation method according to any one of claim 1 to 8 obtains, is characterized in that, is made up of: Cr the raw material of following percentage by weight 2o 35 ~ 39%, Al 2o 355 ~ 92%, M xo 0.1 ~ 10%, wherein, described M is alkali metal or alkaline-earth metal.
CN201210197359.3A 2012-06-14 2012-06-14 Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof Expired - Fee Related CN102698814B (en)

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Publication number Priority date Publication date Assignee Title
CN103301830A (en) * 2013-05-24 2013-09-18 上海师范大学 Preparation method and application of chromium oxide/aluminum oxide catalyst
CN103272578B (en) * 2013-06-13 2015-12-23 上海师范大学 A kind of laminar chromium oxide/aluminum oxide catalyst and its preparation method and application
CN104475080B (en) * 2014-11-20 2017-09-29 西安近代化学研究所 A kind of mesoporous chromium oxide-based catalyst for de-hydrogen halide
CN116443944A (en) * 2023-02-13 2023-07-18 中国科学院赣江创新研究院 Rare earth modified mesoporous spinel type ferrite wave-absorbing material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940922A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN101961652A (en) * 2010-10-14 2011-02-02 来安县迅能催化剂有限公司 Catalyst for preparing 2-methyl furan through gas phase hydrogenation of furfural and preparation method thereof
CN102019181A (en) * 2010-10-29 2011-04-20 烟台大学 Mesoporous material and preparation method thereof and synthesis methanol catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940922A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN101961652A (en) * 2010-10-14 2011-02-02 来安县迅能催化剂有限公司 Catalyst for preparing 2-methyl furan through gas phase hydrogenation of furfural and preparation method thereof
CN102019181A (en) * 2010-10-29 2011-04-20 烟台大学 Mesoporous material and preparation method thereof and synthesis methanol catalyst and preparation method thereof

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