CN101590426B - Composite catalyst with molecular sieve coated TiO2 core-shell structure for preparing ethane by dehydrating ethanol - Google Patents
Composite catalyst with molecular sieve coated TiO2 core-shell structure for preparing ethane by dehydrating ethanol Download PDFInfo
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- CN101590426B CN101590426B CN2009100405651A CN200910040565A CN101590426B CN 101590426 B CN101590426 B CN 101590426B CN 2009100405651 A CN2009100405651 A CN 2009100405651A CN 200910040565 A CN200910040565 A CN 200910040565A CN 101590426 B CN101590426 B CN 101590426B
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- molecular sieve
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- ethanol
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title abstract 4
- 239000011258 core-shell material Substances 0.000 title abstract 3
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 53
- 239000005977 Ethylene Substances 0.000 claims description 42
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 40
- 239000002071 nanotube Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 230000018044 dehydration Effects 0.000 claims description 20
- 238000006297 dehydration reaction Methods 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 14
- 241000269350 Anura Species 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 150000001793 charged compounds Chemical group 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 208000005156 Dehydration Diseases 0.000 description 15
- 239000011572 manganese Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 6
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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 present invention provides a composite catalyst with a molecular sieve coated TiO2 core-shell structure with high catalytic activity for preparing ethane by dehydrating ethanol, which is capable of improving conversion rate of the ethanol, and gas generation rate and selectivity of the ethane. The catalyst comprises the components of molecular sieve and TiO2, and is characterized in that: the inner core of the composite catalyst is titanium dioxide assistant, and the outside of the composite catalyst is coated by the molecular sieve or ion exchange modified molecular sieve. The composite catalyst of the core-shell structure, in which the molecular sieve or the ion exchange modified molecular sieve to coat the TiO2, enables surface activity site of the catalyst not to be influenced, effectively embodies the catalysis of the titanium dioxide assistant at the same time, further improves the activity of the catalyst, improves the conversion rate of the ethanol and the yield and the selectivity of the target product ethane, thereby having better catalysis effect.
Description
Technical field
The present invention relates to chemical and technical field of biochemical industry, relate in particular to the new type structure of hud composite catalyst that is used for ethylene preparation by ethanol dehydration.
Technical background
Ethene is a kind of main basic Organic Chemicals, and nearly 75% petrochemicals derive from ethene.The commercial scale of ethene and level are the important symbols of a national chemical industry development level of reflection.At present, ethene mainly is to produce for the catalytic material cracking with the oil, and its reaction temperature is up to 850 ℃ usually.In recent years, the petroleum resources reserves reduce year by year with the increase and the prolongation of exploitation time of yield, and environmental pollution is serious day by day and to the attention of clean energy resource, with non-grain crops such as cassavas is the bio-ethanol of raw material production and to produce ethene with the bio-ethanol that cellulose hydrolysis makes be an important supplement that satisfies in the future ethylene requirements, can reduce dusty gas (SO
2, NO
2) discharging, to improving environment great benefit is arranged.Catalyst is one of key factor of producing ethylene from dehydration of ethanol.Adopt low temperature catalyst, can reduce the technology cost of synthesizing ethylene; Adopt the catalyst of high selectivity, can reduce the separation cost for purification of product, therefore seeking new and effective catalyst can promote effectively that producing ethylene from dehydration of ethanol is crucial.
As far back as 13rd century, people just find that catalytic dehydration of ethanol can make ethene, and after this get ethene with this legal system before the petrochemical industry development always.γ-the Al of present industrial usefulness
2O
3Catalyst reaction temperatures is 450 ℃.And molecular sieve catalyst just begins to have caused people's extensive concern because of its characteristics such as yield, Heat stability is good with etching apparatus not, lower reaction temperature, higher reaction conversion per pass and ethene in the 1980s.TiO
2As a kind of good catalyst and auxiliary agent, with SiO
2, MgO and Al
2O
3Compound tense can promote the dehydration of low-carbon alcohols.TiO is found in experiment
2/ γ-Al
2O
3, TiO
2/ 4A molecular sieve can suitably reduce the catalytic temperature of producing ethylene from dehydration of ethanol, improves ethanol conversion and ethylene selectivity, but TiO
2Coat TiO in the molecular sieve catalyst
2The part active sites of possible covering catalyst.
Through consulting document, do not see the molecular sieve that is useful on ethylene preparation by ethanol dehydration both at home and abroad and coat TiO
2Document, patent and the achievement report of composite catalyst.
Summary of the invention
The purpose of this invention is to provide the molecular sieve coating TiO that the process that is used for preparing ethylene by dehydrating ethanol can improve ethanol conversion, ethene gas production rate and optionally have high catalytic activity
2The nucleocapsid structure composite catalyst.
Composite catalyst of the present invention, its composition are molecular sieve and TiO
2, it is characterized in that: internal core is the titanium dioxide auxiliary agent, outside molecular sieve with molecular sieve or ion-exchanged coats.
It is one of following that the titanium dioxide auxiliary agent of described internal core is selected from: TiO
2The TiO that powder or impurity element mix
2Powder, TiO
2The TiO that nanotube or impurity element mix
2Nanotube.The described outside molecular screening that coats is from one of following: the molecular sieve of the molecular sieve of the molecular sieve of the molecular sieve of A type molecular sieve or its ion-exchanged, Y zeolite or its ion-exchanged, SAPO type or its ion-exchanged, ZSM type or its ion-exchanged.
The TiO that described impurity element mixes
2Powder and TiO
2In the nanotube, its impurity element is selected from one of following or more than one: silver (Ag), nickel (Ni) manganese (Mn), iron (Fe), zinc (Zn), cobalt (Co), scandium (Sc), vanadium (V), chromium (Cr), cerium (Ce), strontium (Sr), platinum (Pt), gold (Au).
The molecular screening of described ion-exchanged is from A type molecular sieve, Y zeolite, SAPO type molecular sieve, the ZSM type molecular sieve of one of following element or more than one modifications: silver (Ag), manganese (Mn), zinc (Zn), vanadium (V), cobalt (Co), cerium (Ce), strontium (Sr), phosphorus (P), iron (Fe), nickel (Ni).
The preparation process of composite catalyst of the present invention is as follows:
1, the selection of crystal seed and processing
Crystal seed can be selected TiO
2Powder or impurity element doped Ti O
2Powder, TiO
2Nanotube or impurity element doped Ti O
2Nanotube.Directly use or be placed in the baking oven and dry, and in Muffle furnace, heat-treat, use after naturally cooling to room temperature.
2, molecular sieve or ion-exchanged molecular sieve coat TiO
2The preparation of nucleocapsid structure composite catalyst
Choose the required molecular sieve or the molecular sieve of ion-exchanged, at the seed surface hydro-thermal synthesis of molecular sieve that step 1 is handled well, washing is filtered and is handled in the Muffle furnace temperature programming after oven for drying, promptly gets the desired molecule sieve naturally after the cooling and coats TiO
2The nucleocapsid structure composite catalyst.By ion-exchanged, washing is filtered and is handled in the Muffle furnace temperature programming after oven for drying with this composite catalyst, promptly gets desired ion exchange modified molecular screen naturally after the cooling and coats TiO
2The nucleocapsid structure composite catalyst
Adopt molecular sieve or ion-exchanged molecular sieve to coat TiO
2The nucleocapsid structure composite catalyst, make that the catalyst surface active position is unaffected, simultaneously the titanium dioxide promoting catalysis also can effectively embody.Can further improve activity of such catalysts, improve ethanol conversion and target product ethylene yield and ethylene selectivity, therefore have better catalytic effect.
Description of drawings
Fig. 1 is that molecular sieve coats TiO
2The nucleocapsid structure composite catalyst structural representation of powder
Fig. 2 is that molecular sieve coats TiO
2The nucleocapsid structure composite catalyst structural representation of nanotube
Fig. 3 is that β-molecular sieve that embodiment 1 makes coats TiO
2The nucleocapsid structure composite catalyst and the β-molecular sieve of powder are respectively applied for ethylene preparation by ethanol dehydration, and its ethylene yield is with the variation of temperature curve
Fig. 4 is that nucleocapsid structure composite catalyst and the β-molecular sieve that the β that makes of embodiment 1-molecular sieve coats the TiO2 powder is respectively applied for ethylene preparation by ethanol dehydration, and its ethanol conversion, ethylene selectivity are with the variation of temperature curve
Fig. 5 is the TiO that the β that makes of embodiment 2-molecular sieve coats
2The nucleocapsid structure composite catalyst and the β-molecular sieve of nanotube are respectively applied for ethylene preparation by ethanol dehydration, and its ethylene yield is with the variation of temperature curve
Fig. 6 is the TiO that the β that makes of embodiment 2-molecular sieve coats
2The nucleocapsid structure composite catalyst and the β-molecular sieve of nanotube are respectively applied for ethylene preparation by ethanol dehydration, and its ethanol conversion, ethylene selectivity are with the variation of temperature curve
Description of reference numerals: indicate " 1 " printed words among Fig. 1-2 and represent molecular sieve, indicate " 2 " printed words and represent TiO
2Powder indicates " 3 " printed words and represents TiO
2Nanotube; Indicate " TiO among Fig. 3-4
2@ β-molecular sieve " on behalf of β-molecular sieve, the curve of printed words coat TiO
2The curve of the nucleocapsid structure composite catalyst of powder; Indicate " TiO among Fig. 5-6
2Nanotube @ β-molecular sieve " on behalf of β-molecular sieve, the curve of printed words coat TiO
2The curve of the nucleocapsid structure composite catalyst of nanotube; Indicate " S among Fig. 4,6
ETHY" curve of printed words represents the ethylene selectivity curve, the curve that indicates " Cetha " printed words is represented the ethanol conversion rate curve
The specific embodiment
Below in conjunction with embodiment content of the present invention is described in further detail.
Embodiment 1
1. choose TiO
2Powder is as crystal seed, weighing 2g.
2. an amount of Al of weighing
2(SO
4)
318H
2O is dissolved in the deionized water at a certain temperature, and stirring adds an amount of down again
Softex kw (CTAB), be designated as solution A;
3. in A solution, add the ethyl orthosilicate of 66ml and the NaOH solution of 0.2M 55ml, fully mix, be designated as solution B;
4. with selected TiO
2The powder crystal kind adds in the solution B, fully stirs crystal seed is evenly disperseed, and is designated as solution C;
5. solution C is transferred in the airtight hydrothermal reaction kettle, crystallization is 48 hours under 140 ℃ of temperature, with gained sample washing, filter, and in 100 ℃ of baking ovens, dry sample D;
6. sample D is heat-treated, handle down 3h for 500 ℃ in Muffle furnace, 2 ℃/min of heating rate cools off naturally that promptly to obtain shell be β-molecular sieve, examines to be TiO
2The nucleocapsid structure composite catalyst of powder.
β-molecular sieve that embodiment 1 is made coats TiO
2In the reaction that the nucleocapsid structure composite catalyst of powder and β-molecular sieve are respectively applied for ethylene preparation by ethanol dehydration, its data are respectively shown in accompanying drawing 3,4.
In accompanying drawing 3, X-axis is a temperature, and Y-axis is an ethylene yield.From accompanying drawing 3 as can be seen, β-molecular sieve coats TiO
2The nucleocapsid composite catalyst of powder can make ethanol dewater in the time of 210 ℃ and produce ethene, and β-molecular sieve catalyst just reacts in the time of 240 ℃, and β-molecular sieve coats TiO
2The ethylene yield of the nucleocapsid composite catalyst of powder apparently higher than β-molecular sieve catalyst, can improve ethylene yield with the climbing speed of temperature greatly, and especially in the time of 300 ℃, ethylene yield improves at most, when being to use β-molecular sieve catalyst about 15 times.
In accompanying drawing 4, X-axis is a temperature, and Y-axis is ethanol conversion, ethylene selectivity.From accompanying drawing 4 as can be seen, β-molecular sieve coats TiO
2The nucleocapsid composite catalyst of powder can improve ethanol conversion and ethylene selectivity greatly when relative low temperature, when reaction temperature is 300 ℃, its ethanol conversion is to use 13 times of β-molecular sieve catalyst, ethylene selectivity is to use 1.11 times of β-molecular sieve catalyst up to 98.41% simultaneously.
In the present embodiment, also can be with the TiO of impurity element doping
2Powder is as crystal seed, and its impurity element is selected from one of following or more than one: silver (Ag), nickel (Ni) manganese (Mn), iron (Fe), zinc (Zn), cobalt (Co), scandium (Sc), vanadium (V), chromium (Cr), cerium (Ce), strontium (Sr), platinum (Pt), gold (Au).Molecular sieve also can be selected the molecular sieve of molecular sieve, ZSM type or its ion-exchanged of molecular sieve, SAPO type or its ion-exchanged of molecular sieve, Y zeolite or its ion-exchanged of A type molecular sieve or its ion-exchanged for use.The molecular screening of described ion-exchanged is from A type molecular sieve, Y zeolite, SAPO type molecular sieve, the ZSM type molecular sieve of one of following element or more than one modifications: silver (Ag), manganese (Mn), zinc (Zn), vanadium (V), cobalt (Co), cerium (Ce), strontium (Sr), phosphorus (P), iron (Fe), nickel (Ni).The technique effect of above-mentioned change is all similar with present embodiment.
Embodiment 2
1. choose TiO
2Nanotube is as crystal seed, weighing 1.5g.
2. an amount of Al of weighing
2(SO
4)
318H
2O is dissolved in the deionized water at a certain temperature, and stirring adds an amount of softex kw (CTAB) down again, is designated as solution A;
3. in A solution, add the ethyl orthosilicate of 66ml and the NaOH solution of 0.2M 55ml, fully mix, be designated as solution B;
4. with selected TiO
2The nanotube crystal seed adds in the solution B, fully stirs crystal seed is evenly disperseed, and is designated as solution C;
5. solution C is transferred in the airtight hydrothermal reaction kettle, crystallization is 48 hours under 150 ℃ of temperature, with gained sample washing, filter, and in 100 ℃ of baking ovens, dry sample D;
6. sample D is heat-treated, handle down 3h for 500 ℃ in Muffle furnace, 2 ℃/min of heating rate cools off naturally that promptly to obtain shell be β-molecular sieve, examines to be TiO
2The nucleocapsid structure composite catalyst of nanotube.
The TiO that β-molecular sieve that embodiment 2 is made coats
2In the reaction that the nucleocapsid structure composite catalyst of nanotube and β-molecular sieve are respectively applied for ethylene preparation by ethanol dehydration, its data are respectively shown in accompanying drawing 5,6.
In accompanying drawing 5, X-axis is a temperature, and Y-axis is an ethylene yield.From accompanying drawing 5 as can be seen, the TiO of β-molecular sieve coating
2The nucleocapsid structure composite catalyst of nanotube can make ethanol produce ethene 210 ℃ of dehydrations, and β-molecular sieve catalyst just reacts in the time of 240 ℃, and the TiO of β-molecular sieve coating
2The ethylene yield of the nucleocapsid structure composite catalyst of nanotube with the climbing speed of temperature apparently higher than β-molecular sieve catalyst, simultaneously can improve ethylene yield greatly, especially in the time of 330 ℃, ethylene yield improves at most, when being to use β-molecular sieve catalyst about 30 times.
In accompanying drawing 6, X-axis is a temperature, and Y-axis is ethanol conversion, ethylene selectivity.From accompanying drawing 6 as can be seen, the TiO of β-molecular sieve coating
2The nucleocapsid structure composite catalyst of nanotube can improve ethanol conversion and selectivity of ethylene greatly when relative low temperature, when reaction temperature is 330 ℃, its ethanol conversion is 30 times of β-molecular sieve catalyst, ethylene selectivity is to use 1.13 times of β-molecular sieve catalyst up to 99.1% simultaneously.
In the present embodiment, also can be with the TiO of impurity element doping
2Nanotube is as crystal seed, and its impurity element is selected from one of following or more than one: silver (Ag), nickel (Ni) manganese (Mn), iron (Fe), zinc (Zn), cobalt (Co), scandium (Sc), vanadium (V), chromium (Cr), cerium (Ce), strontium (Sr), platinum (Pt), gold (Au).Molecular sieve also can be selected the molecular sieve of molecular sieve, ZSM type or its ion-exchanged of molecular sieve, SAPO type or its ion-exchanged of molecular sieve, Y zeolite or its ion-exchanged of A type molecular sieve or its ion-exchanged for use.The molecular screening of described ion-exchanged is from A type molecular sieve, Y zeolite, SAPO type molecular sieve, the ZSM type molecular sieve of one of following element or more than one modifications: silver (Ag), manganese (Mn), zinc (Zn), vanadium (V), cobalt (Co), cerium (Ce), strontium (Sr), phosphorus (P), iron (Fe), nickel (Ni).The technique effect of above-mentioned change is all similar with present embodiment.
Claims (5)
1. a molecular sieve that is used for ethylene preparation by ethanol dehydration coats TiO
2The nucleocapsid structure composite catalyst, its composition is molecular sieve and TiO
2, it is characterized in that: the composite catalyst internal core of explaining is the titanium dioxide auxiliary agent, outside molecular sieve with molecular sieve or ion-exchanged coats.
2. the molecular sieve that is used for ethylene preparation by ethanol dehydration according to claim 1 coats TiO
2The nucleocapsid structure composite catalyst, it is characterized in that: the titanium dioxide auxiliary agent of described internal core is selected from one of following: TiO
2The TiO that powder or impurity element mix
2Powder, TiO
2The TiO that nanotube or impurity element mix
2Nanotube.
3. the molecular sieve that is used for ethylene preparation by ethanol dehydration according to claim 1 coats TiO
2The nucleocapsid structure composite catalyst, it is characterized in that: the described outside molecular screening that coats is from one of following: the molecular sieve of the molecular sieve of the molecular sieve of the molecular sieve of A type molecular sieve or its ion-exchanged, Y zeolite or its ion-exchanged, SAPO type or its ion-exchanged, ZSM type or its ion-exchanged.
4. the molecular sieve that is used for ethylene preparation by ethanol dehydration according to claim 2 coats TiO
2The nucleocapsid structure composite catalyst, it is characterized in that: the TiO that described impurity element mixes
2Powder and TiO
2In the nanotube, its impurity element is selected from one of following or more than one: Ag, Ni, Mn, Fe, Zn, Co, Sc, V, Cr, Ce, Sr, Pt, Au.
5. the molecular sieve that is used for ethylene preparation by ethanol dehydration according to claim 3 coats TiO
2The nucleocapsid structure composite catalyst, it is characterized in that: the molecular screening of described ion-exchanged is from A type molecular sieve or Y zeolite or the SAPO type molecular sieve or the ZSM type molecular sieve of one of following element or more than one modifications: Ag, Mn, Zn, V, Co, Ce, Sr, P, Fe, Ni.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100405651A CN101590426B (en) | 2009-06-25 | 2009-06-25 | Composite catalyst with molecular sieve coated TiO2 core-shell structure for preparing ethane by dehydrating ethanol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100405651A CN101590426B (en) | 2009-06-25 | 2009-06-25 | Composite catalyst with molecular sieve coated TiO2 core-shell structure for preparing ethane by dehydrating ethanol |
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|---|---|
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| CN101590426B true CN101590426B (en) | 2011-06-01 |
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| CN104028255B (en) * | 2014-05-12 | 2015-05-13 | 谷屿 | Magnetic surface-modified nanometer titanium dioxide and preparation method thereof |
| CN104016306B (en) * | 2014-06-30 | 2016-04-06 | 哈尔滨工业大学 | The preparation method of conductor oxidate nanotube/ZSM-5 molecular sieve composite material |
| CN104338550B (en) * | 2014-09-10 | 2017-12-19 | 江苏金聚合金材料有限公司 | A kind of preparation method for handling dust technology and the catalyst for generating alkyl nitrite |
| CN106362787B (en) * | 2016-08-06 | 2019-01-08 | 浙江大学 | A kind of preparation method of the immobilized photochemical catalyst of zeolite |
| CN106236598B (en) * | 2016-08-06 | 2019-01-08 | 浙江大学 | A kind of preparation method of uvioresistant skincare material additive |
| CN108404969B (en) * | 2018-05-09 | 2021-07-02 | 河北伟亿泽科技有限公司 | Core-shell nanoparticles for food sterilization |
| CN111375444B (en) * | 2018-12-27 | 2023-02-03 | 中国科学院广州能源研究所 | Core-shell iron-based catalyst for directly producing aromatic hydrocarbon from synthesis gas and preparation method and application thereof |
| CN113522260B (en) * | 2021-07-27 | 2022-09-20 | 西南化工研究设计院有限公司 | Y molecular sieve coated magnesium oxide-titanium dioxide catalyst and application thereof in ester exchange reaction |
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