CN103285906A - Dehydrogenation catalyst, preparation method and application thereof, and method for preparing cyclohexanone by cyclohexanol dehydrogenation - Google Patents
Dehydrogenation catalyst, preparation method and application thereof, and method for preparing cyclohexanone by cyclohexanol dehydrogenation Download PDFInfo
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- CN103285906A CN103285906A CN2012100506940A CN201210050694A CN103285906A CN 103285906 A CN103285906 A CN 103285906A CN 2012100506940 A CN2012100506940 A CN 2012100506940A CN 201210050694 A CN201210050694 A CN 201210050694A CN 103285906 A CN103285906 A CN 103285906A
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 133
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 30
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001994 activation Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- -1 pure steam Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a dehydrogenation catalyst, and a preparation method and application thereof. The catalyst comprises a supporter and a dehydrogenation active component supported on the support, wherein the supporter is rod-like SBA-15. The invention also provides a method for preparing cyclohexanone by cyclohexanol dehydrogenation. By using the rod-like SBA-15 as the supporter of the dehydrogenation catalyst, the catalyst provided by the invention has higher activity and selectivity than the dehydrogenation catalyst using aluminum trioxide or the like as the supporter in the prior art.
Description
Technical field
The present invention relates to a kind of dehydrogenation and preparation method thereof, and the application in dehydrogenation reaction of dehydrogenation of the present invention, and a kind of cyclohexanol dehydrogenation prepares the method for cyclohexanone.
Background technology
Cyclohexanone is a kind of important intermediate products of polyamide-6 and polyamide-6,6, and in industrial production, it is mainly by the catalytic dehydrogenating reaction production of cyclohexanol.Two types cyclohexanol catalytic dehydrogenation processes is generally arranged, and a kind of is the cyclohexanol high-temperature dehydrogenation that carries out under 320-420 ℃ of temperature, and another kind is the cyclohexanol low-temperature dehydrogenation that carries out under 220-260 ℃ of temperature.
Side reaction such as cyclohexene is owing at high temperature take place easily to become as cyclohexanol dehydrogenation in high-temperature dehydrogenation, and therefore, target product selectively lower influenced the economy of this process thus.
Low-temperature dehydrogenation generally carries out in the presence of copper-based catalysts, yet owing to generally under relatively low temperature, carry out the dehydrogenation of cyclohexanol, therefore, usually conversion ratio is relatively low, conversion ratio for the cyclohexanol that improves this process, existing more research, and most of research all is by improving the catalytic efficiency that catalyst improves this process, improving the conversion ratio of cyclohexanol thus.
GB-A 1081491 discloses Cu/Al
2O
3Catalyst, SU-A465217 discloses Cu/Li/SiO
2Catalyst, SU-A 522853 discloses Cu/K/Al
2O
3Catalyst, aforementioned catalyst generally are to prepare by depositing mantoquita at prefabricated carrier or flooding suitable copper salt solution, and carrier is generally alundum (Al Al
2O
3
People's such as Chang, among Appl.Catal.A103 (1994) 233-42, disclose a kind of under the situation that has complexant to exist, use reducing agent electroless copper or reduce deposition copper on carrier, to prepare the method that copper catalyst is used in the non-oxidizable dehydrogenation of cyclohexanol, used carrier is that surface area is 22.6m
2α-Al of/g
2O
3
This shows that prior art realizes by optimizing carrier generally that in order to improve activity of such catalysts though all obtained certain improvement, activity of such catalysts still remains to be improved.
Summary of the invention
The object of the present invention is to provide higher, the selective dehydrogenation preferably of a kind of activity.
To achieve these goals, the invention provides a kind of dehydrogenation, this catalyst comprises carrier and the dehydrogenation active component that loads on this carrier, and wherein, described carrier is bar-shaped SBA-15.
The invention provides a kind of method for preparing dehydrogenation, this method comprises: the soluble-salt solution of dehydrogenation active component is contacted with carrier, the carrier after the contact is carried out drying, roasting; Wherein, described carrier is bar-shaped SBA-15.
The invention provides the application of a kind of dehydrogenation of the present invention in dehydrogenation reaction.
The invention provides the method that a kind of cyclohexanol dehydrogenation prepares cyclohexanone, this method comprises: under dehydrogenation condition, cyclohexanol is contacted with dehydrogenation, wherein, described dehydrogenation is dehydrogenation of the present invention or the dehydrogenation for preparing according to the preparation method of dehydrogenation of the present invention.
The present invention is by using bar-shaped SBA-15 as the carrier of dehydrogenation, make catalyst of the present invention have higher activity and selective than the employing alchlor of prior art etc. as the dehydrogenation of carrier, supposition be since the special microstructure of bar-shaped SBA-15 make its can be better and dehydrogenation active component carry out combination, and it is more even that dehydrogenation active component can be disperseed, and improved activity of such catalysts and selective thus.And, in preferred embodiment of the present invention, adopt copper and silver can further improve activity of such catalysts of the present invention and selective as active component, supposition is because copper and silver can well disperse on bar-shaped SBA-15 carrier.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that the specific embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
Dehydrogenation of the present invention comprises carrier and the dehydrogenation active component that loads on this carrier, and wherein, described carrier is bar-shaped SBA-15.
The present invention is by using bar-shaped SBA-15 as the carrier of dehydrogenation, make catalyst of the present invention have higher activity and selective than the employing alchlor of prior art etc. as the dehydrogenation of carrier, supposition be since the special microstructure of bar-shaped SBA-15 make its can be better and dehydrogenation active component carry out combination, and it is more even that dehydrogenation active component can be disperseed, and improved activity of such catalysts and selective thus.
Among the present invention, described bar-shaped SBA-15 can be the formed body of bar-shaped SBA-15, also can be for directly being bar-shaped SBA-15 (being generally Powdered), and the present invention does not have specific (special) requirements to this.
Among the present invention, being that bar-shaped SBA-15 can realize purpose of the present invention as long as guarantee described carrier, can be the known hole dimension of technical staff in the synthetic field of molecular sieve as the hole dimension of the bar-shaped SBA-15 of described carrier.At the present invention, for the activity that further improves described dehydrogenation of the present invention and selective, the present inventor finds in research process, be the 6-10 nanometer in the most probable aperture of bar-shaped SBA-15 carrier, pore volume is 0.5-1.5 milliliter/gram, when specific area is the 600-700 meters squared per gram, can make described catalyst have higher catalytic activity.More preferably, the most probable aperture of SBA-15 is the 6-6.5 nanometer, and pore volume is 0.8-1.2 milliliter/gram, and specific area is the 600-660 meters squared per gram.Further, the length of the rod of described bar-shaped SBA-15 carrier can be selected in wideer scope and change, and for example, can be the 30-100 micron usually.
The SBA-15 that satisfies above-mentioned condition can be commercially available.For example: be purchased the SBA-15 from high-tech share Co., Ltd of Changchun Jilin University.
Among the present invention, as long as guarantee that described carrier is that bar-shaped SBA-15 can realize purpose of the present invention, the present invention does not have specific (special) requirements to kind and the consumption of described dehydrogenation active component, its optional wider range, specifically can select according to prior art, at the present invention, preferred described dehydrogenation active component contains Cu, more preferably described dehydrogenation active component also contains one or more among Au, Ag, Pd, Pt, Rh, Ru, Ir and the Os, preferred especially described dehydrogenation active component contains Cu and Ag, and the weight ratio of Cu and Ag is 1-100: 1, be preferably 5-20: 1.In the presence of aforementioned dehydrogenation active component, the activity of dehydrogenation of the present invention can further improve, and supposition is because copper and silver can well disperse on bar-shaped SBA-15 carrier.
Optional wider range of dehydrogenation active component in the dehydrogenation of the present invention and the content of carrier, specifically can select with reference to prior art, at the present invention, dehydrogenation active component is 1-50 weight % in the content of oxide in the preferred described dehydrogenation, and the content of carrier is 50-99 weight %.More preferably under the situation, dehydrogenation active component is 2-20 weight % in the content of oxide in the described dehydrogenation, and the content of carrier is 80-98 weight %.
Dehydrogenation of the present invention can be prepared with reference to the whole bag of tricks of prior art, for example can adopt conventional immersion process for preparing, can select according to the concrete form of bar-shaped SBA-15 carrier, if for example carrier is the formed body of bar-shaped SBA-15, for example then can selecting, dry impregnation method (being equi-volume impregnating) is prepared, if carrier directly is bar-shaped SBA-15 (being generally Powdered), the impregnation method of then can selecting for example just to wet is flooded preparation.Among the present invention, the preferred bar-shaped SBA-15 of powder that adopts prepares dehydrogenation, when the bar-shaped SBA-15 that adopts powder prepares dehydrogenation, can select just wet impregnation method to prepare catalyst of the present invention, described just wet impregnation rule is as carrying out as follows: the soluble-salt solution of dehydrogenation active component is contacted with bar-shaped SBA-15 carrier, the carrier after the contact is carried out drying, roasting.Wherein, when dehydrogenation active component was multiple element, the method that the soluble-salt solution of dehydrogenation active component contacts with bar-shaped SBA-15 carrier can be undertaken by following two kinds of methods: (1) contacted with carrier after the soluble-salt of various active component can being formed a kind of mixed solution again; (2) also different soluble salts of active components can be made into the aqueous solution separately, then carrier be contacted (any with the order that various soluble salts of active components solution contact) successively with various soluble salts of active components solution.
According to the preparation method of dehydrogenation of the present invention, the character of described bar-shaped SBA-15 has had detailed description aforementioned in to the description of dehydrogenation, does not repeat them here.
According to the preparation method of dehydrogenation of the present invention, being chosen in of the kind of described dehydrogenation active component is aforementioned to detailed description has been arranged in the description of dehydrogenation, does not repeat them here.
Preparation method according to dehydrogenation of the present invention, optional wider range of the kind of the soluble-salt of described dehydrogenation active component, soluble-salt commonly used all can be used for the present invention, for example can be in acetate, sulfate and the nitrate one or more, be preferably nitrate, specifically, when described active component is Cu, Ag, described soluble copper salt can be in copper nitrate, copper sulphate, copper acetate and the copper chloride one or more, is preferably copper nitrate; Described soluble silver salt can be in silver nitrate, silver sulfate, silver acetate and the silver chlorate one or more, is preferably silver nitrate.
Preparation method according to dehydrogenation of the present invention, optional wider range of the consumption of described soluble-salt, can select according to prior art, at the present invention, in the feasible dehydrogenation for preparing of the consumption of preferred described soluble-salt, dehydrogenation active component is 1-50 weight % in the content of oxide, is preferably 2-20 weight %, the content of carrier is 50-99 weight %, is preferably 80-98 weight %.
Among the present invention, optional wider range of the solution kind of described soluble-salt solution is generally the aqueous solution, depending on the circumstances or the needs of the situation, can add other organic solvent in the aqueous solution, and described organic solvent can be alcohol, ketone, oxolane, hexane and toluene etc.
Preparation method according to dehydrogenation of the present invention, optional wider range of the condition of described drying, roasting, the drying of prior art, the condition of roasting all can realize purpose of the present invention, and for example the temperature of described drying is generally 100-200 ℃, and the time is 0.5-10 hour.And the present inventor finds in research process unexpectedly, adopts bar-shaped SBA-15 of the present invention as carrier material, and the temperature by rational control roasting can further improve the activity of dehydrogenation of the present invention and selective.Therefore, at the present invention, the temperature of preferred described roasting is 300-700 ℃, and more preferably 450-650 ℃, the time is 0.5-12 hour, is preferably 1-8 hour.
According to the dehydrogenation that method of the present invention prepares, need before use usually to reduce earlier and make active component Cu, Ag the activation.The used reducing agent of described reduction can be the various reducing agents of routine, for example, and hydrogen, carbon monoxide, pure steam, hydrazine, formaldehyde and sodium borohydride etc.Be preferably hydrogen.The temperature that the condition of described reduction generally includes activation is 80-500 ℃, is preferably 100-450 ℃.
The application of dehydrogenation in dehydrogenation reaction that the invention provides a kind of dehydrogenation of the present invention or adopt the preparation method of dehydrogenation of the present invention to prepare.Dehydrogenation of the present invention is specially adapted to the reaction that cyclohexanol dehydrogenation prepares cyclohexanone.
Catalyst of the present invention makes catalyst of the present invention dehydrogenation of the present invention be used for dehydrogenation reaction and has higher activity and selective by adopting bar-shaped SBA-15 as carrier material.
The invention provides the method that a kind of cyclohexanol dehydrogenation prepares cyclohexanone, this method comprises: under dehydrogenation condition, cyclohexanol is contacted with dehydrogenation, wherein, described dehydrogenation is dehydrogenation of the present invention or the dehydrogenation for preparing according to the preparation method of dehydrogenation of the present invention.
Dehydrogenation of the present invention is applied to can select to carry out moulding or not moulding according to concrete reaction formation in the cyclohexanol dehydrogenation reaction.To this, those skilled in the art all can know.
Except adopting dehydrogenation of the present invention, the dehydrogenation condition that described cyclohexanol dehydrogenation prepares cyclohexanone can carry out with reference to prior art well-known to those skilled in the art.
Be described in detail below in conjunction with the present invention of embodiment, but the invention is not restricted to this.
In embodiment, described bar-shaped SBA-15 carrier is available from high-tech share Co., Ltd of Changchun Jilin University, and specific nature sees Table 1.
Table 1
Among the present invention, adopt gas chromatograph (to purchase in Shanghai Precision Scientific Apparatus Co., Ltd, model is GC128) carry out in the system analysis that each is formed, undertaken quantitatively by proofreading and correct normalization method, all can carry out with reference to prior art, on this basis the evaluation index such as selective of the conversion ratio of ring hexanol, cyclohexanone.
Cyclohexanone selective (%)=(molal quantity of the cyclohexanol that consumes in the molal quantity/reaction of the cyclohexanone of generation) * 100%,
The conversion ratio of cyclohexanol (%)=(molal quantity of the cyclohexanol that consumes in the reaction/be provided to the molal quantity of the raw material cyclohexanol in the reaction) * 100%.
Embodiment 1-6
Present embodiment is used for the preparation of explanation dehydrogenation provided by the invention.
Under nitrogen protection, with bar-shaped SBA-15 carrier in 400 ℃ of down calcinings 10 hours, thereby obtain bar-shaped SBA-15 carrier through thermal activation.
Adopt the bar-shaped SBA-15 carrier of above-mentioned thermal activation, be equipped with dehydrogenation C1-C6 according to just wet impregnation legal system.Just wet impregnation method comprises the aqueous solution with copper nitrate; The aqueous solution of copper nitrate and silver nitrate floods.Regulate the concentration of salt in the aqueous solution, prepare and contain the catalyst C1-C6 that the different activities component is formed, the solid that obtains behind the dipping was placed 4 hours down in room temperature (25 ℃), 120 ℃ of dryings 6 hours.At last, roasting is two hours in the air of dried solid under uniform temperature (specifically seeing Table 2), and feature and the preparation condition of the catalyst for preparing according to preceding method are listed in the table 2.
Comparative Examples 1-2
This Comparative Examples is used for the preparation of the dehydrogenation of explanation prior art.
Method according to embodiment 1 prepares dehydrogenation D1-D2, and different is that (provided by Alcoa, the BET surface area is 156m to use gamma-aluminium oxide carrier (Shanghai chemical reagent one factory), alpha-alumina supports respectively
2/ g, water absorption is 0.35ml/gAl
2O
3) replace bar-shaped SBA-15 carrier, obtain catalyst D1, D2, the feature of described catalyst is listed in the table 2.
Table 2
EXPERIMENTAL EXAMPLE 1
Catalyst C1 and graphite are mixed the back compacting according to mass ratio at 98: 2, obtain the tablet of the catalyst C1 after the compacting of 5 * 5mm;
Get the tablet of the catalyst C1 after 920g suppresses and insert in the tubular reactor of long 0.6m, internal diameter 0.05m, and before reaction, (under 240 ℃ the temperature, use 150L N with the hydrogen activation
2/ h and 7.5L H
2/ h activated catalyst).The gained catalyst is analyzed with EPMA (X-ray microanalyzer), confirms that active component Cu, Ag are dispersed on the carrier.Analyze for EMPA, as measurement device, the accelerating potential of electron gun is set to 20KV to use JXA-8600M (Nippon Denshi K.K.), and probe current is 2.0 * 10
-8A.
After the activation, at 0.7h
-1Liquid hourly space velocity (LHSV) under, cyclohexanol fed in the tubular reactor contact with dehydrogenation, the contact temperature is 250 ℃, the conversion ratio of cyclohexanol and cyclohexanone selectively sees Table 3 after 200 hours.
EXPERIMENTAL EXAMPLE 2-6
Method according to EXPERIMENTAL EXAMPLE 1 is carried out cyclohexanol dehydrogenation, and the different catalyst that are to use are C2-C6, and concrete outcome sees Table 3.
Experiment Comparative Examples 1-2
Method according to EXPERIMENTAL EXAMPLE 1 is carried out cyclohexanol dehydrogenation, and the different catalyst that are to use are D1-D2, and concrete outcome sees Table 3.
Table 3
Adopt dehydrogenation of the present invention to carry out catalytic dehydrogenation as can be seen by data in the table, can reach higher conversion ratio in the short period of time, and target product selectivity is higher.
More than describe preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in the above-mentioned specific embodiment under reconcilable situation, can make up by any suitable manner, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible compound modes.
In addition, also can carry out any combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. dehydrogenation, this catalyst comprise carrier and load on dehydrogenation active component on this carrier, it is characterized in that described carrier is bar-shaped SBA-15.
2. dehydrogenation according to claim 1, wherein, the length of the rod of described bar-shaped SBA-15 is the 30-100 micron, and the most probable aperture of preferred described bar-shaped SBA-15 is the 6-10 nanometer, pore volume is 0.5-1.5 milliliter/gram, and specific area is the 600-700 meters squared per gram.
3. dehydrogenation according to claim 1 and 2, wherein, described dehydrogenation active component contains Cu, preferred also contain among Au, Ag, Pd, Pt, Rh, Ru, Ir and the Os one or more, more preferably described dehydrogenation active component contains Cu and Ag, and the weight ratio of Cu and Ag is 1-100: 1, be preferably 5-20: 1.
4. dehydrogenation according to claim 1 and 2, wherein, dehydrogenation active component is 1-50 weight % in the content of oxide in the described dehydrogenation, the content of carrier is 50-99 weight %.
5. method for preparing dehydrogenation, this method comprises: the soluble-salt solution of dehydrogenation active component is contacted with carrier, the carrier after the contact is carried out drying, roasting; It is characterized in that described carrier is bar-shaped SBA-15.
6. method according to claim 5, wherein, the length of the rod of described bar-shaped SBA-15 is the 30-100 micron, and the most probable aperture of preferred described bar-shaped SBA-15 is the 6-10 nanometer, pore volume is 0.5-1.5 milliliter/gram, and specific area is the 600-700 meters squared per gram.
7. according to claim 5 or 6 described methods, wherein, described dehydrogenation active component contains Cu, preferred also contain among Au, Ag, Pd, Pt, Rh, Ru, Ir and the Os one or more, more preferably described dehydrogenation active component contains Cu and Ag, and the weight ratio of Cu and Ag is 1-100: 1, be preferably 5-20: 1; The soluble-salt of described dehydrogenation active component is one or more in acetate, sulfate and the nitrate, is preferably nitrate.
8. according to claim 5 or 6 described methods, wherein, in the feasible dehydrogenation for preparing of the consumption of described soluble-salt, dehydrogenation active component is 1-50 weight % in the content of oxide, and the content of carrier is 50-99 weight %.
9. according to claim 5 or 6 described methods, wherein, the temperature of roasting is 300-700 ℃, is preferably 450-650 ℃, and the time is 0.5-12 hour, is preferably 1-8 hour; The temperature of described drying is 100-200 ℃, and the time is 0.5-10 hour.
10. the application of dehydrogenation in dehydrogenation reaction that the preparation method of any described dehydrogenation prepares among any described dehydrogenation or the claim 5-9 among the claim 1-4.
11. a cyclohexanol dehydrogenation prepares the method for cyclohexanone, this method comprises: under dehydrogenation condition, cyclohexanol is contacted with dehydrogenation, it is characterized in that described dehydrogenation is the dehydrogenation that the preparation method of any described dehydrogenation prepares among any described dehydrogenation or the claim 5-9 among the claim 1-4.
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| CN111135852A (en) * | 2018-11-06 | 2020-05-12 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst with rodlike mesoporous molecular sieve as carrier and preparation method and application thereof |
| CN114797947A (en) * | 2022-05-19 | 2022-07-29 | 兄弟科技股份有限公司 | Efficient dehydrogenation catalyst and application thereof in preparation of pyridine by dehydrogenation of piperidine raw materials |
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