CN103285902B - Dehydrogenation catalyst and preparation method and application thereof, and method for preparing cyclohexanone from cyclohexanol in dehydrogenation mode - Google Patents
Dehydrogenation catalyst and preparation method and application thereof, and method for preparing cyclohexanone from cyclohexanol in dehydrogenation mode Download PDFInfo
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- CN103285902B CN103285902B CN201210050432.4A CN201210050432A CN103285902B CN 103285902 B CN103285902 B CN 103285902B CN 201210050432 A CN201210050432 A CN 201210050432A CN 103285902 B CN103285902 B CN 103285902B
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- dehydrogenation
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- active component
- sba
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 31
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 8
- 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
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052762 osmium 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 5
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000010949 copper Substances 0.000 description 16
- 239000013335 mesoporous material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920001992 poloxamer 407 Polymers 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
- 238000003756 stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 235000012791 bagels Nutrition 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 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
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000007725 thermal activation Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000000052 comparative effect Effects 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
- 238000007598 dipping method 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
- 230000006872 improvement Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 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
- 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
- 229910002091 carbon monoxide Inorganic materials 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation 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
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KJPHTXTWFHVJIG-UHFFFAOYSA-N n-ethyl-2-[(6-methoxypyridin-3-yl)-(2-methylphenyl)sulfonylamino]-n-(pyridin-3-ylmethyl)acetamide Chemical compound C=1C=C(OC)N=CC=1N(S(=O)(=O)C=1C(=CC=CC=1)C)CC(=O)N(CC)CC1=CC=CN=C1 KJPHTXTWFHVJIG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 229910000367 silver sulfate Inorganic materials 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
- 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
- -1 such as Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
The invention provides a dehydrogenation catalyst as well as a preparation method and application thereof. The catalyst comprises a carrier and a dehydrogenation active component loaded on the carrier, wherein the carrier is torus-shaped SBA-15. The invention provides a method for preparing cyclohexanone from cyclohexanol in a dehydrogenation mode. As the torus-shaped SBA-15 is used as the carrier of the dehydrogenation catalyst, the catalyst has higher activity and selectivity than those of the dehydrogenation catalyst with aluminum trioxide and the like as the carrier 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 the method for cyclohexanone is prepared in a kind of cyclohexanol dehydrogenation.
Background technology
Cyclohexanone is the important intermediate products of one of polyamide-6 and polyamide-6,6, and in the industrial production, it is produced primarily of the catalytic dehydrogenating reaction of cyclohexanol.Generally have the cyclohexanol catalytic dehydrogenation processes of two types, a kind of is the cyclohexanol high-temperature dehydrogenation carried out at 320-420 DEG C of temperature, and another kind is the cyclohexanol low-temperature dehydrogenation carried out at 220-260 DEG C of temperature.
High-temperature dehydrogenation is owing at high temperature easily occurring to become the side reactions such as cyclohexene as cyclohexanol dehydrogenation, and therefore, target product selective lower, have impact on the economy of this process thus.
Low-temperature dehydrogenation generally carries out under copper-based catalysts exists, but owing to generally carrying out the dehydrogenation of cyclohexanol at relatively low temperature, therefore, usual conversion ratio is relatively low, in order to improve the conversion ratio of the cyclohexanol of this process, existing more research, and major part research is all the catalytic efficiencies improving this process by improving catalyst, improves 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, Above-mentioned catalytic agent is generally by prefabricated deposited on supports mantoquita or flood suitable copper salt solution and prepare, and carrier is generally alundum (Al2O3) Al
2o
3.
The people's such as Chang, in Appl.Catal.A103 (1994) 233-42, having disclosed one is having complexant to deposit in case, use reducing agent electroless copper or reduction deposited copper on carrier, to prepare the method for cyclohexanol non-oxidative dehydrogenation copper catalyst, carrier used is surface area is 22.6m
2α-the Al of/g
2o
3.
As can be seen here, prior art is in order to improve the activity of catalyst, and generally realize by optimizing carrier, although all obtain certain improvement, the activity of catalyst still has much room for improvement.
Summary of the invention
The object of the present invention is to provide higher, the selective good dehydrogenation of a kind of activity.
To achieve these goals, the invention provides a kind of dehydrogenation, this catalyst comprises carrier and load dehydrogenation active component on this carrier, and wherein, described carrier is donut-like SBA-15.
The invention provides a kind of method preparing dehydrogenation, the method comprises: by the soluble salt solutions of dehydrogenation active component and carrier contact, and the carrier after contact is carried out drying, roasting; Wherein, described carrier is donut-like SBA-15.
The invention provides the application of a kind of dehydrogenation of the present invention in dehydrogenation reaction.
The invention provides a kind of method that cyclohexanone is prepared in cyclohexanol dehydrogenation, the method comprises: under dehydrogenation condition, cyclohexanol is contacted with dehydrogenation, wherein, the described dehydrogenation dehydrogenation that is dehydrogenation of the present invention or prepares according to the preparation method of dehydrogenation of the present invention.
The present invention is by using donut-like SBA-15 as the carrier of dehydrogenation, catalyst of the present invention is made to have higher activity and selectivity compared to employing alchlor of prior art etc. as the dehydrogenation of carrier, supposition be due to the special microstructure of donut-like SBA-15 make its can better and dehydrogenation active component combine, and dehydrogenation active component can disperse more even, which thereby enhance the activity and selectivity of catalyst.Further, in a preferred embodiment of the invention, adopt copper and silver can improve the activity and selectivity of catalyst of the present invention further as active component, supposition is because copper and silver well can disperse on donut-like SBA-15 carrier.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of dehydrogenation, this catalyst comprises carrier and load dehydrogenation active component on this carrier, and wherein, described carrier is donut-like SBA-15.
The present invention is by using donut-like SBA-15 as the carrier of dehydrogenation, catalyst of the present invention is made to have higher activity and selectivity compared to employing alchlor of prior art etc. as the dehydrogenation of carrier, supposition be due to the special microstructure of donut-like SBA-15 make its can better and dehydrogenation active component combine, and dehydrogenation active component can disperse more even, which thereby enhance the activity and selectivity of catalyst.
In the present invention, described donut-like SBA-15 can be the formed body of donut-like SBA-15, also can directly for donut-like SBA-15 (being generally Powdered), the present invention to this without particular/special requirement.
In the present invention, as long as ensure that described carrier is that donut-like SBA-15 can realize object of the present invention, for the present invention, in order to improve the activity and selectivity of dehydrogenation of the present invention further, preferred described SBA-15 is donut-like, and the internal diameter of described donut-like SBA-15 and the ratio of external diameter are preferably 0.3-0.9, are more preferably 0.5-0.85; Average grain diameter is preferably 3-20 μm, is more preferably 3-10 μm; Average thickness is preferably 0.1-2 μm, is more preferably 1-2 μm.The various donut-like that donut-like described in the present invention can it has been generally acknowledged that for this area, such as can for there is opening or not there is the various circular of opening or class is circular, described internal diameter and external diameter refer to the radius of the circle at the inner circumferential place of described bagel and the radius of place, periphery circle respectively; Described average thickness refers to the mean value of the thickness of multiple donut-like SBA-15.The thickness of each donut-like SBA-15 refers to the average thickness of each position of this donut-like SBA-15.The most probable pore size of described SBA-15 can be 7-10nm, is preferably 8-9nm; Pore volume can be 0.5-3 ml/g, is preferably 1-2 ml/g; Specific area can be 600-1000 meters squared per gram, is preferably 650-800 meters squared per gram.
The SBA-15 carrier of donut-like of the present invention can be obtained by various mode, such as, can be commercially available, and also can prepare according to various method of the prior art.
In the present invention, as long as ensure that described carrier is that donut-like SBA-15 can realize object of the present invention, the present invention to the kind of described dehydrogenation active component and consumption without particular/special requirement, its range of choices is wider, specifically can select according to prior art, for the present invention, preferred described dehydrogenation active component contains Cu, more preferably described dehydrogenation active component is also containing Au, Ag, Pd, Pt, Rh, Ru, one or more in Ir and Os, particularly 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.Under the existence of aforementioned dehydrogenation active component, the activity of dehydrogenation of the present invention can improve further, and supposition is because copper and silver well can disperse on donut-like SBA-15 carrier.
The range of choices of the dehydrogenation active component in dehydrogenation of the present invention and the content of carrier is wider, specifically can select with reference to prior art, for the present invention, in preferred described dehydrogenation, dehydrogenation active component is with the content of oxide basis for 1-50 % by weight, and the content of carrier is 50-99 % by weight.More preferably, in situation, in described dehydrogenation, dehydrogenation active component is with the content of oxide basis for 2-20 % by weight, and the content of carrier is 80-98 % by weight.
Dehydrogenation of the present invention can be prepared with reference to the various methods of prior art, such as can adopt conventional infusion process preparation, can select according to the concrete form of donut-like SBA-15 carrier, if such as carrier is the formed body of donut-like SBA-15, such as dry impregnation method (i.e. equi-volume impregnating) then can be selected to be prepared, if carrier is directly donut-like SBA-15 (being generally Powdered), then such as incipient wetness can be selected to carry out dipping preparation.In the present invention, the donut-like SBA-15 of preferred employing powder prepares dehydrogenation, when adopting the donut-like SBA-15 of powder to prepare dehydrogenation, incipient wetness can be selected to prepare catalyst of the present invention, described incipient wetness such as can be carried out as follows: by the soluble salt solutions of dehydrogenation active component and donut-like SBA-15 carrier contact, and the carrier after contact is carried out drying, roasting.Wherein, when dehydrogenation active component is multiple element, the method for the soluble salt solutions of dehydrogenation active component and donut-like SBA-15 carrier contact can be undertaken by the following two kinds method: (1) soluble-salt of various active component can be formed after a kind of mixed solution again with carrier contact; (2) also the soluble-salt of different active components can be made into the aqueous solution separately, then carrier be contacted with the soluble salt solutions of various active component (order contacted with the soluble salt solutions of various active component is any) successively.
According to the preparation method of dehydrogenation of the present invention, the character of described donut-like SBA-15 aforementioned to the description of dehydrogenation in be described in detail, do not repeat them here.
According to the preparation method of dehydrogenation of the present invention, the selection of the kind of described dehydrogenation active component aforementioned to the description of dehydrogenation in be described in detail, do not repeat them here.
According to the preparation method of dehydrogenation of the present invention, the range of choices of the kind of the soluble-salt of described dehydrogenation active component is wider, conventional soluble-salt all can be used for the present invention, can be such as one or more in acetate, sulfate and nitrate, be preferably nitrate, specifically, when described active component is Cu, Ag, described soluble copper salt can be one or more in copper nitrate, copper sulphate, copper acetate and copper chloride, is preferably copper nitrate; Described soluble silver salt can be one or more in silver nitrate, silver sulfate, silver acetate and silver chlorate, is preferably silver nitrate.
According to the preparation method of dehydrogenation of the present invention, the range of choices of the consumption of described soluble-salt is wider, can select according to prior art, for the present invention, the consumption of preferred described soluble-salt makes in the dehydrogenation prepared, and dehydrogenation active component for 1-50 % by weight, is preferably 2-20 % by weight with the content of oxide basis, the content of carrier is 50-99 % by weight, is preferably 80-98 % by weight.
In the present invention, the range of choices of the solution type of described soluble salt solutions is wider, is generally the aqueous solution, depending on the circumstances or the needs of the situation, can add other organic solvent in aqueous, and described organic solvent can be alcohol, ketone, oxolane, hexane and toluene etc.
According to the preparation method of dehydrogenation of the present invention, the range of choices of the condition of described drying, roasting is wider, the drying of prior art, the condition of roasting all can realize object of the present invention, and the temperature of such as described drying is generally 100-200 DEG C, and the time is 0.5-10 hour.And the present inventor finds unexpectedly in research process, adopt donut-like SBA-15 of the present invention as carrier material, the activity and selectivity of dehydrogenation of the present invention can be improved by the temperature reasonably controlling roasting further.Therefore, the temperature for the preferred described roasting of the present invention is 300-700 DEG C, is more preferably 400-600 DEG C, and the time is 0.5-12 hour, is preferably 1-8 hour.
According to the dehydrogenation that method of the present invention prepares, usually need before use first to carry out reducing and active component Cu, Ag being activated.Described reduction reducing agent used can be conventional various reducing agents, such as, and hydrogen, carbon monoxide, alcohol steam, hydrazine, formaldehyde and sodium borohydride etc.Be preferably hydrogen.The temperature that the condition of described reduction generally includes activation is 80-500 DEG C, is preferably 100-450 DEG C.
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 cyclohexanone is prepared in cyclohexanol dehydrogenation.
Catalyst of the present invention, by adopting donut-like SBA-15 as carrier material, makes catalyst of the present invention dehydrogenation of the present invention for having higher activity and selectivity in dehydrogenation reaction.
The invention provides a kind of method that cyclohexanone is prepared in cyclohexanol dehydrogenation, the method comprises: under dehydrogenation condition, cyclohexanol is contacted with dehydrogenation, wherein, the described dehydrogenation dehydrogenation that is dehydrogenation of the present invention or prepares according to the preparation method of dehydrogenation of the present invention.
Dehydrogenation of the present invention is applied in cyclohexanol dehydrogenation reaction and can carries out shaping or not shaping according to the selection of concrete reaction formation.To this, those skilled in the art all can know.
Except adopting dehydrogenation of the present invention, the dehydrogenation condition that cyclohexanone is prepared in described cyclohexanol dehydrogenation can carry out with reference to prior art well-known to those skilled in the art.
Below in conjunction with embodiment, the present invention is described in detail, but the present invention is not limited thereto.
In the present invention, gas chromatograph is adopted (to be purchased from Shanghai Precision Scientific Apparatus Co., Ltd, model is GC128) carry out each analysis formed in system, undertaken quantitatively by correcting normalization method, all can refer to prior art to carry out, on this basis the evaluation index such as the conversion ratio of ring hexanol, the selective of cyclohexanone.
Cyclohexanone selective (%)=(molal quantity of the cyclohexanol consumed in the molal quantity/reaction of the cyclohexanone of generation) × 100%,
The conversion ratio (%) of cyclohexanol=(molal quantity of the molal quantity of the cyclohexanol consumed in reaction/the be provided to raw material cyclohexanol in reaction) × 100%.
The donut-like SBA-15 carrier adopted in following embodiment 1-6 is according to Sun Jinyu; Zhao Dongyuan, the synthesis of " bagel " shape high-sequential big-pore mesoporous molecular sieve SBA-15, SCI; preparation method's preparation of 2000,1 (21): 21 ~ 23.
SBA-15 sample 1:
With DMF (DMF) as cosolvent, by 2.0 grams of Pluronic F-127 ethers-polycyclic oxypropylene ether-Pluronic F-127 ether triblock copolymer surfactant (Aldrich, average molecular mass Mn=5800, molecular formula EO
20pO
70eO
20) be dissolved in 45 grams of distilled water and 30 grams of (4mol/L) hydrochloric acid, at 40 DEG C, add 15 grams of DMF.Stir after 1 hour and add 4.45 grams of ethyl orthosilicates (TEOS, Shenyang chemical reagent work), in 40 DEG C of stirring reactions 24 hours.Former powder mesoporous material is obtained after filtration, washing, drying.By former for gained powder mesoporous material in Muffle furnace 600 DEG C calcining 24 hours, remove template agent, obtain donut-like mesoporous material SBA-15 sample 1.
SBA-15 sample 2:
With DMF (DMF) as cosolvent, by 2.0 grams of Pluronic F-127 ethers-polycyclic oxypropylene ether-Pluronic F-127 ether triblock copolymer surfactant (Aldrich, average molecular mass Mn=5800, molecular formula EO
20pO
70eO
20) be dissolved in 50 grams of distilled water and 30 grams of (4mol/L) hydrochloric acid, at 30 DEG C, add 20 grams of DMF.Stir after 1 hour and add 5.5 grams of ethyl orthosilicates (TEOS, Shenyang chemical reagent work), in 50 DEG C of stirring reactions 24 hours.Former powder mesoporous material is obtained after filtration, washing, drying.By former for gained powder mesoporous material in Muffle furnace 400 DEG C calcining 24 hours, remove template agent, obtain donut-like mesoporous material SBA-15 sample 2.
SBA-15 sample 3:
With DMF (DMF) as cosolvent, by 2.0 grams of Pluronic F-127 ethers-polycyclic oxypropylene ether-Pluronic F-127 ether triblock copolymer surfactant (Aldrich, average molecular mass Mn=5800, molecular formula EO
20pO
70eO
20) be dissolved in 45 grams of distilled water and 30 grams of (4mol/L) hydrochloric acid, at 50 DEG C, add 15 grams of DMF.Stir after 1 hour and add 4.5 grams of ethyl orthosilicates (TEOS, Shenyang chemical reagent work), in 60 DEG C of stirring reactions 24 hours.Former powder mesoporous material is obtained after filtration, washing, drying.By former for gained powder mesoporous material in Muffle furnace 700 DEG C calcining 24 hours, remove template agent, obtain donut-like mesoporous material SBA-15 sample 3.
Table 1 is the pore structure parameter of the SBA-15 prepared according to the method described above.
The parameters of donut-like SBA-15 carrier in table 1; comprise the ratio of internal diameter and external diameter, average thickness, most probable pore size, pore volume, BET specific surface area and average particulate diameter all according to Sun Jinyu; Zhao Dongyuan; the synthesis of " bagel " shape high-sequential big-pore mesoporous molecular sieve SBA-15; SCI; 2000, disclosed in 1 (21): 21 ~ 23, method of testing records.
Embodiment 1-6
The present embodiment is for illustration of the preparation of dehydrogenation provided by the invention.
By whole donut-like SBA-15 of above-mentioned synthesis 400 DEG C of roastings 10 hours (thermal activation) under nitrogen protection, obtain the donut-like SBA-15 after thermal activation.
Adopt the donut-like SBA-15 carrier of above-mentioned thermal activation, prepare dehydrogenation C1-C6 according to incipient wetness.Incipient wetness comprises the aqueous solution with copper nitrate; The mixed aqueous solution of copper nitrate and silver nitrate floods.Regulate the concentration of salt in aqueous solution, prepare the catalyst C1-C6 containing different activities component composition, the solid obtained after dipping is placed 4 hours, 120 DEG C of dryings 6 hours under room temperature (25 DEG C).Finally, roasting two hours in the air of dried solid (specifically in table 2) at a certain temperature, feature and the preparation condition of the catalyst prepared according to preceding method are listed in table 2.
Comparative example 1-2
This comparative example is for illustration of the preparation of the dehydrogenation of prior art.
Dehydrogenation D1-D2 is prepared according to the method for embodiment 1, unlike, use gamma-aluminium oxide carrier (Solution on Chemical Reagents in Shanghai one factory) respectively, (provided by Alcoa, BET surface area is 156m to alpha-alumina supports
2/ g, water absorption is 0.35ml/gAl
2o
3) replace donut-like SBA-15 carrier, obtain catalyst D1, D2, the feature of described catalyst is listed in table 2.
Table 2
EXPERIMENTAL EXAMPLE 1
Catalyst C1 is carried out mixing rear compacting according to mass ratio 98: 2 with graphite, obtains the tablet of the catalyst C1 after the compacting of 5 × 5mm;
The tablet getting the catalyst C1 after 920g compacting is inserted in the tubular reactor of long 0.6m, internal diameter 0.05m, and uses Hydrogen activation (at the temperature of 240 DEG C, to use 150L N before the reaction
2/ h and 7.5L H
2/ h activated catalyst).Gained catalyst EPMA (X-ray microanalyzer) analyzes, and confirms that active component Cu, Ag are dispersed on carrier.Analyze for EMPA, use JXA-8600M (NipponDenshi K.K.) as measurement device, the accelerating potential of electron gun is set to 20KV, and probe current is 2.0 × 10
-8a.
After activation, at 0.7h
-1liquid hourly space velocity (LHSV) under, passed in tubular reactor by cyclohexanol and contact with dehydrogenation, Contact Temperature is 240 DEG C, the conversion ratio of cyclohexanol and the selective in table 3 of cyclohexanone after 200 hours.
EXPERIMENTAL EXAMPLE 2-6
Carry out cyclohexanol dehydrogenation according to the method for EXPERIMENTAL EXAMPLE 1, unlike the use of catalyst be C2-C6, concrete outcome is in table 3.
Experimental comparison's example 1-2
Carry out cyclohexanol dehydrogenation according to the method for EXPERIMENTAL EXAMPLE 1, unlike the use of catalyst be D1-D2, concrete outcome is in table 3.
Table 3
| Numbering | Catalyst | Cyclohexanol conversion ratio (%) | Cyclohexanone selective (%) |
| EXPERIMENTAL EXAMPLE 1 | C1 | 75.58 | 99.69 |
| EXPERIMENTAL EXAMPLE 2 | C2 | 74.99 | 99.78 |
| EXPERIMENTAL EXAMPLE 3 | C3 | 75.03 | 99.80 |
| EXPERIMENTAL EXAMPLE 4 | C4 | 73.06 | 98.97 |
| EXPERIMENTAL EXAMPLE 5 | C5 | 71.24 | 99.14 |
| EXPERIMENTAL EXAMPLE 6 | C6 | 72.91 | 98.85 |
| Experimental comparison's example 1 | D1 | 50.91 | 99.23 |
| Experimental comparison's example 2 | D2 | 50.36 | 98.96 |
As can be seen from data in table, adopt dehydrogenation of the present invention to carry out catalytic dehydrogenation, higher conversion ratio can be reached in the short period of time, and target product selectivity is higher.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive 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.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different 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 (16)
1. a dehydrogenation, this catalyst comprises carrier and load dehydrogenation active component on this carrier, it is characterized in that, described carrier is donut-like SBA-15, the internal diameter of described donut-like SBA-15 and the ratio of external diameter are 0.3-0.9, and average thickness is 0.1-2 micron; Described dehydrogenation active component contains Cu, also containing one or more in Au, Ag, Pd, Pt, Rh, Ru, Ir and Os.
2. dehydrogenation according to claim 1, wherein, the most probable pore size of described donut-like SBA-15 is 7-10nm, and pore volume is 0.5-3 ml/g, and specific area is 600-1000 meters squared per gram, and average grain diameter is 3-20 μm.
3. dehydrogenation according to claim 1, wherein, described dehydrogenation active component contains Cu and Ag, and the weight ratio of Cu and Ag is 1-100:1.
4. dehydrogenation according to claim 3, wherein, the weight ratio of described Cu and Ag is 5-20:1.
5. dehydrogenation according to claim 1, wherein, in described dehydrogenation, dehydrogenation active component is with the content of oxide basis for 1-50 % by weight, and the content of carrier is 50-99 % by weight.
6. prepare a method for dehydrogenation, the method comprises: by the soluble salt solutions of dehydrogenation active component and carrier contact, and the carrier after contact is carried out drying, roasting; It is characterized in that, described carrier is donut-like SBA-15, and the internal diameter of described donut-like SBA-15 and the ratio of external diameter are 0.3-0.9, and average thickness is 0.1-2 micron; Described dehydrogenation active component contains Cu, also containing one or more in Au, Ag, Pd, Pt, Rh, Ru, Ir and Os.
7. method according to claim 6, wherein, the most probable pore size of described donut-like SBA-15 is 7-10nm, and pore volume is 0.5-3 ml/g, and specific area is 600-1000 meters squared per gram, and average grain diameter is 3-20 μm.
8. method according to claim 6, wherein, the soluble-salt of described dehydrogenation active component is one or more in acetate, sulfate and nitrate.
9. method according to claim 8, wherein, the soluble-salt of described dehydrogenation active component is nitrate.
10. method according to claim 9, wherein, described dehydrogenation active component contains Cu and Ag, and the weight ratio of Cu and Ag is 1-100:1.
11. methods according to claim 10, wherein, the weight ratio of described Cu and Ag is 5-20:1.
12. methods according to claim 6, wherein, the consumption of described soluble-salt makes in the dehydrogenation prepared, and dehydrogenation active component is with the content of oxide basis for 1-50 % by weight, and the content of carrier is 50-99 % by weight.
13. methods according to claim 6, wherein, the temperature of roasting is 300-700 DEG C, and the time is 0.5-12 hour; The temperature of described drying is 100-200 DEG C, and the time is 0.5-10 hour.
14. methods according to claim 13, wherein, the temperature of roasting is 400-600 DEG C, and the time is 1-8 hour.
The application of dehydrogenation in dehydrogenation reaction that the preparation method of the dehydrogenation in the dehydrogenation in 15. 1 kinds of claim 1-5 described in any one or claim 6-14 described in any one prepares.
The method of cyclohexanone is prepared in 16. 1 kinds of cyclohexanol dehydrogenations, the method comprises: under dehydrogenation condition, cyclohexanol is contacted with dehydrogenation, it is characterized in that, the dehydrogenation that the preparation method that described dehydrogenation is the dehydrogenation in the dehydrogenation in claim 1-5 described in any one or claim 6-14 described in any one prepares.
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| "面包圈"状高有序度大孔径介孔分子筛SBA-15的合成;孙锦玉等;《高等学校化学学报》;20000131;第21卷(第1期);第21-23页 * |
| Preparation and characterization of Pt-Sn/SBA-15 catalysts and their catalytic performances for long chain alkane dehydrogenation;Lu Zexiang 等;《Chinese journal of chemical engineering》;20081231;第16卷(第5期);第740-745页 * |
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