CN117205962A - Preparation and application of oxide-molecular sieve composite material - Google Patents
Preparation and application of oxide-molecular sieve composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000004176 ammonification Methods 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910016507 CuCo Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 241001620634 Roger Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a kind ofCuCoO x Preparation method of SAPO-34 oxide-molecular sieve composite catalyst and application of catalyst in ammonification of ethanol to synthesis of acetonitrile, and specifically the catalyst comprises CuCoO x The composite oxide and the SAPO-34 molecular sieve are prepared by adopting a coprecipitation method and a hydrothermal method respectively, and then the SAPO-34 particles and the CuCoOx oxide particles are mixed according to the mass ratio of 0.25-1.5, and fully and uniformly mixed by using a ball mill. The catalyst has the characteristics of high activity, high selectivity and high stability in a working condition reaction system which is higher than atmospheric pressure. The catalyst has the advantages of easily available raw materials, simple preparation process and excellent catalytic performance, and is suitable for industrial mass production.
Description
Technical Field
The invention relates to a catalyst for preparing acetonitrile by ammonification of ethanol, in particular to CuCoO x Preparation method of SAPO-34 oxide-molecular sieve composite catalyst and application thereof in ammonification of ethanol to synthesis of acetonitrile.
Background
Acetonitrile is an important chemical product that is widely used in the pharmaceutical, agrochemical, organic synthesis and petrochemical industries. The current industrial production of acetonitrile is separated from byproducts of acrylonitrile synthesis by ammoxidation of propylene, the yield is severely limited by the starting condition of an acrylonitrile device, along with the increase of the demand, the current industrial demand can not be met, and the development of a production process taking acetonitrile as a target product is a key for solving the increasing demand of acetonitrile in the market.
Compared with the technical routes of acetic acid ammonification and dehydration and ethanol ammonification, the synthesis of acetonitrile by ethanol ammonification has the characteristics of high raw material utilization rate, byproduct hydrogen, milder reaction conditions and the like, so that the method is more interesting.
The key of the process route for synthesizing acetonitrile by ammonification of ethanol is the development of a catalyst, zhang et al [7 ]]In 2009, ni modified Co/gamma-Al 2O3 catalyst is adopted to make the reaction process, under the condition of 100% of ethanol conversion rate, the selectivity of acetonitrile can reach 92.5%, but the reaction temperature is as high as 420 ℃, and the reaction temperature is as high as 420%The piece is relatively harsh. Roger et Al 1981 reported that 15% Cu/Al 2 O 3 Under the action of the catalyst, the catalyst can be used for synthesizing acetonitrile by ammonification of ethanol under the condition that the reaction temperature is 325 ℃. Copper-based catalysts have attracted considerable attention from scientists hereafter.
The reactant ethanol needs to pass through intermediate species such as acetaldehyde, imine and the like to generate acetonitrile, researches show that ethanol to acetaldehyde are a limiting step of the whole process, and the reaction involves hydrogen transfer of activated alcohol, so that an active center of dehydrogenation is required, but from the experimental result, a carrier with a certain dehydration effect is required to interact with the active center of dehydrogenation, so that the subsequent further reaction of the intermediate 1-amino ethanol can be ensured, and the acetonitrile of the target product is obtained. However, in the actual industrial production process, a certain pressure is inevitably generated by the system along with the accumulation of the reaction time, so that NH 3 Partial pressure increases and the catalyst acid sites are replaced by NH 3 Coverage, resulting in a hindered dehydration reaction, a significant decrease in product selectivity. Therefore, it is required to develop a catalyst which has excellent acetonitrile selectivity and can withstand a certain pressure for the industrial production of acetonitrile by actual ammonification of ethanol.
Disclosure of Invention
The present invention addresses the above problems by providing a CuCoO x Preparation of SAPO-34 oxide-molecular sieve composite catalyst and application thereof in synthesizing acetonitrile by ammonification of ethanol.
In order to achieve the above object of the present invention, the present invention adopts the following technical scheme:
the invention provides a catalyst composition of CuCoO x The composite oxide and the SAPO-34 molecular sieve are prepared by adopting a coprecipitation method and a hydrothermal method respectively, and then the SAPO-34 particles and the CuCoOx oxide particles are mixed according to the mass ratio of 0.25-1.5, and then the mixture is fully and uniformly mixed by using a ball mill, wherein the particle size distribution is 10-100 mu m. The catalyst is applied to the ammonification of ethanol to synthesize acetonitrile. CuCoO x Wherein x is a value determined by oxygen of the metal oxide of Cu and the metal oxide of Co. A method for preparing a catalyst comprising the steps of:
(1)CuCoO x preparation of composite oxide: weighing soluble copper salt and cobalt salt according to a required proportion, and dissolving the soluble copper salt and cobalt salt in deionized water to prepare a salt solution A; preparing an equal volume of alkali solution B, placing the alkali solution B in a water bath kettle at 20-50 ℃, and dropwise adding the solution A into the solution B under vigorous stirring; after the dripping is finished, the pH value of the suspension is adjusted to 9-11; then raising the temperature of the water bath to 55-80 ℃, and continuing stirring and crystallizing for 3-8h; filtering, washing, drying, transferring to a muffle furnace, and roasting at 400-650deg.C for 4-6 hr to obtain CuCoO x A composite oxide;
(2) SAPO-34 molecular sieve synthesis: weighing a certain amount of aluminum source and deionized water according to a required proportion, and stirring to uniformly mix the two phases. A certain amount of phosphorus source is weighed and dropwise added into the mixture, and the mixture is stirred for 1h after the addition. A certain amount of silicon source is added into the crystallization mixture dropwise, and the mixture is stirred for 1h after the addition. And (3) dropwise adding a certain amount of template agent into the uniformly mixed crystallization mixture, and stirring for 2 hours until the mixture is uniform after the dropwise adding is finished. Then the gel crystallization mixture which is evenly stirred is transferred into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, aged for 4 to 10 hours at the temperature of 60 to 150 ℃, and then transferred into an oven at the temperature of 180 to 220 ℃ for crystallization for 36 to 65 hours. And after the crystallization time is over, filtering, washing and drying the white slurry at 120 ℃, and roasting the dried solid powder for 4-8 hours at 500-600 ℃ to obtain the solid which is the SAPO-34 molecular sieve.
(3)CuCoO x -SAPO-34 oxide-molecular sieve composite catalyst preparation: mixing SAPO-34 particles and CuCoOx oxide particles in a mass ratio of 0.25-1.5, ball milling for 2-24 hours at room temperature by using a ball mill, fully and uniformly mixing, and reducing in a hydrogen atmosphere to obtain the catalyst.
Further, in the above technical scheme, in the catalyst, cuCoO x The mass percentage of CuO in the composite oxide is 10-30%, and the mass percentage of CoO is 70-90%; cuCoO x The mass percentage of the composite oxide is 40-80wt%, and the mass percentage of the SAPO-34 molecular sieve is 20-60wt%.
Further, in the above technical solution, the preparation method, step (1)The copper salt is copper nitrate and copper chloride; the Co salt is cobalt nitrate and cobalt chloride; the alkali is NaOH, urea or Na 2 CO 3 Or (NH) 4 ) 2 CO 3 One of the aqueous solutions or a mixed aqueous solution of two or more of the aqueous solutions.
Further, in the above technical scheme, in the preparation method, the aluminum source in the step (2) is aluminum nitrate, sodium aluminate, aluminum isopropoxide, aluminum chloride; the phosphorus source is ammonium hydrogen phosphate and phosphoric acid; the silicon source is silica sol, water glass, ethyl orthosilicate and methyl orthosilicate; the template agent is one or more than two template agents selected from Diethylamine (DEA), triethylamine (TEA), TEAOH, piperazine, morpholine, isopropylamine, di-n-propylamine and the like.
Further, in the technical proposal, the molar ratio of the aluminum source, the phosphorus source, the silicon source and the template agent in the step (2) is SiO 2 :Al 2 O 3 :P 2 O 5 Template agent H 2 O＝(0.25-0.6):(0.8-1.0):(0.8-1):(1.9-2.2):(50-80)。
Further, in the technical proposal, the reduction process of the catalyst is 150-500 ℃ and 10% H 2 Reducing in the mixed gas of/He for 1-6 h.
The catalyst is applied to the ammonification of ethanol into acetonitrile under the working condition of more than atmospheric pressure, the reaction temperature is 200-300 ℃, the reaction pressure is 0.15-0.8MPa, and the catalyst has the characteristics of high activity and high selectivity.
The invention has the beneficial effects that:
the catalyst provided by the invention has high acetonitrile selectivity and ethanol conversion rate, excellent stability and good application value in the reaction of synthesizing acetonitrile by ammonifying ethanol under the working condition of being greater than atmospheric pressure.
Detailed Description
Example 1
(1)CuCoO x Preparation of composite oxide: 3.05g of copper nitrate and 11.63g of cobalt nitrate were weighed separately and dissolved in 50mL of deionized water to prepare a mixed salt solution A. 4.35g of sodium carbonate and 2.63g of sodium hydroxide are dissolved in 50mL of deionized water to prepare a mixtureAnd (3) an alkaline solution B. Drop A was added to B with stirring in a 35℃water bath. After the completion of the dropwise addition, the pH of the suspension was adjusted to 9.5 with a 0.5M NaOH solution, and the suspension was transferred to a 70℃thermostat water bath, and the mixture was further stirred and crystallized for 12 hours. Filtering, washing the precipitate with deionized water, oven drying at 100deg.C, transferring to muffle furnace, and calcining at 450deg.C for 4 hr to obtain CuCoO x A composite oxide;
(2) SAPO-34 molecular sieve synthesis: according to the mole ratio of each substance in the synthesis mother liquor of 1Al 2 O 3 :0.3SiO 2 :0.8P 2 O 5 :60H 2 O2 TEAOH weighing a certain amount of pseudo-boehmite and deionized water, stirring for 20min to uniformly mix the two phases. A certain amount of phosphoric acid is weighed and dropwise added into the mixture, and stirring is carried out for 1.5h after the addition. A certain amount of silica sol is added dropwise into the crystallization mixture, and the mixture is stirred for 3 hours after the dropwise addition is finished. A certain amount of TEAOH is added dropwise into the crystallization mixture which is uniformly mixed, and the mixture is stirred for 3 hours after the dripping is finished until the mixture is uniform. Then the gel crystallization mixture which is evenly stirred is transferred into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, aged for 8 hours at 100 ℃, and then transferred into a baking oven at 200 ℃ for crystallization for 44 hours. And after the crystallization time is over, filtering, washing and drying the white slurry at 120 ℃, and roasting the dried solid powder for 6 hours at 550 ℃, wherein the obtained solid is the SAPO-34 molecular sieve.
(3)CuCoO x -SAPO-34 oxide-molecular sieve composite catalyst preparation: 60g of SAPO-34 particles and 40g of CuCoOx oxide particles are mixed, ball-milled for 12 hours at room temperature by using a ball mill, and fully and uniformly mixed, wherein the particle size distribution is 10-100 mu m. Thus obtaining CuCoO x SAPO-34 oxide-molecular sieve composite catalysts.
Comparative example 1
The preparation method is the same as in the step (1) in the example 1 to obtain CuCoO x A composite oxide.
Comparative example 2
The preparation method is the same as in the step (2) in the example 1, and the SAPO-34 molecular sieve is obtained.
Comparative example 3
CuCo is prepared by adopting a fractional precipitation methodO x Composite oxide: weighing 3.05g of copper nitrate, and dissolving the copper nitrate in 15mL of deionized water to prepare a salt solution A; a mixed alkali solution B was prepared by dissolving 4.35g of sodium carbonate and 2.63g of sodium hydroxide in 50mL of deionized water. Drop A was added to B with stirring in a 35℃water bath. After the completion of the dropwise addition, stirring was carried out for 2 hours to obtain a slurry C. 11.63g of cobalt nitrate is added into 35mL of deionized water to prepare a salt solution D, the solution D is added into the slurry C in a dropwise manner, the pH of the suspension is adjusted to 9.5 by using 0.5M NaOH solution, and the suspension is transferred into a constant temperature water bath kettle with the temperature of 70 ℃ for continuous stirring and crystallization for 12 hours. Filtering, washing the precipitate with deionized water, oven drying at 100deg.C, transferring to muffle furnace, and calcining at 450deg.C for 4 hr to obtain CuCoO x A composite oxide; the preparation method of the SAPO-34 is the same as in the step (2) in the example 1, and the SAPO-34 molecular sieve is obtained.
CuCoO x The preparation method of the SAPO-34 oxide-molecular sieve composite catalyst is the same as in the step (3) in the example 1.
Comparative example 4
(1)CuNiO x Preparation of composite oxide: 3.05g of copper nitrate and 11.62g of nickel nitrate were weighed separately and dissolved in 50mL of deionized water to prepare a mixed salt solution A. A mixed alkali solution B was prepared by dissolving 4.35g of sodium carbonate and 2.63g of sodium hydroxide in 50mL of deionized water. Drop A was added to B with stirring in a 35℃water bath. After the completion of the dropwise addition, the pH of the suspension was adjusted to 9.5 with a 0.5M NaOH solution, and the suspension was transferred to a 70℃thermostat water bath, and the mixture was further stirred and crystallized for 12 hours. Filtering, washing the precipitate with deionized water, oven drying at 100deg.C, transferring to muffle furnace, and calcining at 450deg.C for 4 hr to obtain CuNiO x A composite oxide;
the preparation method of the SAPO-34 is the same as in the step (2) in the example 1, and the SAPO-34 molecular sieve is obtained.
CuNiO x The preparation method of the SAPO-34 oxide-molecular sieve composite catalyst is the same as in the step (3) in the example 1.
Example 2
CuCoO x The composite oxide preparation method was the same as in step (1) of example 1, except that "3.05g of copper nitrate and 11.63g of cobalt nitrate" were changed to "2.19g of copper chloride and 5.19g of cobalt chloride";
the preparation method of the SAPO-34 is the same as in the step (2) in the example 1, and the SAPO-34 molecular sieve is obtained.
CuNiO x The preparation method of the SAPO-34 oxide-molecular sieve composite catalyst is the same as in the step (3) in the example 1.
Example 3
CuCoO x The preparation method of the composite oxide is the same as in the step (1) in the example 1, the only difference is that the mixed alkali solution B is prepared by dissolving 4.35g of sodium carbonate and 2.63g of sodium hydroxide in 50mL of deionized water, and the mixed alkali solution B is prepared by dissolving 10.26g of ammonium carbonate in 50mL of deionized water;
the preparation method of the SAPO-34 is the same as in the step (2) in the example 1, and the SAPO-34 molecular sieve is obtained.
CuNiO x The preparation method of the SAPO-34 oxide-molecular sieve composite catalyst is the same as in the step (3) in the example 1.
Example 4
Catalytic performance evaluation: the catalyst activity test was carried out on a fixed bed reactor at a reaction pressure of 0.5MPa. The experimental procedure was as follows: 1g of catalyst (20-40 meshes) and 5g of quartz sand (20-40 meshes) are weighed and mixed uniformly, and then the mixture is filled into a stainless steel reaction tube with the diameter of 10 mm. 10% H was introduced into the reaction tube under atmospheric pressure 2 He gas (20 mL/min) -1 ) After the catalyst was reduced in situ at 300 ℃ for 2 hours, the temperature was reduced to 290 ℃ by purging with nitrogen. Then the raw materials are conveyed into a reaction tube, and the reaction space velocity is 1.0h -1 The molar ratio of the ammonia to the alcohol is 7, the pressure is increased to 0.5MPa, and the chromatographic on-line sampling analysis is carried out after the reaction reaches the stability. The composition of the feed gas phase product was analyzed on-line on an Agilent 6890N chromatograph and the liquid product was analyzed off-line.
Table 1 results of activity tests on catalysts obtained by different preparation methods, reaction conditions: t=290 ℃, p=0.5 MPa
As can be seen from table 1: with CuCoO alone x Compared with oxide, SAPO-34 molecular sieve and industrial copper-based catalyst, cuCoO x The ethanol conversion rate and acetonitrile selectivity on the SAPO-34 oxide-molecular sieve composite catalyst are highest, and the stability is optimal. The experimental result shows that the oxide-molecular sieve composite catalyst has remarkable advantages and improves the catalytic performance.
The present invention is not limited to the embodiments of the present invention.
Specific examples are set forth herein to illustrate embodiments of the invention, with the description of the examples given above only to aid in the understanding of the invention. It should be noted that it will be apparent to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the principle of the invention, and these improvements and modifications fall within the scope of the claims of the invention.
Claims (9)
1. CuCoO x The preparation method of the SAPO-34 oxide-molecular sieve composite catalyst is characterized in that: the catalyst composition is CuCoO x The composite oxide and the SAPO-34 molecular sieve are prepared by adopting a coprecipitation method and a hydrothermal method respectively, and then the SAPO-34 particles and CuCoO are mixed x Mixing oxide particles in a mass ratio of 0.25-1.5, and fully and uniformly mixing by using a ball mill, wherein the particle size distribution is 10-100 mu m; the catalyst is applied to the reaction of synthesizing acetonitrile by ammonification of ethanol, cuCoO x Wherein x is a value determined by oxygen of the metal oxide of Cu and the metal oxide of Co.
2. The method of manufacturing according to claim 1, characterized in that:
(1)CuCoO x preparation of composite oxide: weighing soluble copper salt and cobalt salt according to a required proportion, and dissolving the soluble copper salt and cobalt salt in deionized water to prepare a salt solution A; preparing an equal volume of alkali solution B, placing the alkali solution B in a water bath kettle at 20-50 ℃, and dropwise adding the solution A into the solution B under vigorous stirring; after the dripping is finished, the pH value of the suspension is adjusted to 9-11; then raising the temperature of the water bath to 55-80 ℃, and continuing stirring and crystallizing for 3-8h; filtering, washing, drying, transferring to a muffle furnace, and roasting at 400-650deg.C for 4-6 hr to obtain CuCoO x A composite oxide;
(2) SAPO-34 molecular sieve synthesis: weighing a certain amount of aluminum source and deionized water according to a required proportion, and stirring to uniformly mix the two phases. A certain amount of phosphorus source is weighed and dropwise added into the mixture, and the mixture is stirred for 1h after the addition. A certain amount of silicon source is added into the crystallization mixture dropwise, and the mixture is stirred for 1h after the addition. And (3) dropwise adding a certain amount of template agent into the uniformly mixed crystallization mixture, and stirring for 2 hours until the mixture is uniform after the dropwise adding is finished. Then the gel crystallization mixture which is evenly stirred is transferred into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, aged for 4 to 10 hours at the temperature of 60 to 150 ℃, and then transferred into an oven at the temperature of 180 to 220 ℃ for crystallization for 36 to 65 hours. And after the crystallization time is over, filtering, washing and drying the white slurry at 120 ℃, and roasting the dried solid powder for 4-8 hours at 500-600 ℃ to obtain the solid which is the SAPO-34 molecular sieve.
(3)CuCoO x -SAPO-34 oxide-molecular sieve composite catalyst preparation: mixing SAPO-34 particles and CuCoOx oxide particles in a mass ratio of 0.25-1.5, ball milling for 2-24 hours at room temperature by using a ball mill, fully and uniformly mixing, and reducing in a hydrogen atmosphere to obtain the catalyst.
3. The preparation method according to claim 1 or 2, characterized in that: in the catalyst, cuCoO x The mass percentage of CuO in the composite oxide is 10-30%, and the mass percentage of CoO is 70-90%; cuCoO x The mass percentage of the composite oxide is 40-80wt%, and the mass percentage of the SAPO-34 molecular sieve is 20-60wt%.
4. The preparation method according to claim 2, characterized in that: the copper salt in the step (1) is copper nitrate or copper chloride; the Co salt is cobalt nitrate and cobalt chloride; the alkali is NaOH, urea or Na 2 CO 3 Or (NH) 4 ) 2 CO 3 One of the aqueous solutions or a mixed aqueous solution of two or more of the aqueous solutions.
5. The preparation method according to claim 2, characterized in that: the aluminum source in the step (2) is aluminum nitrate, sodium aluminate, aluminum isopropoxide and aluminum chloride; the phosphorus source is ammonium hydrogen phosphate and phosphoric acid; the silicon source is silica sol, water glass, ethyl orthosilicate and methyl orthosilicate; the template agent is one or more than two template agents selected from Diethylamine (DEA), triethylamine (TEA), TEAOH, piperazine, morpholine, isopropylamine, di-n-propylamine and the like.
6. The preparation method according to claim 2, characterized in that: in the step (2), the molar ratio of the aluminum source, the phosphorus source, the silicon source and the template agent is SiO 2 :Al 2 O 3 :P 2 O 5 Template agent H 2 O＝(0.25-0.6):(0.8-1.0):(0.8-1):(1.9-2.2):(50-80)。
7. The preparation method according to claim 2, characterized in that: the reduction process of the catalyst is 150-300 ℃ and 10% H 2 Reducing in the mixed gas of/He for 1-6 h.
8. The use of the catalyst according to claim 1, wherein: the catalyst is applied to the reaction of synthesizing acetonitrile by ammonifying ethanol under the working condition of being larger than atmospheric pressure.
9. The use according to claim 8, characterized in that: the reaction temperature is 200-500 ℃, and the reaction pressure is 0.15-0.8MPa.
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