CN116328805A - Catalyst for low-carbon alkane selective oxidation of high-value chemicals and preparation method thereof - Google Patents
Catalyst for low-carbon alkane selective oxidation of high-value chemicals and preparation method thereof Download PDFInfo
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- CN116328805A CN116328805A CN202111548025.1A CN202111548025A CN116328805A CN 116328805 A CN116328805 A CN 116328805A CN 202111548025 A CN202111548025 A CN 202111548025A CN 116328805 A CN116328805 A CN 116328805A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
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- 239000000126 substance Substances 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 132
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910052582 BN Inorganic materials 0.000 claims abstract description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 6
- 239000010431 corundum Substances 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 37
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- 239000003795 chemical substances by application Substances 0.000 claims description 11
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
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- 238000003786 synthesis reaction Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
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- 238000001035 drying Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 241000219793 Trifolium Species 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims 1
- RBFRVUKIVGOWND-UHFFFAOYSA-L oxygen(2-);vanadium(4+);sulfate Chemical compound [O-2].[V+4].[O-]S([O-])(=O)=O RBFRVUKIVGOWND-UHFFFAOYSA-L 0.000 claims 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 33
- 239000000047 product Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 239000012071 phase Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
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- 239000011551 heat transfer agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 229910052714 tellurium Inorganic materials 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a catalyst for selectively oxidizing high-value chemicals by using low-carbon alkane and a preparation method thereof, wherein the element composition of the catalyst is Mo 1.0 V a Te b Nb c X d O n Wherein a ranges from 0.2 to 1.0, b ranges from 0.2 to 1.0, c ranges from 0.1 to 0.5, d ranges from 0.1 to 0.5, and n is related to the oxidation states and contents of Mo, V, te and Nb. X is one or more of simple substance silicon powder, silicon carbide powder, quartz powder, corundum powder, silicon nitride and boron nitride. Catalyst active powder and diluted heat conducting agentMixing the binder and the forming auxiliary agent uniformly, then directly tabletting and forming or extruding and forming, and roasting the formed catalyst in inert gas at 300-500 ℃ for 0.5-10 hours. The catalyst with the regular shape is used in the low-carbon alkane selective oxidation reaction, and the target product has high selectivity and excellent reaction stability.
Description
Technical Field
The invention provides a preparation method of a low-carbon alkane selective oxidation catalyst and application of the catalyst in catalyzing low-carbon alkane selective oxidation of high-value chemicals in the presence of molecular oxygen.
Background
For the process of catalytically converting low-carbon alkane into high-value chemicals, such as preparing ethylene by catalytic oxidative dehydrogenation of ethane, preparing acrylic acid by one-step selective oxidation of propane, preparing acrylonitrile by ammoxidation, and the like, many reports exist, and the catalyst with the best performance is known as a Mo-V-Te-Nb-O system. Extensive basic research has been conducted on this catalyst system in which the M1 phase with an orthogonal structure is the key active phase for the conversion of lower alkanes to higher value chemicals: the X-ray diffraction pattern (XRD) of the M1 phase (ICSD 55097) has characteristic diffraction peaks at 2θ=6.6 °, 7.7 °, 8.9 °, 22.1 ° and 27.1 °, and its morphology is generally rod-like: the cross section is a (001) crystal face, and is the active center position of the low-carbon alkane for catalytic conversion into high-value chemicals. However, to date, there has been no disclosure regarding the formation of Mo-V-Te-Nb-O catalyst systems, in part because of the particular sensitivity of catalyst structure and performance to manufacturing parameters, the difficulty of obtaining a high performance catalyst, and the difficulty of repeated catalyst preparation, further formation for pilot demonstration of insufficient research power. In addition, the molded M1 phase catalyst particles have larger size, usually millimeter, and a single tube pilot plant reactor with larger size is needed to complete the evaluation of the catalyst.
Because a large amount of heat is generated in the oxidation reaction process of low-carbon alkane such as ethane, particularly under the conditions of high load and high temperature and high pressure, a high-temperature part is formed in a catalyst bed layer by a large amount of heat generated by the reaction, and the heat accumulation at the hot spot part can cause the deep oxidation of target products such as ethylene to be increased so as to reduce the selectivity and the yield, and the thermal decomposition of active components of the catalyst is easy to cause, so that the deactivation of the catalyst is accelerated, and the danger such as temperature runaway and the like can be brought about. In particular an oxide catalyst comprising a tellurium (Te) component: te in catalyst 4+ Is easily reduced into simple substance tellurium (Te in the low-carbon alkane reaction at high temperature 0 ) And precipitates (Russian Journal of Physical Chemistry, P1133, volume 90, stage 6, 2016) to destroy the catalyst structure and thus permanently deactivate it. In future industrial processes, to ensure low alkane conversion, the molten salt temperature needs to be continuously increased. The initial use temperature of the catalyst is reduced, the difference between the hot spot temperature and the molten salt is reduced, and the temperature rise range of the catalyst is increased, so that the service life of the catalyst is prolonged. The purpose of increasing the catalyst activity is to reduce the initial use temperature of the catalyst. The service life of the catalyst is prolonged, and the premise is that the selectivity of the target product is not reduced.
Disclosure of Invention
The invention aims to provide a catalyst for selectively oxidizing high-value chemicals by using low-carbon alkane and a preparation method thereof.
A process for preparing catalyst used for selectively oxidizing high-value chemical from low-carbon alkane includes such steps as preparing Mo 1.0 V a Te b Nb c X d O n Wherein a ranges from 0.2 to 1.0, b ranges from 0.2 to 1.0, c ranges from 0.1 to 0.5, d ranges from 0.1 to 0.5, and n is of a size related to the oxidation states and contents of Mo, V, te and Nb. X is one or more of simple substance silicon powder, silicon carbide powder, quartz powder, corundum powder, silicon nitride and boron nitride.
The preparation method of the catalyst comprises the following steps:
(1) Dissolving Mo source and Te source in water at 50-90 deg.C to obtain solution A, dissolving V source in water at 50-90 deg.C to obtain solution B, dissolving Nb source in water at 50-90 deg.C to obtain solution C, dropping solution B into solution A at 60-90 deg.C to obtain solution D, and dropping solution C into solution D to obtain solution E; transferring the solution E into a stainless steel synthesis kettle to generate hydrothermal reaction (kept at 160-210 ℃ for 2-72 hours) to obtain a precipitate, drying at 60-110 ℃ to obtain a catalyst filter cake, performing preliminary breaking and ball milling on the filter cake to obtain a catalyst precursor, and roasting the catalyst precursor in an inert atmosphere at 500-700 ℃ to obtain the catalyst active powder.
(2) Uniformly mixing the catalyst active powder with a diluted heat-conducting agent, a binder and a forming auxiliary agent, and then directly tabletting for forming or extruding for forming to obtain a formed catalyst; the formed catalyst is solid or hollow particles in the shape of sphere, cylinder, hollow cylinder, clover or gear; the diluted heat-conducting agent is one or more of simple substance silicon powder, silicon carbide powder, quartz powder, corundum powder, silicon nitride and boron nitride, and the addition amount of the diluted heat-conducting agent is 0.1-90 wt% of the weight of the catalyst active powder; the binder is one or more of silica gel, starch, polyethylene glycol, polymethyl cellulose and polyethyl cellulose, and the addition amount of the binder is 0.1-10wt% of the weight of the catalyst active powder; the forming auxiliary agent is one or more forming auxiliary agents selected from water, graphite, silica sol, glycerin and cellulose, and the addition amount of the forming auxiliary agent is 0.1-10wt% of the weight of the catalyst active powder. "wt%" in the above description means weight percent.
Based on the above technical scheme, preferably, molybdenum acid, ammonium paramolybdate or molybdenum oxide is adopted as the Mo source, ammonium metavanadate, vanadium oxide or vanadyl sulfate is adopted as the V source, tellurium dioxide or telluric acid is adopted as the Te source, niobium oxalate or niobium pentoxide is adopted as the Nb source, and the like.
Based on the technical scheme, preferably, the surface active agent can be also used in the preparation process of the molybdenum vanadium tellurium niobium catalyst precursor, the surface active agent is a cationic surface active agent, preferably a quaternary ammonium salt surface active agent, such as cetyltrimethylammonium bromide and octadecyl dimethyl benzyl ammonium chloride, and the mol ratio of Mo to the surface active agent is 1.0:0.1-0.5.
Based on the above technical scheme, preferably, the catalyst active powder is an M1 phase pure phase material or a mixed crystal phase material composed of M1 and M2 phases, and the numbers of M1 and M2 in an Inorganic Crystal Structure Database (ICSD) are 55097 and 55098 respectively.
Based on the technical scheme, the addition amount of the diluted heat conducting agent is preferably 20-60 wt% of the weight of the catalyst active powder, and more preferably, the addition amount of the diluted heat conducting agent is 30-50 wt% of the weight of the catalyst active powder.
Based on the technical scheme, the addition amount of the binder is preferably 3-7wt% of the weight of the catalyst active powder.
Based on the technical scheme, the addition amount of the forming additive is preferably 3-7 wt% of the weight of the catalyst active powder.
The catalyst for the selective oxidation of high-value chemicals by using low-carbon alkane, which is prepared by the method, is disclosed.
The invention uses the catalyst with specific shape in the reaction of low-carbon alkane selective oxidation high-value chemicals. Take as an example the use of ethane oxidative dehydrogenation: in the presence of molecular oxygen, the reaction is carried out in a reaction device for preparing ethylene by oxidative dehydrogenation of ethane. The raw material gas comprises 5-40% of ethane, 20-95% of air and 0-40% of water, the total volume percentage composition of the raw material gas is 100%, the reaction temperature is 300-500 ℃, the reaction pressure is normal pressure-1.0 MPaG, and the total space velocity of the reaction is 500h -1 ～8000h -1 . "MPaG" means that the pressure gauge at the inlet of the single tube reactor displays pressure in MPa.
Based on the technical proposal, the preferable raw material gas volume percentage composition is 20-30% of ethane, 40-70% of air, 10-30% of water, the total volume percentage composition of the raw material gas is 100%, the reaction temperature is 350-450 ℃, the reaction pressure is 0.2-0.5 MPaG, and the total space velocity of the reaction is 2000-5000 h -1 。
In the preparation process of the Mo-V-Te-Nb-O catalyst system, the key point is that the X component is added into the catalyst active powder, so that partial reaction heat can be timely and effectively dispersed and removed in the low-carbon alkane selective oxidation high-value chemical, the hot spot temperature is reduced, and the double purposes of improving the selectivity of target products and prolonging the service life of the catalyst are achieved. The prepared catalyst has higher low-carbon alkane conversion rate, target product selectivity and excellent reaction stability, can run in a wider temperature range without temperature runaway, and can effectively improve the stability of the catalyst. The formed catalyst can be used for converting light alkane into target product under the condition of high selectivity and high yield.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD) of the catalyst active powder prepared in example 1.
Detailed Description
In the present invention, the term "lower alkane" refers to ethane and propane.
In the present invention, the term "single tube" refers specifically to a single tube reactor used in a reaction apparatus for producing ethylene by oxidative dehydrogenation of ethane.
In the present invention, the term "hot spot temperature" refers to the highest temperature of the bed actually measured in a reactor for producing ethylene by oxidative dehydrogenation of ethane, and is a highest temperature point existing in the axial direction of a single-tube reactor.
In the present invention, the term "set temperature" refers specifically to the temperature of the molten salt actually set in the reaction apparatus for producing ethylene by oxidative dehydrogenation of ethane.
In the present invention, the term "inlet pressure" refers to the pressure actually set at the inlet of a single-tube reactor in a reactor for producing ethylene by oxidative dehydrogenation of ethane, and is actually realized by controlling the outlet pressure of the single-tube reactor.
In the present invention, the term "deep oxidation product" refers to the sum of carbon dioxide and carbon monoxide, without acetic acid.
In the present invention, the term "shaped catalyst" refers to a catalyst having a regular shape such as a sphere, a cylinder, a hollow cylinder, and the like.
In the present invention, the reaction of preparing ethylene by oxidative dehydrogenation of ethane is described as an example of selective oxidation of lower alkane, but the scope of application of the catalyst described in the present invention is not limited thereto.
The ethane oxidative dehydrogenation reaction is an exothermic reaction, so that the hot spot temperature is higher than the set temperature of molten salt. At higher reaction space velocity, set temperature and set pressure, the reaction speed is increased, so that the hot spot temperature is usually obviously higher than the molten salt temperature, and as a result, the amount of deep oxidation products generated by the oxidation reaction is obviously increased, and the adverse effects of reduced ethylene selectivity of target products, shortened service life of the catalyst and the like are caused. The inventor of the present invention found that when a certain amount of diluted heat conducting agent is added to the active powder of the catalyst, the temperature difference between the hot spot temperature of the bed layer and the set temperature of the reaction electric furnace can be obviously reduced, thereby advantageously reducing the generation amount of deep oxidation products, improving the selectivity of ethylene and prolonging the service life of the catalyst, and simultaneously obviously reducing the carbon dioxide emission.
In the invention, ethane, air and water (if any) are preheated and mixed and then enter a single tube filled with a formed catalyst to perform oxidative dehydrogenation reaction, the main product is ethylene, the byproducts are deep oxidation products and acetic acid, and the formation of water is accompanied. The product is fully separated into gas-liquid two phases after secondary cooling: the vapor phase materials include ethylene, ethane, deep oxidation products, oxygen and nitrogen, and the liquid phase materials include acetic acid and water. Sampling analysis was started after 6 hours of single tube reaction operation.
Ethane conversion and product selectivity were calculated according to the following formula:
conversion (%) = (amount of ethane in feed-amount of ethane in discharge) ×100%/amount of ethane in feed
Product selectivity (%) = (mi×ni)/(Σmi×ni) ×100%
( Mi, the amount of substance of a certain product i; ni-the number of carbon atoms contained in the molecule of a certain product i )
In the invention, all the examples and comparative examples have a material balance of 98-102%.
The following examples further illustrate the invention, but are not intended to limit it.
Example 1
The preparation procedure of the molybdenum vanadium tellurium niobium catalyst precursor is shown in patent ZL201410198867.2. Except that the dosage of various raw materials is amplified 10000 times, and a specially-made 500L high-pressure stainless steel synthesis kettle is used. Namely, a temperature programming hydrothermal synthesis method is adopted to prepare the Mo-V-Te-Nb-O catalyst. Firstly, weighing and proportioning ammonium molybdate, vanadyl sulfate, telluric acid and niobium oxalate, respectively dissolving in hot deionized water, respectively heating for 30-60 minutes, slowly mixing the solutions together in sequence, continuously stirring for 10-30 minutes, adding a certain amount of surfactant CTAB (the mass ratio of the CTAB/Mo=0.04), continuously stirring for 3-10 minutes, transferring the mixture into a 500L stainless steel tube synthesis kettle, heating the mixture to 180 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 20 hours, naturally cooling the mixture to room temperature, taking out, filtering and drying the obtained gray black filter cake, grinding the gray black filter cake in a ball mill, placing the dried gray black filter cake in a batch type atmosphere roasting rotary kiln, introducing nitrogen with a flow of 50ml/min, continuously preserving heat for 2 hours at a heating rate of 3 ℃/min, and naturally cooling the obtained product, namely the roasted black catalyst active powder. 2000g of the catalyst active powder is taken, 1000g of silicon carbide powder, 100g of silica gel and 100g of graphite are respectively and sequentially added, and after uniform mixing, the mixture is pressed into a cylinder with the outer diameter and the height of 5mm. After the obtained cylindrical catalyst is roasted for 5 hours at 500 ℃ in nitrogen, 2000g of the roasted cylindrical catalyst is used for ethane oxidative dehydrogenation single-tube reaction, and the reaction conditions are as follows: setting the temperature to 360 ℃ and reacting the total volume space velocity for 2000h -1 The volume ratio of ethane, air and water vapor was 25:65:10, and the reaction was carried out at an inlet pressure of 0.25 MPaG. The reaction results are: ethane conversion was 55.1%, ethylene selectivity was 92.1% and hot spot temperature was 397 ℃. The reaction results are shown in Table 1.
The X-ray diffraction (XRD) spectrum of the catalyst active powder prepared by the embodiment is shown in figure 1, and only the characteristic diffraction peak of the M1 phase catalyst appears.
Example 2
The procedure for the preparation of the catalyst in this example was as described in example 1, except that the silicon carbide powder was added in an amount of 500g.
2000g of the above cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same reaction conditions as in example 1. The reaction results are: ethane conversion was 59.1%, ethylene selectivity was 90.4% and hot spot temperature was 404 ℃. The reaction results are shown in Table 1.
Example 3
The procedure for the preparation of the catalyst in this example was as described in example 1, except that the silicon carbide powder was added in an amount of 1400g.
2000g of the above cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same reaction conditions as in example 1. The reaction results are: ethane conversion was 35.4%, ethylene selectivity was 95.5% and hot spot temperature was 381 ℃. The reaction results are shown in Table 1.
Example 4
The procedure for the preparation of the catalyst in this example was as described in example 1, except that the amount of silicon carbide powder added was 100g.
2000g of the above cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same reaction conditions as in example 1. The reaction results are: ethane conversion was 55.1%, ethylene selectivity was 70.4%, hot spot temperature was 420 ℃ -435 ℃ (fluctuation), and the reaction was in an unstable state. The reaction results are shown in Table 1.
Example 5
The procedure for the preparation of the catalyst in this example is as described in example 1, the different catalyst shapes being hollow cylinders with an outer diameter and a height of 5mm and an inner diameter of 3 mm.
2000g of the above cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same reaction conditions as in example 1. The reaction results are: ethane conversion was 63.3%, ethylene selectivity was 92.5% and hotspot temperature was 389 ℃. The reaction results are shown in Table 1.
Example 6
The procedure for the preparation of the catalyst in this example is as described in example 1, the different catalyst shapes being spheres with a diameter of 5mm.
2000g of the above sphere catalyst was used for oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion was 60.3%, ethylene selectivity was 91.4% and hot spot temperature was 392 ℃. The reaction results are shown in Table 1.
Example 7
The catalyst preparation procedure in this example was as described in example 1, the different catalyst shapes being gear shapes with equivalent diameters of 5mm.
2000g of the above gear-shaped catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same reaction conditions as in example 1. The reaction results are: ethane conversion was 54.4%, ethylene selectivity was 90.0% and hotspot temperature was 388 ℃. The reaction results are shown in Table 1.
Example 8
The procedure for the preparation of the catalyst in this example is as described in example 5, except that the dilute thermal conductor is silica fume and the binder is starch.
2000g of the above cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same reaction conditions as in example 1. The reaction results are: ethane conversion was 54.3%, ethylene selectivity was 88.4% and hot spot temperature was 392 ℃. The reaction results are shown in Table 1.
Example 9
The procedure for the preparation of the catalyst in this example is as described in example 5, except that the amount of silica gel is 20g.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion 60.3%, ethylene selectivity 91.2% and hot spot temperature 391 ℃. The reaction results are shown in Table 1. It should be noted that the hollow cylinder catalyst in this example has a lower strength than the catalyst obtained in example 5.
Example 10
The procedure for the preparation of the catalyst in this example is as described in example 5, except that the graphite is used in an amount of 20g.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion was 62.5%, ethylene selectivity was 92% and hot spot temperature was 393 ℃. The reaction results are shown in Table 1. It should be noted that the catalyst in this example is difficult to mold, and the molding die is vulnerable.
Example 11
The procedure for the preparation of the catalyst in this example is as described in example 5, the different diluted heat transfer agent being quartz powder, the binder being silica gel, the shaping aid being silica sol. The dosage of the binder and the forming additive is 70g.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion was 54.9%, ethylene selectivity was 88.0% and hotspot temperature was 388 ℃. The reaction results are shown in Table 1.
Example 12
The procedure for the preparation of the catalyst in this example is as described in example 10, except that the binder is polyethylene glycol and the shaping aid is glycerol.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion was 53.0%, ethylene selectivity was 87.7% and hot spot temperature was 390 ℃. The reaction results are shown in Table 1.
Example 13
The procedure for the preparation of the catalyst in this example is as described in example 12, the different diluted heat transfer agent being corundum powder and the shaping aid being cellulose.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion was 51.0%, ethylene selectivity was 85.0% and hotspot temperature was 387 ℃. The reaction results are shown in Table 1.
Example 14
The procedure for the preparation of the catalyst in this example was as described in example 5, except that the diluted heat transfer agent was silicon nitride powder (1200 g), the binder was polyethyl cellulose, and the forming aid was cellulose. The dosage of the binder and the forming additive is 70g.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion 58.0%, ethylene selectivity 90.3% and hot spot temperature 390 ℃. The reaction results are shown in Table 1.
Example 15
The procedure for the preparation of the catalyst in this example was as described in example 5, except that the diluted heat transfer agent was boron nitride powder (1000 g), the binder was polyethyl cellulose (150 g), and the forming aid was glycerol (70 g).
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion 58.6%, ethylene selectivity 90.2% and hot spot temperature 391 ℃. The reaction results are shown in Table 1.
Example 16
The procedure for the preparation of the catalyst in this example is as described in example 5, except that the amounts of silicon carbide, silica gel and graphite used are 800g, 150g, respectively, and the shape is clover-shaped with an equivalent diameter of 5mm.
2000g of the clover-shaped catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion was 61.0%, ethylene selectivity was 89.9% and hot spot temperature was 392 ℃. The reaction results are shown in Table 1.
Example 17
The procedure for the preparation of the catalyst in this example was as described in example 16, except that the catalyst was shaped as a four-leaf grass row.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion 61.1%, ethylene selectivity 90.2% and hot spot temperature 392 ℃. The reaction results are shown in Table 1.
Example 18
The catalyst preparation procedure in this example is as described in example 5.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. Catalyst stability evaluation tests were conducted for 1015 hours at this steady state condition and the results are set forth in Table 3. From the results, it can be seen that there was little change in catalyst activity.
Comparative example 1
The catalyst preparation procedure in this comparative example was as described in example 5, except that no thermally conductive diluent was added.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: the ethane conversion rate is 44.7%, the ethylene selectivity is 60.2%, the hot spot temperature is severely fluctuated at 430-450 ℃, and the selectivity of the deep oxidation product is high (more than 35.0%). The reaction results are shown in Table 2.
Comparative example 2
The procedure for the catalyst preparation in this comparative example was as described in example 5, except that no binder was added.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion was 64.3%, ethylene selectivity was 92.6% and hotspot temperature was 388 ℃. The reaction results are shown in Table 2.
It should be noted that the catalyst in this example has poor strength and low yield.
Comparative example 3
The procedure for the preparation of the catalyst in this comparative example was as described in example 5, except that no shaping aid was added.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: ethane conversion 61.8%, ethylene selectivity 91.4% and hot spot temperature 390 ℃. The reaction results are shown in Table 2.
It should be noted that the catalyst in this example is difficult to mold, and the catalyst is relatively expensive to mold equipment.
Comparative example 4
The procedure for the preparation of the catalyst in this comparative example was as described in example 5, except that no binder and no forming aids were added. In this example, the catalyst powder was difficult to shape after mixing with the silicon carbide powder, and was still substantially in the form of powder, and the strength of the resulting small portion of the hollow cylindrical catalyst was also poor.
Comparative example 5
The procedure for the preparation of the catalyst in this comparative example was as described in example 5, except that no diluent heat conductor, binder and forming aid were added.
2000g of the hollow cylindrical catalyst was used for the oxidative dehydrogenation of ethane in a single tube reaction under the same conditions as in example 1. The reaction results are: the ethane conversion rate is 41.5%, the ethylene selectivity is 58.0%, the hot spot temperature is severely fluctuated at 430-450 ℃, and the deep oxidation is serious. The reaction results are shown in Table 2.
Comparative example 6
Catalyst preparation procedure in this comparative example 2000g of the hollow cylindrical catalyst described above was used for the oxidative dehydrogenation of ethane in a single tube reaction as described in comparative example 5 under the same reaction conditions as in example 1. A catalyst stability evaluation test was conducted for 1015 hours under this steady state condition, and the results are shown in Table 3. The decrease in catalyst activity was more pronounced compared to example 18.
The reaction results in Table 1, examples 1 to 17
Table 2, comparative examples 1 to 5 show the results of the reactions
Table 3, evaluation results of catalyst stability (example 18 and comparative example 6)
Claims (10)
1. A method for preparing a catalyst for selectively oxidizing high-value chemicals by using low-carbon alkane, which is characterized by comprising the following steps: the element composition of the catalyst is Mo 1.0 V a Te b Nb c X d O n Wherein a is 0.2-1.0, b is 0.2-1.0, c is 0.1-0.5, d is 0.1-0.5, n is related to oxidation states and contents of Mo, V, te and Nb, and X is one or more of elemental silicon powder, silicon carbide powder, quartz powder, corundum powder, silicon nitride and boron nitride;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving Mo source and Te source in water at 50-90 deg.C to obtain solution A, dissolving V source in water at 50-90 deg.C to obtain solution B, dissolving Nb source in water at 50-90 deg.C to obtain solution C, dropping solution B into solution A at 60-90 deg.C to obtain solution D, and dropping solution C into solution D to obtain solution E; transferring the solution E into a stainless steel synthesis kettle for hydrothermal reaction to obtain a precipitate, drying at 60-110 ℃ to obtain a catalyst filter cake, performing preliminary breaking and ball milling on the filter cake, and roasting at 500-700 ℃ in an inert atmosphere to obtain catalyst active powder;
(2) Uniformly mixing the catalyst active powder with a diluted heat-conducting agent, a binder and a forming auxiliary agent, and then directly tabletting for forming or extruding for forming to obtain a formed catalyst; the formed catalyst is solid or hollow particles in the shape of sphere, cylinder, hollow cylinder, clover or gear; the diluted heat conducting agent is one or more of simple substance silicon powder, silicon carbide powder, quartz powder, corundum powder, silicon nitride and boron nitride, the addition amount of the diluted heat conducting agent is 0.1-90 wt% of the weight of the catalyst active powder, the binder is one or more of silica gel, starch, polyethylene glycol, polymethyl cellulose and polyethyl cellulose, the addition amount of the binder is 0.1-10 wt% of the weight of the catalyst active powder, the forming auxiliary agent is one or more of water, graphite, silica sol, glycerol and cellulose, and the addition amount of the forming auxiliary agent is 0.1-10 wt% of the weight of the catalyst active powder;
(3) Roasting the formed catalyst in inert gas at 300-500 deg.c for 0.5-10 hr.
2. The method for preparing a catalyst according to claim 1, wherein: molybdenum source adopts molybdic acid, ammonium paramolybdate or molybdenum oxide, V source adopts ammonium metavanadate, vanadium oxide or vanadyl sulfate, te source adopts tellurium dioxide or telluric acid, and Nb source adopts niobium oxalate or niobium pentoxide.
3. The method for preparing a catalyst according to claim 1, wherein: the active powder of the catalyst is an M1 phase pure phase material or a mixed crystal phase material consisting of M1 and M2 phases.
4. The method for preparing a catalyst according to claim 1, wherein: the addition amount of the diluted heat-conducting agent is 20-60 wt% of the weight of the catalyst active powder.
5. The method for preparing a catalyst according to claim 1, wherein: the addition amount of the binder is 3-7wt% of the weight of the catalyst active powder.
6. The method for preparing a catalyst according to claim 1, wherein: the catalyst active powder is added with a forming additive which is one or more of water, graphite, silica sol, glycerin and cellulose, and the preferable addition amount of the forming additive is 3-7wt% of the weight of the catalyst active powder.
7. The method for preparing a catalyst according to claim 4, wherein: the addition amount of the diluted heat-conducting agent is 30-50 wt% of the weight of the catalyst active powder.
8. A catalyst for the selective oxidation of higher value chemicals from lower alkanes prepared by the process of any one of claims 1-7.
9. Use of the catalyst of claim 8 for the selective oxidation of lower alkanes to higher value chemicals.
10. The use according to claim 9, characterized in that: in the reaction for preparing ethylene by oxydehydrogenation of ethane in the presence of molecular oxygen, the raw material gas comprises 5-40% of ethane, 20-95% of air and 0-40% of water, the total volume percentage composition of the raw material gas is 100%, the reaction temperature is 300-500 ℃, the reaction pressure is normal pressure-1.0 MPaG, and the total space velocity of the reaction is 500h -1 ～8000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, it is: the raw material gas comprises 20-30% of ethane, 40-70% of air and 10-30% of water, the total volume percentage composition of the raw material gas is 100%, the reaction temperature is 350-450 ℃, the reaction pressure is 0.2-0.5 MPaG, and the total space velocity of the reaction is 2000-5000 h -1 。
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