CN116328796B - Mo-V-Te-Nb system catalyst and preparation method thereof - Google Patents
Mo-V-Te-Nb system catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN116328796B CN116328796B CN202111584382.3A CN202111584382A CN116328796B CN 116328796 B CN116328796 B CN 116328796B CN 202111584382 A CN202111584382 A CN 202111584382A CN 116328796 B CN116328796 B CN 116328796B
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- water
- temperature
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims description 32
- 239000010955 niobium Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 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 16
- 150000007524 organic acids Chemical class 0.000 claims description 15
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 14
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 claims description 14
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 78
- 230000007547 defect Effects 0.000 abstract description 44
- 239000001294 propane Substances 0.000 abstract description 39
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 38
- 230000003647 oxidation Effects 0.000 abstract description 29
- 238000007254 oxidation reaction Methods 0.000 abstract description 29
- 239000002131 composite material Substances 0.000 abstract description 21
- 238000000975 co-precipitation Methods 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 10
- 230000033228 biological regulation Effects 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract description 4
- 238000011105 stabilization Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000002950 deficient Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- -1 natural gas alkanes Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012073 inactive phase Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Mo-V-Te-Nb system catalyst and a preparation method thereof. According to the preparation method disclosed by the invention, the coprecipitation process is designed into three stages of a composite phase small cluster combination stage, a defect site precursor formation stage and a defect site structure aging stabilization stage, when the process enters different stages, the coprecipitation condition is changed rapidly in a step-like manner, the defect site of the composite phase is generated maximally, the generation of non-selective oxidation defect site is inhibited, the accurate regulation and control of the defect structure type of the active site of the Mo-V-Te-Nb system catalyst is realized, and the problem that the defect site type distribution of the Mo-V-Te-Nb system catalyst for preparing acrylic acid by oxidizing propane is wider is solved.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a Mo-V-Te-Nb system catalyst and a preparation method thereof.
Background
Acrylic acid belongs to basic organic chemical raw materials, and mainly has three application fields: the first large application area is adhesive, with a ratio of about 59.8%; the second largest field of application is superabsorbent resins, accounting for about 19.9%; the third largest application field is other industries such as water treatment agent, and the like, and the ratio is about 8 percent.
Acrylic acid and its derivative products are widely applied to various industries such as coating, textile, chemical fiber, adhesive, leather, washing, papermaking, plastics, rubber, medical treatment, oilfield chemistry, etc., penetrate into various fields such as daily life, high new materials, etc., and have wide market space. The super absorbent resin is one of the most promising fine chemical products in the downstream acrylic acid industry, is mainly used for producing sanitary products such as paper diapers, feminine sanitary napkins and the like, and accounts for more than 90% of the demand of the super absorbent resin. In addition to the traditional sanitary article field, new varieties, new functions and application fields of the super absorbent resin are continuously developed in various countries in the world, such as cable coating materials, food packaging materials, agriculture and forestry soil moisture preservation, waste liquid solidification treatment and the like, and the extension of downstream industries can enable the consumption amount of the super absorbent resin to continuously and rapidly increase.
The low-carbon alkane exists widely worldwide, and can bring great economic benefit by converting the low-carbon alkane into chemical products with high added value. Therefore, the 21 st century petrochemical raw material is likely to be turned to be mainly based on cheaper natural gas alkanes, and the transfer of the raw material route from alkene to alkane is one of the important points of research and development of the new century petrochemical technology. To date, only a few reactions have been carried out to produce maleic anhydride, for example, ethylene by steam cracking of ethane, propylene by dehydrogenation of propane, and selective oxidation of butane. Possible commercial alkane activation technologies in the 21 st century include ethane to acetic acid, isobutane to methacrylic acid, propane to acrylic acid, and the like.
Propane is one of the important components of natural gas, liquefied petroleum gas, and coalbed methane. With the accelerated exploitation of unconventional oil gas such as shale gas, the potential supply amount of propane is more. They are generally used as fuel or burned off by emptying, and the resource waste is large. How to convert the low-carbon alkane into chemical products with high added value, reduces the dependence on petroleum, has huge economic benefit and potential social benefit of delaying the exhaustion of petroleum. Therefore, the research on the aspects of preparing propylene by oxidative dehydrogenation of propane, preparing acrolein by selective oxidation of propane, preparing acrylic acid, preparing acrylonitrile by ammoxidation of propane and the like is significant. The industrial production process for preparing the acrylic acid by using the low-cost and abundant-reserve propane instead of propylene as the raw material greatly reduces the production cost of the acrylic acid and improves the market competitiveness. Compared with the existing acrylic acid preparing process by oxidizing propylene in two steps, the acrylic acid preparing process by oxidizing propane in one step has obvious cost advantage. First, the raw propane is low in price. In the propylene oxidation process, the cost of raw material propylene accounts for about 80% of the total processing cost of acrylic acid, and the price of propane is about 50% of the price of propylene; and secondly, the construction investment of the production device is low. The propane oxidation process is basically the same as the products in the propylene oxidation process, and other public engineering and product post-treatment separation and purification systems are basically the same except for an oxidation unit. For the oxidation unit, only one reactor and one catalyst are needed in the propane oxidation process, and two reactors and two catalysts are needed in the propylene oxidation process, so that the investment of the reactors is at least doubled, and the cost of the catalysts is higher.
In the patent application JPH0710801A, mo 1V0.3Te0.23Nb0.12Ox is firstly reported to be used as a catalyst for preparing acrylic acid from propane, the catalyst is prepared by rotary evaporation and drying, the acrylic acid yield is 48% -50%, and the catalyst is a composite metal oxide system with the best acid energy for directly preparing propylene by catalyzing propane. The research eyes of the related researchers are directed to the development of Mo-V-Te-Nb system catalysts. Patent application CN103691457A discloses a preparation method of a Mo-V-Te-Nb system catalyst, which adopts citric acid and niobium to prepare a solution A, and other solutions C, and then ammonium nitrate is added after mixing to prepare sol, and the sol is evaporated to dryness and calcined to obtain the catalyst. Patent application CN108503529a provides a method for preparing a catalyst for preparing acrylic acid by catalytic oxidation of propane, the catalyst in the method is composed of a molybdenum vanadium tellurium niobium catalyst and a stabilizer, and the stabilizer is selected from SiC, al 2O3 or SiO 2.
The Mo-V-Te-Nb system catalyst has a plurality of defect sites with different structural characteristics, and corresponds to different reaction capacities and characteristics. Each component is essential for the formation of the active phase of the catalyst for the selective oxidation of propane to acrylic acid. Mo and V participate in the formation of acid sites, thereby realizing the activation of propane molecules, and therefore, mo and V are key elements for preparing the effective structure of the catalyst. Te has a lone pair electron, and the existence of Te is related to an active phase of acrylic acid, and can effectively abstract H on allyl, so that a reaction path is along a reaction intermediate propylene, and then the reaction proceeds towards the direction of generating acrolein and then oxidizing acrylic acid, and further, the deep oxidation of acrylic acid on Mo and V oxides can be inhibited, so that acrylic acid exists stably, but the existence of Te also causes a certain loss of propane conversion rate. The distribution and proportion of the defect bit structure type determine the selectivity of the catalyst. The effect of Nb is not as obvious as that of other elements, on one hand, the introduction of Nb is beneficial to forming isolated V-center octahedron, so that the active sites of the catalyst are separated and the structure is stabilized, and on the other hand, the improvement and stabilization of the Te content on the surface of the catalyst can be promoted, and the formation of acrylic acid is beneficial. The Mo-V-Te-Nb system catalyst is mainly prepared by a coprecipitation method, and the defect site structure is closely related to the coprecipitation condition. Traditional coprecipitation conditions, including precipitation pH, temperature and stirring rate, can lead to various and similar types and proportions of defective site structures, thereby making it difficult to improve the reaction selectivity.
Disclosure of Invention
The invention aims to provide a Mo-V-Te-Nb system catalyst and a preparation method thereof, which are used for solving the problem of wider distribution of defect site types of the Mo-V-Te-Nb system catalyst for preparing acrylic acid by propane oxidation.
According to the preparation method disclosed by the invention, the coprecipitation process is designed into three stages of a composite phase small cluster combination period, a defect site precursor formation period and a defect site structure aging stabilization period, when the process enters different stages, the coprecipitation condition is changed rapidly in a step-like manner, the defect site of the composite phase is generated maximally, the generation of non-selective oxidation defect sites is inhibited, and the accurate regulation and control of the defect structure type of the active site of the Mo-V-Te-Nb system catalyst are realized.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of a Mo-V-Te-Nb system catalyst, which comprises the following steps:
Heating molybdate, vanadate and telluric acid to dissolve in water, and regulating the pH value of the solution to 4.5-6 to obtain a solution a;
heating and dissolving niobium oxalate and organic acid in water to obtain a solution b;
The temperature of the solution a and the temperature of the solution b are adjusted to be 50-90 ℃, the solution b is added into the solution a and continuously stirred, and precipitation is generated, so that suspension c is obtained;
Reducing the temperature of the suspension c to 35-75 ℃, and regulating the pH value to 1.5-3.0 to obtain a suspension d;
Transferring the suspension d into a hydrothermal synthesis kettle, crystallizing at the temperature of 150-250 ℃ to obtain a catalyst precursor after crystallization;
and roasting the catalyst precursor to obtain the catalyst.
The Mo-V-Te-Nb system catalyst prepared by the preparation method is suitable for the reaction of preparing acrylic acid by selectively oxidizing propane. In the catalyst prepared by the method, the regulation and control generation of a target active defect structure is realized, the generation of a composite phase defect position is maximized, the generation of a non-selective oxidation defect position is restrained, and the accurate regulation and control of the type of the active defect structure of the precursor of the Mo-V-Te-Nb system catalyst is realized.
According to the preparation method of the invention, preferably, the chemical formula of the catalyst is Mo aVbTecNbdOx, wherein Mo, V, te, nb is an active component, and a, b, c and d are 1 (0.20-0.35), 0.20-0.35 and 0.10-0.25. The dosages of molybdate, vanadate, telluric acid and niobium oxalate are determined according to the proportion of each element in the target catalyst.
According to the production method of the present invention, preferably, the molybdate is ammonium heptamolybdate or ammonium molybdate tetrahydrate.
According to the preparation method of the present invention, preferably, the vanadate is ammonium metavanadate or ammonium vanadate.
According to the preparation method of the present invention, preferably, when molybdate, vanadate and telluric acid are dissolved in water by heating, the addition amount of the water is 6 to 12 times of the total addition mass of the molybdate, vanadate and telluric acid.
According to the production method of the present invention, preferably, the step of dissolving molybdate, vanadate and telluric acid in water by heating comprises:
adding molybdate, vanadate and telluric acid into water at room temperature, heating to 70-95 ℃, stirring for dissolution, wherein the stirring speed is 100-300 r/min.
According to the preparation method of the present invention, preferably, the organic acid is citric acid or oxalic acid.
According to the preparation method of the present invention, preferably, the mass ratio of the niobium oxalate to the organic acid is 1:0.6 to 2.4.
According to the production method of the present invention, preferably, when niobium oxalate and an organic acid are dissolved in water by heating, the water is added in an amount of 5 to 10 times the total mass of niobium oxalate and the organic acid.
According to the production method of the present invention, preferably, the step of dissolving niobium oxalate and an organic acid in water by heating comprises:
Adding niobium oxalate and organic acid into water at room temperature, heating to 50-90 ℃ and stirring for dissolution, wherein the stirring speed is 100-200 r/min.
According to the preparation method of the present invention, preferably, when the temperature of the solution a is adjusted to 50 to 90 ℃, the stirring rate is adjusted to 400 to 700r/min; and adding the solution b with the same temperature into the solution a and continuously stirring, wherein the stirring rate of the solution a is kept unchanged in the adding process, and precipitation is gradually generated in the solution a, so as to obtain the suspension c.
According to the preparation method of the invention, preferably, the suspension c is stirred for 30min, then the temperature is reduced to 35-75 ℃, the stirring speed is kept unchanged, and the pH value is regulated to 1.5-3.0, so as to obtain the suspension d.
According to the production method of the present invention, preferably, the pH is adjusted by adding ammonia water.
According to the production method of the present invention, preferably, the time for crystallization is 18 to 36 hours.
According to the production method of the present invention, preferably, the baking treatment includes: in the air atmosphere, the temperature is raised to 300-500 ℃ within 1h, the mixture is roasted for 2-5 h under the temperature condition, and the mixture is cooled to the room temperature; in nitrogen atmosphere, 500-800 deg.c, preferably 500-800 deg.c, is raised to 3 hr, and the mixture is roasted for 2-4 hr and cooled to room temperature under nitrogen protection. The second stage roasting is high temperature roasting in nitrogen atmosphere, and the catalyst is prevented from being excessively oxidized to generate an inactive phase under the high temperature condition.
In a preferred embodiment, the preparation method comprises the steps of:
adding molybdate, vanadate and telluric acid into water at room temperature, heating to 70-95 ℃, stirring for dissolution, wherein the stirring speed is 100-300 r/min, and regulating the pH value of the solution to 4.5-6 to obtain a solution a;
Adding niobium oxalate and organic acid into water at room temperature, heating to 50-90 ℃, stirring for dissolution, and obtaining solution b, wherein the stirring speed is 100-200 r/min;
the temperature of the solution a is reduced to 50-90 ℃, and the stirring speed is adjusted to 400-700 r/min; the temperature of the solution b is adjusted to be the same as that of the solution a, and then the solution b is added into the solution a and continuously stirred, and precipitation is gradually generated in the solution a, so as to obtain a suspension c with the pH value of about 1.1;
the temperature of the suspension c is reduced to 35-75 ℃, and the pH value is regulated to 1.5-3.0, so as to obtain suspension d;
Transferring the suspension d into a hydrothermal synthesis kettle, crystallizing at the temperature of 150-250 ℃ for 18-36 hours to obtain a catalyst precursor after crystallization;
Roasting the catalyst precursor, which comprises the following steps: in an air atmosphere, the temperature is raised to 300-500 ℃ within 1h, roasting is carried out for 2-5 h under the temperature condition, and cooling is carried out to room temperature; and in a nitrogen atmosphere, the temperature is increased to 500-800 ℃ within 3h, roasting is carried out for 2-4h under the temperature condition, and the catalyst is obtained after cooling to room temperature under the protection of nitrogen.
In another aspect of the invention, the Mo-V-Te-Nb system catalyst obtained by the preparation method is suitable for the reaction of preparing acrylic acid by selectively oxidizing propane.
For alkane catalytic oxidation, the reaction network mainly comprises three reaction paths of selective oxidation, deep oxidation and combustion reaction. Each reaction path is dominated by a different defect structure type: "-Mo-O-Mo- [ cavity ] -Mo-" single-phase defects dominate the combustion reaction, "-X-metal-O-X-metal- [ cavity ] -X-metal-" Mo-deficient single-phase defects dominate the deep oxidation, "-Mo-O-X-metal- [ cavity ] -Mo-" composite phase defects dominate the selective oxidation. The distribution and proportion of the defect structure type determine the selectivity of the catalyst. The composite metal oxide is mainly prepared by a coprecipitation method, and the defect structure is closely related to the coprecipitation condition. Conventional coprecipitation conditions, including precipitation pH, temperature and stirring rate, can make the types and proportions of defective structures diverse, thereby making it difficult to improve the reaction selectivity. Compared with the existing preparation process of the acrylic acid catalyst prepared by propane oxidation, the preparation process of the acrylic acid catalyst is divided into a composite phase small cluster combination period, a composite phase defect site precursor formation period and a defect site structure aging stabilization period. The method can maximally generate the defect sites of the '-Mo-O-X metal- [ cavity ] -Mo-', inhibit the generation of nonselective oxidation defect sites, and realize the precise regulation and control of the defect structure types of the active sites of the Mo-V-Te-Nb system catalyst.
The process of the composite phase small cluster combination period adopts higher pH value and temperature and combines lower stirring rate to form the composite phase small cluster with uniformly combined metal oxide unit cells; after the composite phase small clusters are formed, the pH value and the temperature are rapidly reduced in a step manner, the stirring rate is increased, and the composite phase small clusters enter a 'composite phase defect position precursor forming period', and are combined and agglomerated into a precursor with a defect structure; after the formation of the composite phase defect site precursor is stable, the pH value is increased again in a step-like manner, the temperature is reduced, and the composite phase defect site precursor enters a 'defect site structure aging stable period', so that the formed optimal defect structure is further consolidated.
The catalyst prepared by the invention can realize the generation of composite phase defect sites and the accurate regulation and control of active site defect structure types, and can greatly improve the conversion rate of propane and the selectivity of acrylic acid in the reaction process.
Drawings
FIG. 1 is an XRD pattern of a catalyst for producing acrylic acid by oxidation of propane, which is prepared in example 1 of the present invention, and a catalyst for producing acrylic acid by oxidation of propane, which is prepared in a conventional manner in comparative example 1.
Fig. 2a and 2b are SEM scanning electron microscope images of the catalyst prepared in example 1 of the present invention and the catalyst prepared in the conventional method of comparative example 1, respectively.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, etc., including ranges for each) can generally be approximations that vary (+) or (-) as appropriate in 0.1 or 1.0 increments. All numerical designations are to be understood as preceded by the term "about". Unless otherwise indicated, all starting materials herein are commercially available, and the equipment used in the present invention may be conventional in the art or may be conventional in the art.
Example 1
The preparation method of the invention is used for preparing a Mo-V-Te-Nb system catalyst, and comprises the following steps:
1) 3.05g of ammonium molybdate, 0.49g of ammonium metavanadate, 0.97g of telluric acid and 40mL of deionized water are added into a No. 1 beaker according to the proportion of Mo, V, te, nb content in the catalyst so as to be completely dissolved at 75 ℃ under the condition of 120r/min, and ammonia water is added after the dissolution, and the pH value of the solution is adjusted to 5.4, thus obtaining solution a.
2) 1.85G of niobium oxalate, 1.85g of oxalic acid and 40mL of deionized water were added in a No. 2 beaker to be completely dissolved at 75℃and 120r/min, to obtain a solution b.
3) Rapidly cooling the solution a to 60 ℃, regulating the rotating speed to 600r/min, simultaneously cooling the solution b to 60 ℃, slowly dripping the solution b into the solution a when the temperature of the solution a is reduced to 60 ℃ and the temperature of the solution b is reduced to 60 ℃, and gradually generating precipitation in the solution a to obtain the suspension c with the pH value of about 1.1.
4) And (3) after the sediment in the solution a is generated, rapidly reducing the temperature of the suspension c to 45 ℃, adding ammonia water, and regulating the pH value to 1.8 to obtain the suspension d.
5) And (3) transferring the suspension liquid d into a hydrothermal synthesis kettle, crystallizing at 180 ℃ for 30 hours, and obtaining a catalyst precursor after crystallization.
6) Roasting the catalyst precursor, which comprises the following steps: in an air atmosphere, the temperature is increased to 400 ℃ within 1h, roasting is carried out for 2h under the temperature condition, and cooling is carried out to normal temperature; and in a nitrogen atmosphere, the temperature is increased to 600 ℃ within 3h, roasting is carried out for 2h under the temperature condition, and the catalyst is cooled to room temperature under the protection of nitrogen, so that the Mo 1V0.24Te0.24Nb0.17 system catalyst is obtained.
Comparative example 1
This comparative example used a conventional process to prepare a Mo-V-Te-Nb system catalyst comprising the steps of:
1) 3.05g of ammonium molybdate, 0.49g of ammonium metavanadate, 0.97g of telluric acid and 40mL of deionized water are added into a No. 1 beaker according to the proportion of Mo, V, te, nb content in the catalyst so as to be completely dissolved at 80 ℃ and 120r/min, and a solution a is obtained.
2) 1.85G of niobium oxalate, 1.85g of oxalic acid and 40mL of deionized water were added in a No. 2 beaker to be completely dissolved at 80℃and 120r/min, to obtain a solution b.
3) And (3) regulating the stirring speed of the solution a to 200r/min, slowly dripping the solution b into the solution a, gradually generating precipitation in the solution a, and continuously stirring for 30min to obtain a suspension c.
4) And c, transferring the suspension into a hydrothermal synthesis kettle, crystallizing at 180 ℃ for 30 hours to obtain a catalyst precursor after crystallization.
5) Roasting the catalyst precursor, which comprises the following steps: in an air atmosphere, the temperature is increased to 400 ℃ within 1h, roasting is carried out for 2h under the temperature condition, and cooling is carried out to normal temperature; and in a nitrogen atmosphere, the temperature is increased to 600 ℃ within 3h, roasting is carried out for 2h under the temperature condition, and the catalyst is cooled to room temperature under the protection of nitrogen, so that the Mo 1V0.24Te0.24Nb0.17 system catalyst is obtained.
FIG. 1 is an XRD pattern of a catalyst for producing acrylic acid by oxidation of propane, which is prepared in example 1 of the present invention, and a catalyst for producing acrylic acid by oxidation of propane, which is prepared in a conventional manner in comparative example 1. The MoVTeNbO catalyst is mainly composed of three crystal phases: an orthorhombic M1 phase (Te 2M20O57, m=mov, nb), a hexagonal M2 phase (Te 0.33MO3.33, m=mo, V, nb), and a small amount of monoclinic TeMo 5O16 phase. In the process of propane selective oxidation, the M1 phase mainly plays a role in activating propane, the M2 phase and the M1 phase have a synergistic effect, on one hand, a good oxygen transfer effect is achieved, lattice oxygen is conveyed to the M1 phase, and in addition, the M2 phase can also convert propylene which is an intermediate product of the reaction into acrylic acid, so that higher acrylic acid selectivity is achieved. M1 phase: 2 theta is 22.1 degrees, 26.2 degrees, 26.8 degrees, 27.3 degrees, 28.2 degrees and 45.2 degrees are classified into M1 phase; m2 phase: 2 theta is positioned at 22.1 degrees, 28.2 degrees, 36.5 degrees, 44.7 degrees and 45.2 degrees, and is reduced to M2 phase; mo 5-x(V/Nb)xO14: 2θ=7.7°,8.7 °,22.1 °,23.3 °,24.9 °,31.5 °,32.4 °,33.5 ° Mo 5-x(V/Nb)xO14 °. The catalyst prepared by the method has the advantages that the diffraction peak intensity of the corresponding main active phases M1 and M2 is enhanced, the diffraction peak intensity of the auxiliary active Mo 5-x(V/Nb)xO14 is weakened, and compared with the traditional preparation method, the preparation method provided by the invention can fully expose active defect sites and improve the oxidation-reduction capability of the catalyst.
Fig. 2a and fig. 2b are SEM scanning electron microscope results of the catalyst prepared in example 1 of the present invention and the catalyst prepared in the conventional method of comparative example 1, respectively, and the regulation and control of the target active defect site structure is achieved by adopting the coprecipitation condition step control method provided in the present invention.
Example 2
In example 1, the stirring rate 600r/min in step 3 was changed to 120r/min, which is a cost example.
Example 3
In example 1, the pH value was adjusted by adding ammonia water in step 1 instead of adjusting the pH value without adding ammonia water, which is a cost example.
Example 4
In example 1, the pH value was adjusted by adding ammonia water in step 4 instead of adjusting the pH value without adding ammonia water, which is a cost example.
Example 5
In example 1, the cost of reducing the temperature of the solution a to 60 ℃ in step 3 was changed to the cost of keeping the temperature of the solution a unchanged.
Example 6
In example 1, the temperature of the c suspension in step 4 was reduced to 45 ℃ and the c suspension was kept unchanged, thus obtaining a cost example.
Example 7
In example 1, the dissolution temperature in step 1 was changed to 70℃to obtain a cost example.
Example 8
In example 1, the dissolution temperature in step 1 was changed to 80℃to obtain a cost example.
Example 9
In example 1, the dissolution temperature in step 1 was changed to 85℃to obtain a cost example.
Example 10
In example 1, the dissolution temperature in step 1 was changed to 95℃to obtain a cost example.
Example 11
In example 1, the dissolution temperature in step 1 was changed to 65℃to obtain a cost example.
Example 12
In example 1, the pH of the solution in step 1 was changed to 4.8, i.e. the cost example.
Example 13
In example 1, the pH of the solution in step 1 was changed to 5.2, i.e., the cost example.
Example 14
In example 1, the pH of the solution in step 1 was changed to 5.6, i.e., the cost example.
Example 15
In example 1, the pH of the solution in step 1 was changed to 6.0, i.e., the cost example.
Example 16
In example 1, the pH of the solution in step 1 was changed to 4.2, i.e. the cost example.
Example 17
In example 1, the pH of the solution in step 1 was changed to 6.2, i.e. the cost example.
Example 18
In example 1, the rotation speed 600r/min in the step 3 is changed to 450r/min, namely the cost example.
Example 19
In example 1, the rotation speed 600r/min in the step 3 is changed to 500r/min, namely the cost example.
Example 20
In example 1, the rotation speed 600r/min in the step 3 is changed to 550r/min, namely the cost example.
Example 21
In example 1, the rotation speed 600r/min in the step 3 is changed to 650r/min, namely the cost example.
Example 22
In example 1, the rotation speed 600r/min in the step 3 is changed to 700r/min, namely the cost example.
Example 23
In example 1, the rotational speed 600r/min in step 3 was changed to 360r/min, which is a cost example.
Example 24
In example 1, the rotation speed 600r/min in the step 3 is changed to 750r/min, namely the cost example.
Example 25
In example 1, the pH of the solution in step 4 was changed to 2.0, i.e., the cost example.
Example 26
In example 1, the pH of the solution in step 4 was changed to 2.2, i.e. the cost example.
Example 27
In example 1, the pH of the solution in step 4 was changed to 2.4, i.e. the cost example.
Example 28
In example 1, the pH of the solution in step 4 was changed to 2.8, i.e. the cost example.
Example 29
In example 1, the pH of the solution in step 4 was changed to 3.0, i.e., the cost example.
Example 30
In example 1, the pH of the solution in step 4 was changed to 1.3, i.e. the cost example.
Example 31
In example 1, the pH of the solution in step 4 was changed to 3.2, i.e. the cost example.
The samples prepared in the above examples were subjected to activity evaluation, which was performed on a micro fixed bed reactor. Catalyst loading 2g, reaction temperature 390 ℃, oxygen/propane (volume) =4, water/propane (volume) =6, nitrogen balance in raw material gas, raw material gas space velocity gshv=1800 mL/(g·h), pressure is normal pressure; the propane, nitrogen and oxygen enter the mixer through the pressure reducing valve and the preheater from the gas steel bottle to mix, the trace water is injected into the vaporizer through the micro flow pump, vaporized at 200 ℃, enters the mixer to mix with the propane, nitrogen and oxygen, and enters the reactor. The specific catalytic activities are shown in Table 1.
Table 1 shows the conversion of propane, the selectivity of acrylic acid and the yield of acrylic acid during the reaction of preparing acrylic acid by oxidizing propane by using the catalyst prepared in the examples of the present invention.
From the evaluation data of example 1 and comparative example 1, it can be seen that the catalyst for producing acrylic acid by oxidation of propane prepared by the conventional method has a large gap in terms of conversion rate of propane, selectivity of acrylic acid and yield of acrylic acid as compared with the catalyst prepared by the present invention, which indicates that the catalyst prepared by the conventional method fails to sufficiently expose active defect sites and fails to improve oxidation-reduction ability. From the evaluation data of examples 1 and 2, it can be seen that the stirring rate plays a very critical role in the co-precipitation process, and that too low stirring rate is detrimental to the agglomeration of the composite phase small cluster combinations into a precursor with a defective structure in the co-precipitation process. From the evaluation data of example 1, example 3 and example 4, it can be seen that the adjustment of the pH value is advantageous for the formation of complex phase small clusters of homogeneous combinations of individual metal oxide unit cells and consolidation of the preferred defect structure during the co-precipitation process. From the evaluation data of example 1, example 5 and example 6, it can be seen that a stepwise change in temperature during the coprecipitation process is advantageous for the formation of small clusters of complex phases with a uniform combination of individual metal oxide unit cells and for the consolidation of the preferred defect structure. It can be seen from the evaluation data of example 7 and example 11 that too low a temperature is detrimental to the formation of small clusters of the composite phase in which the individual metal oxide unit cells are uniformly combined. From the evaluation data of examples 12, 15, 16 and 17, it can be seen that adjusting the pH too high or too low is detrimental to the formation of complex phase small clusters of uniform combinations of individual metal oxide unit cells. From the evaluation data of examples 18, 22, 23, and 24, it can be seen that too high or too low stirring rate during the co-precipitation process affects the agglomeration of the composite phase small cluster combinations into a precursor with a defective structure. From the evaluation data of examples 25, 29 and 30, 31 it can be seen that pH values adjusted too high or too low during the co-precipitation process are detrimental to further consolidating the preferred defect structure that has formed.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (15)
1. The preparation method of the Mo-V-Te-Nb system catalyst is characterized by comprising the following steps of:
Heating molybdate, vanadate and telluric acid to dissolve in water, and regulating the pH value of the solution to 4.5-6 to obtain a solution a;
heating and dissolving niobium oxalate and organic acid in water to obtain a solution b;
The temperature of the solution a and the temperature of the solution b are adjusted to be 50-90 ℃ which is the same, and the stirring speed of the solution a is adjusted to 400-700 r/min; adding the solution b into the solution a and continuously stirring, wherein the stirring rate of the solution a is kept unchanged in the adding process, and precipitation is gradually generated in the solution a to obtain suspension c;
Reducing the temperature of the suspension c to 35-75 ℃, and regulating the pH value to 1.5-3.0 to obtain a suspension d;
Transferring the suspension d into a hydrothermal synthesis kettle, crystallizing at the temperature of 150-250 ℃ to obtain a catalyst precursor after crystallization;
and roasting the catalyst precursor to obtain the catalyst.
2. The preparation method according to claim 1, wherein the catalyst has a chemical formula of Mo aVbTecNbdOx, wherein a: b: c: d is 1 (0.20-0.35): (0.10-0.25).
3. The method of claim 1, wherein the molybdate is ammonium heptamolybdate or ammonium molybdate tetrahydrate.
4. The method according to claim 1, wherein the vanadate is ammonium metavanadate or ammonium vanadate.
5. The preparation method according to claim 1, wherein when molybdate, vanadate and telluric acid are dissolved in water by heating, the addition amount of the water is 6 to 12 times of the total addition mass of the molybdate, vanadate and telluric acid.
6. The method of claim 1, wherein the step of dissolving the molybdate, vanadate and telluric acid in water by heating comprises:
adding molybdate, vanadate and telluric acid into water at room temperature, heating to 70-95 ℃, stirring for dissolution, wherein the stirring speed is 100-300 r/min.
7. The method according to claim 6, wherein the organic acid is citric acid or oxalic acid.
8. The preparation method according to claim 6, wherein the mass ratio of the niobium oxalate to the organic acid is 1:0.6 to 2.4.
9. The method according to claim 6, wherein the amount of the water added is 5 to 10 times the total mass of niobium oxalate and the organic acid when the niobium oxalate and the organic acid are dissolved in water by heating.
10. The method of claim 6, wherein the step of dissolving niobium oxalate and an organic acid in water by heating comprises:
Adding niobium oxalate and organic acid into water at room temperature, heating to 50-90 ℃ and stirring for dissolution, wherein the stirring speed is 100-200 r/min.
11. The method according to claim 1, wherein the suspension d is obtained by stirring the suspension c for 30min, then reducing the temperature to 35-75 ℃, maintaining the stirring rate unchanged, and adjusting the pH to 1.5-3.0.
12. The preparation method according to claim 1 or 11, wherein the pH is adjusted by adding ammonia.
13. The method according to claim 1, wherein the crystallization time is 18 to 36 hours.
14. The method of manufacturing according to claim 1, wherein the baking treatment comprises: roasting for 2-5 h at 300-500 ℃ in an air atmosphere, and cooling to room temperature; roasting for 2-4 h at 500-800 ℃ in nitrogen atmosphere, and cooling to room temperature under nitrogen protection.
15. A Mo-V-Te-Nb system catalyst obtainable by the process according to any one of claims 1 to 14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111584382.3A CN116328796B (en) | 2021-12-22 | 2021-12-22 | Mo-V-Te-Nb system catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111584382.3A CN116328796B (en) | 2021-12-22 | 2021-12-22 | Mo-V-Te-Nb system catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116328796A CN116328796A (en) | 2023-06-27 |
| CN116328796B true CN116328796B (en) | 2024-06-04 |
Family
ID=86874805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111584382.3A Active CN116328796B (en) | 2021-12-22 | 2021-12-22 | Mo-V-Te-Nb system catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116328796B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328988A (en) * | 2000-06-12 | 2002-01-02 | 株式会社日本触媒 | Process for preparing acrylic acid |
| JP2003511213A (en) * | 1999-11-15 | 2003-03-25 | サウディ ベーシック インダストリーズ コーポレーション | Catalyst for catalytic oxidation of propane to acrylic acid, its production and use |
| EP1704919A1 (en) * | 2005-03-25 | 2006-09-27 | Arkema France | Process for preparing improved catalysts for selective oxidation of propane into acrylic acid |
| JP2007044668A (en) * | 2005-08-12 | 2007-02-22 | Nippon Kayaku Co Ltd | Method for producing composite metal oxide catalyst and application of the catalyst |
| WO2009022780A1 (en) * | 2007-08-13 | 2009-02-19 | Lg Chem, Ltd. | Method of preparing improved catalyst for production of acrylic acid |
| CN101612564A (en) * | 2008-06-26 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of Mo-V-Te-Nb-O catalyst, its preparation method and application |
| CN101722017A (en) * | 2008-10-22 | 2010-06-09 | 中国科学院大连化学物理研究所 | Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof |
| CN103071514A (en) * | 2013-01-29 | 2013-05-01 | 新兴能源科技有限公司 | Preparation method of catalyst for preparing acrylic acid with propylene by one-step catalytic oxidation |
| CN103691457A (en) * | 2013-12-24 | 2014-04-02 | 济南开发区星火科学技术研究院 | Catalyst for preparing acrylic acid through propane selective oxidation and preparation method of catalyst |
| CN113600199A (en) * | 2021-09-07 | 2021-11-05 | 中国华能集团清洁能源技术研究院有限公司 | Metallic copper catalyst, and preparation method and application thereof |
-
2021
- 2021-12-22 CN CN202111584382.3A patent/CN116328796B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003511213A (en) * | 1999-11-15 | 2003-03-25 | サウディ ベーシック インダストリーズ コーポレーション | Catalyst for catalytic oxidation of propane to acrylic acid, its production and use |
| CN1328988A (en) * | 2000-06-12 | 2002-01-02 | 株式会社日本触媒 | Process for preparing acrylic acid |
| EP1704919A1 (en) * | 2005-03-25 | 2006-09-27 | Arkema France | Process for preparing improved catalysts for selective oxidation of propane into acrylic acid |
| JP2007044668A (en) * | 2005-08-12 | 2007-02-22 | Nippon Kayaku Co Ltd | Method for producing composite metal oxide catalyst and application of the catalyst |
| WO2009022780A1 (en) * | 2007-08-13 | 2009-02-19 | Lg Chem, Ltd. | Method of preparing improved catalyst for production of acrylic acid |
| CN101612564A (en) * | 2008-06-26 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of Mo-V-Te-Nb-O catalyst, its preparation method and application |
| CN101722017A (en) * | 2008-10-22 | 2010-06-09 | 中国科学院大连化学物理研究所 | Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof |
| CN103071514A (en) * | 2013-01-29 | 2013-05-01 | 新兴能源科技有限公司 | Preparation method of catalyst for preparing acrylic acid with propylene by one-step catalytic oxidation |
| CN103691457A (en) * | 2013-12-24 | 2014-04-02 | 济南开发区星火科学技术研究院 | Catalyst for preparing acrylic acid through propane selective oxidation and preparation method of catalyst |
| CN113600199A (en) * | 2021-09-07 | 2021-11-05 | 中国华能集团清洁能源技术研究院有限公司 | Metallic copper catalyst, and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| "The effect of pH on structural and catalytic properties of MoVTeNbO catalysts";J.M. Oliver et al.;《Applied Catalysis A: General》;20041231;第67-76页 * |
| MoVTeNbO催化剂的制备;党欣语;;人生十六七;20170815(第23期);第77页 * |
| 丙烷氧化脱氢制丙烯Ce_xNi_(3-x)V_2O_8催化剂的研究;董国良;斯琴塔娜;照日格图;;内蒙古师范大学学报(自然科学汉文版);20080715(第04期);第102-105页 * |
| 丙烷选择氧化制丙烯酸复合金属氧化物催化剂的研究;郑伟;于振兴;张平;张宇航;付红英;张晓丽;胡信国;;工业催化;20081015(第10期);第152-155页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116328796A (en) | 2023-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105413725B (en) | Vanadium phosphorus catalyst and preparation method thereof | |
| CN105381809B (en) | The preparation method of vanadium-phosphor oxide catalyst for hydro carbons selective oxidation | |
| CN103663559B (en) | Dibismuth trimolybdenum dodecaoxide nanocrystalline as well as preparation method and application thereof | |
| CN107866240A (en) | Catalyst for preparing maleic anhydride and preparation method thereof | |
| EP3650120A1 (en) | Fluidized-bed catalyst applicable to haloarylnitrile production, and preparation and application thereof | |
| CN115254100A (en) | For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation | |
| CN112973746A (en) | Preparation method of supported vanadium phosphorus oxygen catalyst, catalyst prepared by preparation method and application of catalyst | |
| CN103071514B (en) | A kind of preparation method preparing acrylic acid catalyst for propylene one step catalytic oxidation | |
| CN107175119B (en) | A kind of preparation method and applications of load-type vanadium phosphor oxide catalyst | |
| CN101703941A (en) | Mo-V-Te-Nb-O composite metallic oxide catalyst as well as preparation method and application thereof | |
| CN115837275A (en) | Perovskite type high-entropy oxide and preparation method and application thereof | |
| CN116328796B (en) | Mo-V-Te-Nb system catalyst and preparation method thereof | |
| CN101778669B (en) | Method of preparing improved catalyst for production of acrylic acid | |
| CN107029700A (en) | A kind of catalyst of propane preparing acrylonitrile by ammoxidation and preparation method thereof | |
| CN104607220B (en) | Vanadium-phosphorus oxide catalyst for preparing maleic anhydride through cyclohexane oxidation, and preparation method thereof | |
| CN112844400A (en) | Bi-based polyacid catalyst and application thereof in preparation of 2-methylacrolein by oxidation of 2-methyl propylene | |
| CN108503529B (en) | Method for preparing acrylic acid from propane | |
| CN113842934B (en) | Oxidation catalyst and preparation method and application thereof | |
| Han et al. | Preparation and effect of Mo-V-Cr-Bi-Si oxide catalysts on controlled oxidation of methane to methanol and formaldehyde | |
| CN114768845A (en) | Preparation method and application of nitrogen-doped carbon quantum dot/bimetal supported catalyst | |
| CN1931434A (en) | Prepn process of catalyst for catalytic oxidation of propane to prepare acryl aldehyde | |
| CN100408164C (en) | Titaniun-vanadium-tin comprising catalyst and process for the preparation of phthalic anhydride | |
| CN104107696B (en) | The preparation method of prepared by acrolein oxidation acrylic acid catalyst | |
| CN103386307A (en) | Preparation method for Ni-Mg/Al2O3 catalyst | |
| CN113000044A (en) | Carbon dioxide oxidation ethane dehydrogenation catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |