CN111013568A - Molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion and preparation method thereof - Google Patents
Molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion and preparation method thereof Download PDFInfo
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- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 46
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910003455 mixed metal oxide Inorganic materials 0.000 title claims abstract description 42
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 42
- 239000011733 molybdenum Substances 0.000 title claims abstract description 42
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000009841 combustion method Methods 0.000 title description 2
- 238000002485 combustion reaction Methods 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 9
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- -1 alkaline earth metal salt Chemical class 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound 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
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010171 Li2MoO4 Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion and a preparation method thereofaMobOxWherein M is at least one of Be, Mg, Ca, Sr and Ba; a is 1-10; b is 1-10; x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion. The invention can obviously reduce the combustion amount of ammonia, thereby keeping higher oxygen content of a reaction system, avoiding organic byproducts from generating polymerization and carbonization so as to block the pore canal of the catalyst, simultaneously inhibiting the reduction of high valence metal ions in the catalyst,the catalyst is prevented from being deactivated, so that the catalyst can keep high activity for a long time, and the industrial production of the acrylonitrile can be ensured to be carried out stably for a long time.
Description
Technical Field
The invention belongs to the technical field of molybdenum-based mixed metal oxides, and particularly relates to a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion and a preparation method thereof, which are suitable for synthesizing unsaturated nitrile, especially at least one unsaturated nitrile in acrylonitrile and methacrylonitrile by ammonia oxidation of low-carbon hydrocarbon.
Background
In the production process of acrylonitrile by propylene ammoxidation, the influence of oxygen content in the reaction system on the catalyst is very important. When the oxygen content is lower, the deep oxidation is inhibited, the selectivity of acrylonitrile is increased, the selectivity of organic byproducts such as acrolein, acrylic acid and the like is also increased, and organic substances such as the acrolein, the acrylic acid and the like are easy to polymerize so as to form carbon deposit to block the pore channels of the catalyst. In addition, the reduction of the oxygen content makes it easy for the metal ions in the high valence state to be reduced by the organic vapor to become inactive metal ions in the low valence state, thereby deactivating the catalyst.
Disclosure of Invention
In order to solve the technical problems, the invention provides a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion comprising a supported molybdenum-based mixed metal oxide and a molybdate adjuvant, said molybdate adjuvant having the formula:
MaMobOx
wherein M is at least one of Be, Mg, Ca, Sr and Ba;
a is 1-10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion.
The molybdate auxiliary agent can also be in a supporting type, and the chemical formula is as follows:
MaMobOx/40～80％-SiO2；
a is 1-10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion.
The addition amount of the molybdate auxiliary agent is 0.05-10% of the total weight of the molybdenum-based mixed metal oxide.
The supported molybdenum-based mixed metal oxide has the following chemical formula:
AaBbCcDdBieMofOx/40～60％wt-SiO2
wherein A is at least one of Li, Na, K, Rb, Cs, Sm, In, Ca, Sr, Ba and Tl;
b is at least one of Fe, Co, Mg, Mn, Ni, Ti, V and Zn;
c is at least one of Ce, Eu, P, Sb, Ge, Te and La;
d is at least one of Sn, B, Pt, Pd, Ga, Ag, Cu, Nd and Pr;
a is 0.05 to 3.0;
b is 0.1 to 10;
c is 0.05 to 6.0;
d is 0 to 2.0;
e is 0.2 to 6.0;
f is 8.0-16.0;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion.
The supported molybdenum-based mixed metal oxide can also be of the formula:
Mo1VaMbNbcOd/40～60％wt-SiO2
wherein M is at least one of Te, Sb, Mn, Ag, Ce and Ni;
a is 0.05 to 1.0;
b is 0.05 to 1.0;
c is 0.05 to 1.0;
d is the number of oxygen atoms required to satisfy the oxidation state of the metal ion.
When the molybdate additive is MaMobOxThe method for preparing the molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion is as follows: and fully mixing the molybdate auxiliary agent and the supported molybdenum-based mixed metal oxide to obtain the molybdenum-based mixed metal oxide.
When the molybdate additive is MaMobOx/40～80％-SiO2xThe method for preparing the molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion is as follows:
loading a molybdate additive precursor compound on a silicon dioxide carrier by an impregnation method, roasting to obtain a molybdate additive (silicon dioxide supported molybdate additive), and mixing the molybdate additive precursor compound with a supported molybdenum-based mixed metal oxide to obtain the molybdenum-based mixed metal oxide.
The molybdate additive precursor compound comprises molybdate and alkaline earth metal salt, wherein the molybdate is one or more of ammonium heptamolybdate and ammonium tetramolybdate; the alkaline earth metal salt is one or more of magnesium nitrate, beryllium nitrate, calcium nitrate, strontium nitrate and barium nitrate.
The invention also provides application of the molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion, which is suitable for the reaction of synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon.
The lower hydrocarbon is at least one of propylene, propane, isobutene and isobutane.
The unsaturated nitrile is at least one of acrylonitrile and methacrylonitrile.
The beneficial results of the invention are: the molybdenum-based mixed metal oxide catalyst containing the molybdate auxiliary agent and used for ammoxidation of low-carbon hydrocarbon can obviously reduce the combustion amount of ammonia, so that the reaction system keeps higher oxygen content, organic byproducts are prevented from being polymerized and carbonized to block catalyst pore passages, reduction of high-valence metal ions in the catalyst is also inhibited, catalyst inactivation is prevented, the catalyst can keep high activity for a long time, and the industrial production of acrylonitrile can be ensured to be stably carried out for a long time. In addition, the silica-supported molybdate auxiliary has better effect of reducing the ammonia combustion amount.
Detailed Description
The present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited by the examples, and those skilled in the art who have the above-mentioned disclosure will still be able to make some insubstantial modifications and adaptations to the present invention.
The catalytic reaction conditions are as follows:
catalyst loading: 380 g; the reaction temperature is 440 ℃; the aminoalkene ratio is 1.2; the empty-to-olefin ratio is 9.5; propylene WWH 0.08; the reaction pressure was 80 KPa.
Comparative example 1
The catalyst is a standard catalyst (supported molybdenum-based mixed metal oxide catalyst) without an additive and has a chemical formula of K0.085Cs0.075Mg1.875Fe1.971Ni6.382Ce0.475Cu0.005Bi0.488Mo12O/50％wt-SiO2。
Comparative example 2
The catalyst was the standard catalyst of comparative example 1 to which Li was added in an amount of 0.5% by weight based on the total weight of the standard catalyst2MoO4(Standard catalyst in comparative example 1 with Li2MoO4Mixed uniformly to obtain the supported molybdenum-based mixed metal oxide catalyst).
Example 1
The catalyst is the standard catalyst in comparative example 1 added with BeMoO of 0.5 percent of the total weight of the standard catalyst4(Standard catalyst from comparative example 1 with BeMoO4Mixed uniformly to obtain the supported molybdenum-based mixed metal oxide catalyst).
Example 2
The catalyst is MgMoO added to the standard catalyst in comparative example 1 in an amount of 0.5 wt% based on the total weight of the standard catalyst4。
Example 3
The catalyst is CaMoO added to the standard catalyst in comparative example 1 in an amount of 0.5 wt% based on the total weight of the standard catalyst4。
Example 4
The catalyst was the standard catalyst of comparative example 1 with the addition of SrMoO in an amount of 0.5% by weight of the total weight of the standard catalyst4。
Example 5
The catalyst was the standard catalyst of comparative example 1 to which BaMoO was added in an amount of 0.5% by weight based on the total weight of the standard catalyst4。
Example 6
The catalysts obtained in comparative example 1 and examples 1 to 5 were subjected to a reaction for synthesizing acrylonitrile by ammoxidation of propylene, and the results of the catalytic reaction are shown in Table 1.
TABLE 1 comparison of catalysts obtained in comparative example 1, examples 1 to 5
Note: xC3＝Is the propylene conversion; y isANFor acrylonitrile yield, YHCNAs hydrocyanic acid yield; y isACNYield was acetonitrile.
Example 7
The catalyst is MgMoO added to the standard catalyst in comparative example 1 in an amount of 0.1 wt% based on the total weight of the standard catalyst4。
Example 8
The catalyst is MgMoO added to the standard catalyst in comparative example 1 in an amount of 0.3 wt% based on the total weight of the standard catalyst4。
Example 9
The catalyst is MgMoO added to the standard catalyst in comparative example 1 in an amount of 1 wt% based on the total weight of the standard catalyst4。
Example 10
The catalyst is MgMoO added to the standard catalyst in comparative example 1 in an amount of 5 wt% based on the total weight of the standard catalyst4。
Example 11
The catalysts obtained in comparative example 1 and examples 7 to 10 were subjected to a reaction for synthesizing acrylonitrile by ammoxidation of propylene, and the results of the catalytic reaction are shown in Table 2.
TABLE 2 comparison of catalysts obtained in comparative example 1, examples 7 to 10
Note: xC3＝Is the propylene conversion; y isANFor acrylonitrile yield, YHCNAs hydrocyanic acid yield; y isACNYield was acetonitrile.
Claims (10)
1. A molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion, characterized by: comprises a supported molybdenum-based mixed metal oxide and a molybdate additive, wherein the molybdate additive has the following chemical formula:
MaMobOx
wherein M is at least one of Be, Mg, Ca, Sr and Ba;
a is 1-10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
the addition amount of the molybdate auxiliary agent is 0.05-10% of the total weight of the molybdenum-based mixed metal oxide.
2. A molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion, characterized by: comprises a supported molybdenum-based mixed metal oxide and a molybdate additive, wherein the molybdate additive has the following chemical formula:
MaMobOx/40～80％-SiO2；
wherein a is 1-10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
the addition amount of the molybdate auxiliary agent is 0.05-10% of the total weight of the molybdenum-based mixed metal oxide.
3. A molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as claimed in claim 1 or 2, wherein: the supported molybdenum-based mixed metal oxide has the following chemical formula:
AaBbCcDdBieMofOx/40～60％wt-SiO2
wherein A is at least one of Li, Na, K, Rb, Cs, Sm, In, Ca, Sr, Ba and Tl;
b is at least one of Fe, Co, Mg, Mn, Ni, Ti, V and Zn;
c is at least one of Ce, Eu, P, Sb, Ge, Te and La;
d is at least one of Sn, B, Pt, Pd, Ga, Ag, Cu, Nd and Pr;
a is 0.05 to 3.0;
b is 0.1 to 10;
c is 0.05 to 6.0;
d is 0 to 2.0;
e is 0.2 to 6.0;
f is 8.0-16.0;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion.
4. A molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as claimed in claim 1 or 2, wherein: the supported molybdenum-based mixed metal oxide has the following chemical formula:
Mo1VaMbNbcOd/40～60％wt-SiO2
wherein M is at least one of Te, Sb, Mn, Ag, Ce and Ni;
a is 0.05 to 1.0;
b is 0.05 to 1.0;
c is 0.05 to 1.0;
d is the number of oxygen atoms required to satisfy the oxidation state of the metal ion.
5. A method of preparing a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as defined in claim 1, wherein: and fully mixing the molybdate auxiliary agent and the supported molybdenum-based mixed metal oxide to obtain the molybdenum-based mixed metal oxide.
6. A method of preparing a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as defined in claim 2, wherein: loading a molybdate auxiliary precursor compound on a silicon dioxide carrier by an impregnation method, roasting to obtain a molybdate auxiliary, and then fully mixing the molybdate auxiliary and a supported molybdenum-based mixed metal oxide to obtain the molybdenum-based mixed metal oxide.
7. A method of preparing a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as defined in claim 6, wherein: the molybdate additive precursor compound comprises molybdate and alkaline earth metal salt, wherein the molybdate is one or more of ammonium heptamolybdate and ammonium tetramolybdate; the alkaline earth metal salt is one or more of magnesium nitrate, beryllium nitrate, calcium nitrate, strontium nitrate and barium nitrate.
8. Use of a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as claimed in claim 1 or 2, wherein: the method is suitable for the reaction of synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon.
9. Use of a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as defined in claim 8, wherein: the lower hydrocarbon is at least one of propylene, propane, isobutene and isobutane.
10. Use of a molybdenum-based mixed metal oxide catalyst capable of reducing ammonia combustion as defined in claim 8, wherein: the unsaturated nitrile is at least one of acrylonitrile and methacrylonitrile.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU667230A1 (en) * | 1976-04-06 | 1979-06-15 | Ордена Ленина Институт Химической Физики Ан Ссср | Catalyst for oxidation of cyclohexane |
| JPH0358962A (en) * | 1989-07-28 | 1991-03-14 | Nitto Chem Ind Co Ltd | Production of acrylonitrile by ammoxidation of propane |
| CN1226461A (en) * | 1997-12-05 | 1999-08-25 | 标准石油公司 | Improvement of performance of used molybdenum based catalysts by addition of ammonium dimolybdate |
| US20070260085A1 (en) * | 2006-05-02 | 2007-11-08 | Innovene Usa Llc | In situ modification of molybdenum-based catalysts |
| CN102395551A (en) * | 2009-04-16 | 2012-03-28 | 沙特基础工业公司 | A process for producing an unsaturated carboxylic acid from an alkane |
| CN104144910A (en) * | 2012-02-29 | 2014-11-12 | 三菱丽阳株式会社 | Method for producing acrylonitrile |
| CN106064095A (en) * | 2009-10-09 | 2016-11-02 | 三菱丽阳株式会社 | The manufacture method of composite oxide catalysts and the manufacture method of acrylonitrile |
-
2019
- 2019-12-18 CN CN201911307814.9A patent/CN111013568A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU667230A1 (en) * | 1976-04-06 | 1979-06-15 | Ордена Ленина Институт Химической Физики Ан Ссср | Catalyst for oxidation of cyclohexane |
| JPH0358962A (en) * | 1989-07-28 | 1991-03-14 | Nitto Chem Ind Co Ltd | Production of acrylonitrile by ammoxidation of propane |
| CN1226461A (en) * | 1997-12-05 | 1999-08-25 | 标准石油公司 | Improvement of performance of used molybdenum based catalysts by addition of ammonium dimolybdate |
| US20070260085A1 (en) * | 2006-05-02 | 2007-11-08 | Innovene Usa Llc | In situ modification of molybdenum-based catalysts |
| CN102395551A (en) * | 2009-04-16 | 2012-03-28 | 沙特基础工业公司 | A process for producing an unsaturated carboxylic acid from an alkane |
| CN106064095A (en) * | 2009-10-09 | 2016-11-02 | 三菱丽阳株式会社 | The manufacture method of composite oxide catalysts and the manufacture method of acrylonitrile |
| CN104144910A (en) * | 2012-02-29 | 2014-11-12 | 三菱丽阳株式会社 | Method for producing acrylonitrile |
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