CN115569650A - Catalyst for synthesizing unsaturated aldehyde and preparation method thereof - Google Patents
Catalyst for synthesizing unsaturated aldehyde and preparation method thereof Download PDFInfo
- Publication number
- CN115569650A CN115569650A CN202110765934.4A CN202110765934A CN115569650A CN 115569650 A CN115569650 A CN 115569650A CN 202110765934 A CN202110765934 A CN 202110765934A CN 115569650 A CN115569650 A CN 115569650A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- value range
- solution
- aging
- salt
- 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.)
- Pending
Links
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
- B01J23/70—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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a catalyst for synthesizing unsaturated aldehyde and a preparation method thereof, wherein the synthesized catalyst comprises the following components: mo 20 W a Bi b Fe c Co d Ce e X f Y g O h a/iZ; x is an alkali metal or alkaline earth metal element; y is any one or combination of more of nickel, tellurium, strontium, manganese, copper, tin or titanium; z is a carrier; the value range of a is 0 to 5; the value range of b is 0.5-6.0; c takingThe value range is 1 to 10.0; the value range of d is 5-20; the value range of e is 0.1-5.0; the value range of f is 0.05-5; g ranges from 0 to 10, and h is the total number of oxygen atoms required to satisfy the valence of other elements. Compared with the prior art, the catalyst prepared by the invention increases the utilization rate of metal elements, is beneficial to controlling the selective oxidation process of reaction raw materials, can prepare methacrolein with high yield, and simultaneously reduces CO x The conversion rate of reactants is more than 99 percent, the selectivity of the methacrolein reaches 92 percent, and the CO byproduct is discharged x The selectivity is less than 5%.
Description
Technical Field
The present invention relates to a mixed metal oxide catalyst containing Mo, and more particularly, to a catalyst for synthesizing unsaturated aldehydes and a method for preparing the same.
Background
Methyl Methacrylate (MMA) is an important organic chemical raw material and a polymerization monomer, is mainly used for producing polymethyl methacrylate, polyvinyl chloride auxiliary agents ARC, acrylic fibers, medical high polymer materials and the like, is a high-end material in the fields of aerospace, electronic information, optical fiber, robots and the like, and has wide application.
The synthesis of MMA by using isobutene as a raw material has the advantages of wide raw material source, high atom utilization rate, small environmental pollution and the like, wherein the selective oxidation of isobutene to prepare Methacrolein (MAL) is the first step of MMA production by an isobutene method and is also a key step. The method for producing corresponding unsaturated aldehyde and unsaturated carboxylic acid by using isobutene or tertiary butanol as raw materials is widely implemented in industry, but the problems of large heat release amount, easy deep oxidation of isobutene, complex side reaction, low yield of the product MAL, large using amount of the catalyst and the like still exist in the production process. In the production process of the catalyst, the problems of high energy consumption, serious pollution, serious equipment corrosion and the like exist. The development of a green process and a method for synthesizing the catalyst, the preparation of the selective oxidation catalyst with high activity, high selectivity and high stability is the key for improving the yield and the economy of the MAL preparation method by the isobutene method.
Various patents have disclosed methods and processes for synthesizing catalysts for the gas phase oxidation of tertiary butanol or isobutylene to produce methacrolein. The catalyst is mainly related to the composition, the proportion and the preparation method of the catalyst. The commonly used catalyst is a composite metal oxide with Mo-Bi-Fe-Co as a main component, and the electronic structure of the catalyst is improved by adding other metal elements, so that the catalytic performance is improved. A general purposeThe preparation method comprises the steps of dissolving various metal salts serving as raw materials in water to obtain two to four parts of raw material solutions, mixing the raw material solutions, adjusting the pH value to obtain slurry, drying, roasting and the like to obtain the catalyst active component. Some of the patents also relate to the use of the Mo-Bi-Fe-Co active component produced with SiO 2 And Al 2 O 3 After mechanical mixing of the carriers, molding is carried out, and the mechanical property and the catalytic property of the catalyst are further improved.
In CN 10983381A, zhang Suojiang and the like mix Mo, bi, fe, cu, ce and Co to prepare slurry, the slurry is directly dried and dehydrated after aging for a plurality of hours, and then is roasted to obtain the catalyst, the catalyst is used for preparing methacrolein by oxidizing tertiary butanol, the conversion rate is 98.3%, and the selectivity of the methacrolein is 86.1%.
CN 1308074C discloses (Mo + W) a Bi b Fe c Sb d The preparation process of mixed metal oxide catalyst includes mixing various metal salt solutions to prepare slurry, stirring at proper temperature for several hr, spray drying, forming and roasting. The prepared catalyst is used for preparing methacrolein by oxidizing isobutene, the conversion rate is 97.8%, and the selectivity of methacrolein is 88.3%.
CN 1314887C discloses a method for preparing a catalyst consisting of Mo, bi, fe, cu, sb, pb and Yb, which comprises the steps of dissolving and mixing metal salts uniformly, adjusting pH, aging, directly evaporating the obtained slurry to dryness at 150-250 ℃, mixing the obtained solid with a carrier, and then roasting at high temperature to obtain the mixed metal oxide catalyst. The obtained catalyst is applied to tertiary butanol or isobutylene gas phase oxidation to prepare methacrolein, the reactant conversion rate is 96.7%, and the MAL selectivity is 86.2%.
CN 103914001A discloses that the active component is Mo 12 Bi a Fe b Co c Ce d Yb e X f Y g Z h O x The carrier is SiO 2 Or Al 2 O 3 The catalyst for synthesizing methacrolein and methacrylic acid, the catalyst preparation process comprising: firstly, respectively dissolving the compounds of corresponding component elements in water, mixing and stirring uniformlyAdjusting pH = 4-9 with ammonia water, stirring and curing at 50-90 ℃, evaporating and forming, and finally roasting and activating at 400-700 ℃ for 1-10 hours.
Wang Guofang, etc. to synthesize Mo-Bi-V series metal oxide catalyst, and the slurry obtained in the synthesis process is filtered, washed with water, dried and roasted to obtain the catalyst. However, when the catalyst is used for the reaction of preparing methacrolein by selective oxidation of isobutene, the catalyst activity is low, the conversion rate is lower than 80%, and the product selectivity is about 80%.
The disclosed catalyst for preparing methylacrolein by gas-phase oxidation of tert-butyl alcohol or isobutene is prepared through ageing mixed metal slurry, direct baking, baking solid, and calcining and shaping. A large amount of water exists in the catalyst synthetic slurry, the drying process is direct, and the energy consumption is large due to evaporation of a large amount of water. In addition, a large amount of nitrate and ammonia substances exist in the slurry, and a large amount of volatile nitrate substances are discharged in the drying process, so that the equipment is seriously corroded. In the high-temperature roasting process, because the solid obtained by direct drying still contains a large amount of organic nitrate radical and ammonia radical substances, a large amount of toxic NO can be generated by roasting x The gases, and in addition, the formation of acidic species also cause significant corrosion of the equipment. Particularly, the method for preparing the catalyst by direct drying can cause uneven distribution of metal components, so that the selectivity of the methacrolein is low, the consumption of raw materials and the energy consumption for product separation are increased, and the production cost of MMA is increased.
Disclosure of Invention
The invention aims to solve the problems and provide a method for preparing tert-butyl alcohol or preparing methacrolein by gas phase oxidation of isobutene with low energy consumption, environmental protection and high efficiency, the prepared catalyst is applied to selective oxidation of isobutene and/or tert-butyl alcohol to prepare methacrolein, the activity of the catalyst is kept, the selectivity of methacrolein can be obviously improved, CO is reduced 2 The amount of discharge of (c).
The purpose of the invention is realized by the following technical scheme:
the first object of the present application is to protect a catalyst for the synthesis of unsaturated aldehydes, the catalystThe catalyst comprises the following components: mo 20 W a Bi b Fe c Co d Ce e X f Y g O h /iZ；
Wherein X is an alkali metal or alkaline earth metal element;
wherein Y is any one or combination of more of nickel, tellurium, strontium, manganese, copper, tin or titanium;
wherein Z is a carrier;
wherein the value range of a is 0-5; the value range of b is 0.5-6.0; the value range of c is 1-10.0; the value range of d is 5-20; the value range of e is 0.1-5.0; the value range of f is 0.05-5; g ranges from 0 to 10, and h is the total number of oxygen atoms required by the valence of other elements;
wherein i is the mass ratio of the carrier to the active components of the catalyst, and the value range of i is 0-10.
Further, wherein Z is SiO 2 SiC or Al 2 O 3 One or a mixture thereof.
A second object of the present application is to protect a method for preparing the above catalyst for the synthesis of unsaturated aldehydes, comprising the steps of:
preparing a mixed solution A containing Mo: sequentially adding a molybdenum-containing raw material, a tungsten-containing raw material and a potassium-containing raw material into deionized water according to a metering ratio, and uniformly stirring to obtain a precursor mixed solution A;
preparing a mixed solution containing Fe, co, bi and Ce: sequentially adding soluble iron salt, cobalt salt, bismuth salt, cerium salt, salt corresponding to X and salt corresponding to Y into a nitric acid solution according to a metering ratio to prepare a mixed metal salt solution B;
and dropwise adding the mixed metal salt solution B into the precursor mixed solution A under the stirring state, adjusting the pH value by using ammonia water after dropwise adding, aging, adding the binder and the carrier, continuously stirring and aging, filtering, washing, drying and roasting to obtain a catalyst finished product.
Further, the pH value of the mixed slurry is adjusted by ammonia water, so that the pH value is more than or equal to 2 and less than or equal to 10.
Further, the mass ratio of the carrier to the catalyst active component is 0 to 10.
Further, the mass ratio of the binder to the catalyst active component is 0 to 1.
Further, the aging process is that the mixed slurry is in a suspension state through continuous or intermittent stirring, the aging temperature is 40-180 ℃, preferably 50-120 ℃, and the aging time is 1-24 hours, preferably 6-12 hours.
Further, the roasting temperature is 400-650 ℃, preferably 450-550 ℃.
A third object of the present application is to protect the use of one of the above catalysts in the preparation of methacrolein by the gas phase oxidation of tert-butanol or isobutylene.
Furthermore, in the reaction for preparing the methacrolein by the gas phase oxidation of the tertiary butanol or the isobutene, the reaction temperature is 320-400 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1) The technical scheme can greatly reduce the energy consumption in the production process of the catalyst and reduce toxic NO x The emission of pollutants reduces the corrosion of acid gas to equipment.
2) The technical scheme can obviously increase the utilization rate of metal elements, the active metal of the catalyst is more uniformly distributed, the selective oxidation process of reaction raw materials is more favorably controlled, the methacrolein can be prepared with high yield, and the CO is reduced x And (4) discharging.
3) The catalyst prepared by the technical scheme is used for preparing methacrolein by gas phase oxidation of tertiary butanol or isobutene, the conversion rate of reactants is more than 99 percent, the selectivity of the methacrolein reaches 92 percent, and CO byproduct is generated x The selectivity is less than 5%.
Detailed Description
In the preparation method of the catalyst for preparing the methacrolein by the gas phase oxidation of the tertiary butanol or the isobutene, the binder and the carrier are added in the process of metal solution precipitation and aging at a proper pH value and temperature, the obtained slurry can be filtered and washed after aging, and then the catalyst product is obtained by drying and roasting, and the prepared catalyst has high activity and selectivity.
The specific synthesis steps are as follows:
a) Preparing a Mo-containing mixed solution: sequentially adding a molybdenum-containing raw material, a tungsten-containing raw material and an alkali metal raw material into deionized water, and uniformly stirring to obtain a precursor mixture;
b) Sequentially adding soluble metal salts such as iron salt, cobalt salt, nickel salt, bismuth salt, manganese salt, cesium salt and the like into a nitric acid solution to prepare a mixed metal salt solution;
c) Adding the solution B into the solution A under a stirring state and at a proper temperature, adjusting the pH value by using ammonia water after the dropwise adding is finished, continuously stirring, and aging for a plurality of hours;
d) Adding a binder and a carrier into the slurry, and continuously stirring and aging for a period of time;
e) And D, filtering, washing, drying and roasting the slurry obtained in the step D to obtain the catalyst.
The composition of the finally prepared catalyst was: mo 20 W a Bi b Fe c Co d Ce e X f Y g O h /iZ；
Wherein X is an alkali metal or alkaline earth metal element;
wherein Y is any one or combination of more of nickel, tellurium, strontium, manganese, copper, tin or titanium;
wherein Z is a carrier;
wherein the value range of a is 0-5; the value range of b is 0.5-6.0; the value range of c is 1-10.0; the value range of d is 5-20; the value range of e is 0.1-5.0; the value range of f is 0.05-5; g ranges from 0 to 10, and h is the total number of oxygen atoms required by the valence of other elements;
wherein i is the mass ratio of the carrier to the active components of the catalyst, and the value range of i is 0-10.
Wherein Z is SiO 2 SiC or Al 2 O 3 One or a mixture thereof.
And adjusting the pH value of the mixed slurry by ammonia water to ensure that the pH value is not less than 2 and not more than 10.
The mass ratio of the carrier to the active components of the catalyst is 0-10.
The mass ratio of the binder to the catalyst active component is 0-1.
The mixed slurry is kept in a suspension state by continuous or intermittent stirring, the aging temperature is 40-180 ℃, preferably 50-120 ℃, and the aging time is 1-24 hours, preferably 6-12 hours.
The calcination temperature is 400-650 deg.C, preferably 450-550 deg.C.
In the process of implementation, the skilled person can refer to the implementation processes in the examples, and adjust the process according to the parameter ranges defined above, so that the catalyst product with ideal performance can be realized.
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
40 g of ammonium molybdate and 0.4 g of potassium nitrate were dissolved in 120 g of distilled water at 50 ℃ under stirring to obtain a solution (A). In 120 g of 10% dilute nitric acid solution, 44 g of cobalt nitrate, 7 g of iron nitrate, 4 g of cerium nitrate, 14 g of bismuth nitrate and 1.0 g of cesium nitrate were dissolved, respectively, to prepare an aqueous solution (B). The solution (B) was added dropwise to the solution (A) at 50 ℃ with vigorous stirring to prepare a slurry C, and stirring was carried out for 1 hour after completion of the dropwise addition. And then ammonia water with the concentration of 10% is dripped into the slurry C, the pH value is adjusted to be 4, after the aging is continued for 12 hours, the slurry is directly dried at the temperature of 100 ℃, and a solid sample is roasted at the temperature of 500 ℃ to prepare the catalyst.
Example 2
40 g of ammonium molybdate and 0.4 g of potassium nitrate were dissolved in 120 g of distilled water at 50 ℃ under stirring to obtain a solution (A). In 120 g of 8% dilute nitric acid solution, 40 g of cobalt nitrate, 8 g of iron nitrate, 4 g of cerium nitrate, 14 g of bismuth nitrate and 1.0 g of cesium nitrate were dissolved, respectively, to prepare an aqueous solution (B). Dropwise adding the solution (B) into the solution (A) under vigorous stirring at 50 ℃ to prepare slurry C, stirring for 1 hour after dropwise adding, then dropwise adding ammonia water with the concentration of 10% into the slurry C, adjusting the pH value of the solution C to 4 to prepare slurry D, continuously stirring and aging for 12 hours, carrying out suction filtration, washing to obtain a solid sample, and drying at 100 ℃. Then the solid sample is roasted at 500 ℃ to prepare the catalyst.
Example 3
40 g of ammonium molybdate and 0.4 g of potassium nitrate were dissolved in 120 g of distilled water with stirring at 80 ℃ to obtain a solution (A). In 120 g of 10% dilute nitric acid solution, 40 g of cobalt nitrate, 5 g of nickel nitrate and 12 g of iron nitrate, 4 g of cerium nitrate, 15 g of bismuth nitrate and 1.0 g of cesium nitrate were dissolved, respectively, to prepare an aqueous solution (B). Dropwise adding the solution (B) into the solution (A) under vigorous stirring at 80 ℃ to obtain slurry C, continuously stirring for 1 hour after dropwise adding, then dropwise adding 10% ammonia water into the slurry C, and adjusting the pH of the solution C to 5 to obtain slurry D. And D, continuously stirring and aging for 15 hours, carrying out suction filtration, washing to be neutral, and drying the obtained solid sample at 100 ℃. Then the solid sample is roasted at 500 ℃ to prepare the catalyst.
Example 4
40 g of ammonium molybdate and 0.3 g of potassium nitrate were dissolved in 120 g of distilled water at 50 ℃ under stirring to obtain a solution (A). In 120 g of 8% dilute nitric acid solution, 40 g of cobalt nitrate, 10 g of nickel nitrate and 18 g of iron nitrate, 3 g of cerium nitrate, 15 g of bismuth nitrate and 1.0 g of cesium nitrate were dissolved, respectively, to prepare an aqueous solution (B). The solution (B) was added dropwise to the solution (A) at 50 ℃ with vigorous stirring to prepare a slurry C, and stirring was carried out for 1 hour after completion of the dropwise addition. Then, 10% aqueous ammonia was added dropwise to the slurry C, and the pH of the solution C was adjusted to 5.5 to obtain a slurry D. After aging for 6 hours with continued stirring, 20 g of alumina was added to D, followed by 5 g of a 10% glycerol solution to make slurry E. And E, after aging for 6 hours, carrying out suction filtration, washing to be neutral, and drying the obtained solid sample at 100 ℃. Then the solid sample is roasted at 500 ℃ to prepare the catalyst.
Example 5
40 g of ammonium molybdate, 1.0 g of metatungstic acid and 0.5 g of potassium nitrate were dissolved in 120 g of distilled water at 50 ℃ under stirring to obtain a solution (A). In 120 g of 10% dilute nitric acid solution, 44 g of cobalt nitrate, 5 g of manganese nitrate and 20 g of iron nitrate, 4 g of cerium nitrate, 16 g of bismuth nitrate and 1.0 g of cesium nitrate were dissolved, respectively, to prepare an aqueous solution (B). The solution (B) was added dropwise to the solution (A) at 50 ℃ with vigorous stirring to prepare a slurry C, and stirring was carried out for 1 hour after completion of the dropwise addition. Then, 10% ammonia water was added dropwise to the slurry C, and the pH of the solution C was adjusted to 6.5 to obtain a slurry D. D after aging for 10 hours with continued stirring, 10 grams of alumina was added to D followed by 5 grams of a 10% glycerol solution to make slurry E. And E, after aging for 10 hours, carrying out suction filtration and washing to obtain a solid sample, and drying at 100 ℃. Then the solid sample is roasted at 500 ℃ to prepare the catalyst.
Example 6
40 g of ammonium molybdate, 3.0 g of ammonium metatungstate and 0.5 g of potassium nitrate were dissolved in 120 g of distilled water at 50 ℃ under stirring to obtain a solution (A). An aqueous solution (B) was prepared by dissolving 40 g of cobalt nitrate, 10 g of manganese nitrate and 20 g of iron nitrate, 4 g of cerium nitrate, 15 g of bismuth nitrate and 1.0 g of cesium nitrate in 120 g of 5% dilute nitric acid solution, respectively. The solution (B) was added dropwise to the solution (A) at 50 ℃ with vigorous stirring to prepare a slurry C, and stirring was carried out for 1 hour after completion of the dropwise addition. Then, 10% ammonia water was added dropwise to the slurry C, and the pH of the solution C was adjusted to 6.5 to obtain a slurry D. D after aging for 4 hours with continued stirring, 10 g of silica sol was added to D to obtain slurry E. And E, after aging for 6 hours, carrying out suction filtration, washing to be neutral, and drying the obtained solid sample at 100 ℃. Then the solid sample is roasted at 500 ℃ to prepare the catalyst.
Example 7
40 g of ammonium molybdate and 0.5 g of potassium nitrate were dissolved in 120 g of distilled water at 50 ℃ under stirring to obtain a solution (A). An aqueous solution (B) was prepared by dissolving 44 g of cobalt nitrate, 10 g of manganese nitrate and 20 g of iron nitrate, 4 g of cerium nitrate, 15 g of bismuth nitrate, 1.0 g of cesium nitrate and 3.0 g of citric acid in 120 g of 5% dilute nitric acid solution, respectively. The solution (B) was added dropwise to the solution (A) at 50 ℃ with vigorous stirring to prepare a slurry C, and stirring was carried out for 1 hour after completion of the dropwise addition. Then, 10% ammonia water was added dropwise to the slurry C, and the pH of the solution C was adjusted to 6 to obtain a slurry D. And D, continuously stirring and aging for 12 hours, carrying out suction filtration, washing to obtain a solid sample, and drying at 100 ℃. Then the solid sample is roasted at 500 ℃ to prepare the catalyst.
Example 8
40 g of ammonium molybdate, 1.0 g of ammonium metatungstate and 0.5 g of potassium nitrate were dissolved in 120 g of distilled water at 50 ℃ under stirring to obtain a solution (A). An aqueous solution (B) was prepared by dissolving 44 g of cobalt nitrate, 24 g of iron nitrate, 3 g of cerium nitrate, 16 g of bismuth nitrate and 1.3 g of cesium nitrate in 120 g of 10% dilute nitric acid solution, respectively. The solution (B) was added dropwise to the solution (A) at 60 ℃ with vigorous stirring to prepare a slurry C, and stirring was carried out for 1 hour after completion of the dropwise addition. Then, 10% ammonia water was added dropwise to the slurry C, and the pH of the solution C was adjusted to 6.0 to obtain a slurry D. D after aging for 10 hours with continued stirring, 10 grams of alumina, 1 gram of antimony oxide was added to D followed by 3 grams of 10% glycerol solution to make slurry E. And E, after aging for 6 hours, carrying out suction filtration and washing to obtain a solid sample, and drying at 100 ℃. Then the solid sample is roasted at 500 ℃ to prepare the catalyst.
Experiment of oxidation reaction
The catalyst prepared in the above examples 1 to 8 was screened into particles of 20 to 40 mesh and used in the reaction for preparing methacrolein by the oxidation of t-butanol. Mixing the catalyst particles with quartz sand according to the volume ratio of 1:1 to obtain the diluted catalyst. 10ml of the diluted catalyst was weighed and charged into a stainless steel reaction tube. The performance of the catalyst is tested by taking tert-butyl alcohol as a reaction raw material and air as an oxidant, reacting at 400 ℃ under normal pressure. Specific data are shown in the following table:
TABLE 1 Oxidation reaction conditions and results
It can be seen that since no carrier and binder were added during the synthesis of examples 2 and 3, the performance of the catalyst obtained after washing with water and filtration was inferior to that of the other examples. The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. Method for synthesizing unsaturated aldehydeA catalyst, characterized in that the composition of the catalyst is: mo 20 W a Bi b Fe c Co d Ce e X f Y g O h /iZ；
Wherein X is an alkali metal or alkaline earth metal element;
wherein Y is any one or combination of more of nickel, tellurium, strontium, manganese, copper, tin or titanium;
wherein Z is a carrier;
wherein the value range of a is 0-5.0; the value range of b is 0.5-6.0; the value range of c is 1-10.0; the value range of d is 5-20; the value range of e is 0.1-5.0; the value range of f is 0.05-5; g ranges from 0 to 10, and h is the total number of oxygen atoms required by the valence of other elements;
wherein i is the mass ratio of the carrier to the active component of the catalyst, and the value range of i is 0-10.
2. The catalyst for synthesizing unsaturated aldehydes according to claim 1, wherein Z is SiO 2 SiC or Al 2 O 3 One or a mixture thereof.
3. A method for preparing the catalyst for synthesizing unsaturated aldehydes as set forth in claim 1, comprising the steps of:
preparing a mixed solution A containing Mo: sequentially adding a molybdenum-containing raw material, a tungsten-containing raw material and a potassium-containing raw material into deionized water according to a metering ratio, and uniformly stirring to obtain a precursor mixed solution A;
preparing a mixed solution containing Fe, co, bi and Ce: sequentially adding soluble iron salt, cobalt salt, bismuth salt, cerium salt, salt corresponding to X and salt corresponding to Y in a nitric acid solution according to a metering ratio to obtain a mixed metal salt solution B;
and dropwise adding the mixed metal salt solution B into the precursor mixed solution A under the stirring state, adjusting the pH value by using ammonia water after dropwise adding, aging, adding the binder and the carrier, continuously stirring and aging, filtering, washing, drying and roasting to obtain a catalyst finished product.
4. The method according to claim 3, wherein the pH of the mixed slurry is adjusted with aqueous ammonia so that the pH is 2 or more and 10 or less.
5. The method of claim 3, wherein the mass ratio of the carrier to the active component of the catalyst is 0 to 10.
6. The method of claim 3, wherein the mass ratio of the binder to the active ingredient of the catalyst is 0 to 1.
7. The method of claim 3, wherein the aging process is carried out by suspending the mixed slurry with continuous or intermittent stirring, the aging temperature is 40-180 ℃, and the aging time is 1-24h.
8. The method of claim 3, wherein the calcination temperature is 400 to 650 ℃.
9. Use of the catalyst of claim 1 in the gas phase oxidation of tert-butanol or isobutylene to produce methacrolein.
10. The use of the catalyst according to claim 9 in the preparation of methacrolein by the gas phase oxidation of tert-butyl alcohol or isobutylene, wherein the reaction temperature is 320-400 ℃ in the preparation of methacrolein by the gas phase oxidation of tert-butyl alcohol or isobutylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110765934.4A CN115569650A (en) | 2021-07-06 | 2021-07-06 | Catalyst for synthesizing unsaturated aldehyde and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110765934.4A CN115569650A (en) | 2021-07-06 | 2021-07-06 | Catalyst for synthesizing unsaturated aldehyde and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115569650A true CN115569650A (en) | 2023-01-06 |
Family
ID=84580042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110765934.4A Pending CN115569650A (en) | 2021-07-06 | 2021-07-06 | Catalyst for synthesizing unsaturated aldehyde and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115569650A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100592A (en) * | 1987-02-17 | 1988-11-16 | 日本触媒化学工业株式会社 | The oxide catalyst of the alkene or the tertiary alcohol and production method thereof |
| EP0304867A2 (en) * | 1987-08-26 | 1989-03-01 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Process for preparation of methacrolein and methacrylic acid from methyl tert.-butyl ether |
| CN1119638A (en) * | 1994-05-31 | 1996-04-03 | 株式会社日本触媒 | Catalyst for production of unsaturated aldehyde and unsaturated carboxylic acid and method for production of unsaturated aldehyde and unsaturated carboxylic acid by the use of the catalyst |
| JPH0910588A (en) * | 1995-06-30 | 1997-01-14 | Mitsubishi Rayon Co Ltd | Preparation of catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid |
| CN1448380A (en) * | 2002-03-29 | 2003-10-15 | 株式会社日本触媒 | Process for production of unsaturated aldehyde |
| JP2007061763A (en) * | 2005-09-01 | 2007-03-15 | Asahi Kasei Chemicals Corp | Oxide catalyst for production of methacrolein, its manufacturing method and manufacturing method of methacrolein using it |
| US20100323881A1 (en) * | 2009-06-22 | 2010-12-23 | Shanghai Huayi Acrylic Acid Co., Ltd. | Preparation process of a catalyst used for gas phase oxidation of light alkenes to unsaturated aldehydes |
| WO2012063771A1 (en) * | 2010-11-10 | 2012-05-18 | 日本化薬株式会社 | Catalyst for producing methacrolein and methacrylic acid, and process for production thereof |
| CN103420820A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Production method of methylacrolein |
| FR2994973A1 (en) * | 2012-09-03 | 2014-03-07 | Arkema France | PROCESS FOR THE PRODUCTION OF METHACRYLIC ACID |
| CN104220162A (en) * | 2012-03-01 | 2014-12-17 | 沙特基础工业公司 | Molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
| CN104437533A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst of methacrylaldehyde and methacrylic acid, as well as preparation method of catalyst for synthesizing methacrylaldehyde and methacrylic acid |
| CN105498795A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst and preparation method thereof |
-
2021
- 2021-07-06 CN CN202110765934.4A patent/CN115569650A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100592A (en) * | 1987-02-17 | 1988-11-16 | 日本触媒化学工业株式会社 | The oxide catalyst of the alkene or the tertiary alcohol and production method thereof |
| EP0304867A2 (en) * | 1987-08-26 | 1989-03-01 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Process for preparation of methacrolein and methacrylic acid from methyl tert.-butyl ether |
| CN1119638A (en) * | 1994-05-31 | 1996-04-03 | 株式会社日本触媒 | Catalyst for production of unsaturated aldehyde and unsaturated carboxylic acid and method for production of unsaturated aldehyde and unsaturated carboxylic acid by the use of the catalyst |
| JPH0910588A (en) * | 1995-06-30 | 1997-01-14 | Mitsubishi Rayon Co Ltd | Preparation of catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid |
| CN1448380A (en) * | 2002-03-29 | 2003-10-15 | 株式会社日本触媒 | Process for production of unsaturated aldehyde |
| JP2007061763A (en) * | 2005-09-01 | 2007-03-15 | Asahi Kasei Chemicals Corp | Oxide catalyst for production of methacrolein, its manufacturing method and manufacturing method of methacrolein using it |
| US20100323881A1 (en) * | 2009-06-22 | 2010-12-23 | Shanghai Huayi Acrylic Acid Co., Ltd. | Preparation process of a catalyst used for gas phase oxidation of light alkenes to unsaturated aldehydes |
| WO2012063771A1 (en) * | 2010-11-10 | 2012-05-18 | 日本化薬株式会社 | Catalyst for producing methacrolein and methacrylic acid, and process for production thereof |
| CN104220162A (en) * | 2012-03-01 | 2014-12-17 | 沙特基础工业公司 | Molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
| CN103420820A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Production method of methylacrolein |
| FR2994973A1 (en) * | 2012-09-03 | 2014-03-07 | Arkema France | PROCESS FOR THE PRODUCTION OF METHACRYLIC ACID |
| CN104437533A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst of methacrylaldehyde and methacrylic acid, as well as preparation method of catalyst for synthesizing methacrylaldehyde and methacrylic acid |
| CN105498795A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李静霞等: "稀土元素对Mo-Bi 系复合催化剂选择氧化异丁烯制甲基丙烯醛的影响", 《化学反应工程与工艺》, vol. 28, no. 4 * |
| 赖群萍等: "Mn 对异丁烯选择氧化制甲基丙烯醛Mo-Bi-Fe-Co-Cs-K复合氧化物催化剂的促进作用及其机理", 《分子催化》, vol. 26, no. 1 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101291757B1 (en) | Method for producing a nanocrystalline bismuth-molybdenum mixed oxide | |
| US7544633B2 (en) | Catalyst for partial oxidation and preparation method thereof | |
| US8114805B2 (en) | Method of preparing heteropoly acid catalyst | |
| CN102553624B (en) | Preparation method of catalyst for synthesizing methacrylic acid | |
| JPH0242540B2 (en) | ||
| US20040192545A1 (en) | Method for preparing a catalyst for partial oxidation of propylene | |
| CN101778669B (en) | Method of preparing improved catalyst for production of acrylic acid | |
| JP3797148B2 (en) | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| CN115569650A (en) | Catalyst for synthesizing unsaturated aldehyde and preparation method thereof | |
| CN112619645A (en) | Catalyst for preparing acrylic acid and preparation method and application thereof | |
| JP4200744B2 (en) | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| JP5362370B2 (en) | Method for producing catalyst for synthesis of methacrylic acid | |
| JP2005169311A (en) | Production method for complex oxide catalyst | |
| KR20040084092A (en) | Method for preparing catalysts for partial oxidation of propylene and iso-butylene | |
| JP3790130B2 (en) | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| JP4273565B2 (en) | Process for the preparation of complex oxide catalysts for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids | |
| JP2006513033A (en) | Novel heteropolyacid catalyst and production method thereof | |
| JPH0615178A (en) | Preparation of catalyst for production of methacrylic acid | |
| CN112547082B (en) | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof | |
| CN113546636B (en) | Catalyst for preparing methylacrolein from isobutene or tertiary butanol and preparation method thereof | |
| CN112657502B (en) | Catalyst for preparing methylacrolein and preparation method and application thereof | |
| JPH05285390A (en) | Production of oxidation catalyst | |
| KR20090038745A (en) | Preparation of catalyst with controlled tellurium contents | |
| JPH0686932A (en) | Production of catalyst for producing methacrylic acid | |
| KR20040009755A (en) | A catalyst compositon for gaseous partial oxidation of propylene and method for preparing the same |
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 |