CN107282057B - Catalyst for synthesizing acrolein and acrylic acid - Google Patents
Catalyst for synthesizing acrolein and acrylic acid Download PDFInfo
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- CN107282057B CN107282057B CN201610227758.8A CN201610227758A CN107282057B CN 107282057 B CN107282057 B CN 107282057B CN 201610227758 A CN201610227758 A CN 201610227758A CN 107282057 B CN107282057 B CN 107282057B
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- 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
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- 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
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- 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
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- 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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a catalyst for synthesizing acrolein and acrylic acid. The technical scheme is as follows: the catalyst for synthesizing the acrolein and the acrylic acid comprises the following components in parts by weight: 35-80 parts of macroporous Si-Al oxide carrier; and active component carried thereon, 20-65 parts; the active component is represented by Mo in atomic number12BiaNicQsYeZfOx(ii) a Wherein Q is at least one selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn and Fe; y is at least one selected from K, Rb, Na, Li or Cs; z is at least one of La, Ce or Sm; a is the number of Bi atoms; c is the number of Ni atoms; s is the number of Q atoms; e is the number of Y atoms; f is the number of Z atoms; x is the total number of oxygen atoms required to satisfy the valences of the other elements.
Description
Technical Field
The present invention relates to a catalyst for synthesizing acrolein and acrylic acid, a preparation method of the catalyst, an application of the catalyst in synthesizing acrolein and acrylic acid, and a synthesis method of the acrolein and acrylic acid.
Background
Acrylic acid (CH)2CH — COOH) is the simplest unsaturated carboxylic acid, which is an important organic synthetic raw material and synthetic resin monomer. Acrylic acid is mainly used for synthesizing high-grade water-absorbent resin, a water treatment agent and the like, a part of acrylic acid is used for esterification to prepare acrylic esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like, and an acrylic ester polymer is mainly applied to the fields of adhesives, coatings, textiles, plastics, leather, paper making and the like.
In recent years, acrylic acid and series products thereof are rapidly developed, in 2013, the worldwide production of acrylic acid and esters thereof reaches 607.6 mt/a, which is increased by 17.8% compared with 515.6 mt/a at the end of 2010, and the current production devices of acrylic acid are mainly concentrated in the United states, Europe, Japan and China, wherein China is the country where the production capacity of acrylic acid is fastest in recent years, and China exceeds the United states and Europe at the same time in 2012 and becomes the country where the production capacity of acrylic acid devices is greatest in the world. The large-scale equipment for industrially producing acrylic acid all over the world adopts propylene oxidation technology, which has been in the history for decades, and a great deal of technology development makes the production process perfect.
The catalyst forming preparation process in the prior art generally comprises the steps of preparing slurry, spraying, kneading, extruding and forming, and finally roasting. However, the inventors of the present application have found that in the reaction of propylene to produce acrolein and acrylic acid, a large amount of heat is generated, hot spots are very easily generated, and the final reaction effect of the catalyst is determined only by the easiness of the active component on the shaped catalyst which the propylene substrate can contact, so that it is difficult to prepare the catalyst with a reasonable dispersion of the active component in the catalyst technology of the art.
The Chinese patent CN1564709 can overcome the layering between metal salts generated in the process of preparing the catalyst by coprecipitation to a certain extent by adding organic carboxylic acid, so that each metal is more uniformly distributed in the precipitation process, thereby improving the performance of the catalyst.
The Chinese patent CN1089081C takes Mo, Bi and Fe as basic elements, avoids the generation of hot spots in the reaction and can avoid the peroxidation by adjusting the types and the contents of the elements and further adjusting the filling mode of the catalyst in a reactor. But the prior catalyst has the problem of low total yield of acrolein and acrylic acid.
However, in the reaction of preparing acrolein and acrylic acid by propylene oxidation, a large amount of heat is accompanied, and the final reaction effect of the catalyst is determined only by the difficulty of the active components on the formed catalyst which can be contacted by reaction substrate propylene, so that the prepared catalyst has highly dispersed active components and a large amount of macroporous structures, and has obvious benefits on the improvement of the propylene oxidation reaction effect and the heat dissipation of a catalyst bed layer.
Disclosure of Invention
The invention provides a catalyst, which aims to solve the technical problem that the activity and selectivity of the catalyst in the reaction for producing acrolein and acrylic acid by oxidizing propylene in the prior art are low. The catalyst is used for the reaction of producing acrolein and acrylic acid by propylene oxidation, and has the characteristics of high yield of acrolein and acid and good stability.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst.
The invention also provides the application of the catalyst in the production of acrolein and acrylic acid by propylene oxidation.
The fourth technical problem to be solved by the present invention is to provide a method for synthesizing acrolein and acid using the catalyst described in one of the above technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the catalyst for synthesizing the acrolein and the acrylic acid comprises the following components in parts by weight:
35-80 parts of macroporous Si-Al oxide carrier;
and active component carried thereon, 20-65 parts;
the active component is represented by Mo in atomic number12BiaNicQsYeZfOx；
Wherein Q is at least one selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn and Fe; y is at least one selected from K, Rb, Na, Li or Cs; z is at least one of La, Ce or Sm; a is the number of Bi atoms; c is the number of Ni atoms; s is the number of Q atoms; e is the number of Y atoms; f is the number of Z atoms; x is the total number of oxygen atoms required to satisfy the valences of the other elements.
In the technical scheme, the value range of a is preferably 0.05-6.0.
In the technical scheme, the value range of c is preferably 0.05-6.0.
In the technical scheme, the value range of s is preferably 0.05-6.0.
In the technical scheme, the value range of e is preferably 0-0.5.
In the technical scheme, the value range of f is preferably 0-5.0.
More preferably, Q comprises Fe and X, X is selected from at least one of Mg, Co, Ca, Be, Cu, Zn, Pb and Mn, namely the activity expression is as follows: mo12BiaFebNicXdYeZfOx，
In the technical scheme, the value range of b is preferably 0.05-4.0.
In the technical scheme, the value range of d is preferably 0.2-6.0.
In the above technical solution, the average pore diameter of the macroporous Si-Al oxide support is preferably 0.5 to 2.5 μm.
In the above technical scheme, the Si/Al molar ratio of the macroporous Si-Al oxide support is not particularly limited. Such as but not limited to 0.5-3.
As a further more preferable technical scheme, when the catalyst is prepared by the steps of firstly loading Fe and Mo by using a mixed impregnation liquid of Fe and Mo required according to the molar ratio of Mo to Fe for the carrier, roasting, then further loading the rest active elements and roasting, the conversion rate of propylene and the total yield of aldehyde and acid are higher than other loading sequences. The molar ratio of Mo to Fe is most preferably 0.5-4, and most preferably 0.5-2.
The key point of the catalyst of the present invention is not in the geometry and size of the catalyst, so there is no particular limitation on the shape and size of the catalyst, and various shapes and sizes of existing supports can be used in the present invention and comparable results are obtained. For example, the carrier of the present invention may take the form of a sphere, raschig ring, or cylinder, etc. The spherical diameter can be preferably 3-5 mm; the outer diameter of the raschig ring can be preferably 4-7 mm, the inner diameter is preferably 1.5-3 mm, and the length is preferably 3-5 mm; the cylindrical outer diameter can be preferably 4-7 mm, and the length is preferably 3-5 mm.
To solve the second technical problem, the invention adopts the following technical scheme: the method for preparing the catalyst according to any one of the above technical problems comprises the following steps:
(a) dissolving all required Fe compounds and required Mo compounds according to the molar ratio of Mo to Fe of 0.5-2 in water to obtain a Fe-Mo mixed solution, and adjusting the pH value of the solution to 3-6 by using ammonia water to obtain an aqueous solution I.
(b) And mixing the macroporous Si-Al oxide carrier with the aqueous solution I, drying and roasting to obtain the catalyst precursor alpha.
(c) And dissolving the required amount of soluble salts of Bi, Ni, X, Y and Z and the balance of Mo in water to obtain the aqueous dispersion II.
(d) And mixing the catalyst precursor alpha with the water dispersion II, drying and roasting to obtain the catalyst.
In the above technical scheme, the roasting temperature in step (b) and/or step (d) is preferably 400-.
The macroporous Si-Al oxide supports described therein can be prepared by methods known in the art or obtained from commercial sources. If homemade, but not limited to, the preparation method comprising the following steps can be adopted:
(1) mixing 1400-1600 parts of polyethylene glycol, 1900-2100 parts of polyethylene glycol and epoxy resin, heating for melting, rapidly adding diethylenetriamine while stirring vigorously, transferring the reaction liquid into a crystallization kettle, crystallizing for 3-5 hours at 60-80 ℃ to obtain a milky white solid, repeatedly washing to remove the polyethylene glycol, and drying to obtain the porous polymer template beta.
(2) Dissolving tetraethyl orthosilicate and aluminum isopropoxide in ethanol according to the required Si/Al molar ratio, adding a porous polymer template beta, uniformly mixing, adding ammonia water under vigorous stirring, filtering out precipitates, drying, roasting, and finally forming by rolling balls, extruding strips or tabletting to obtain the macroporous Si-Al oxide carrier.
The preparation method of the partial macroporous Si-Al oxide comprises the following steps: mixing 90 g of polyethylene glycol 1500, 70 g of polyethylene glycol 2000 and 80 g of epoxy resin, heating and melting, rapidly adding 20 g of diethylenetriamine while stirring vigorously, transferring the reaction liquid into a crystallization kettle, crystallizing at 70 ℃ for 4h to obtain a milky white solid, taking out, repeatedly washing to remove the polyethylene glycol, and drying to obtain the porous polymer template beta. And dissolving 208 g of tetraethyl orthosilicate and 204g of aluminum isopropoxide in 500ml of ethanol (the molar ratio Si/Al is 1), adding 100 g of porous polymer template beta, uniformly mixing, adding 400ml of ammonia water under the condition of vigorous stirring, filtering out precipitates, drying, and roasting at 800 ℃ for 2 hours to obtain the carrier. The mean pore diameter of the support was 1.2 μm, as measured by the mercury drop method.
To solve the third technical problem, the technical scheme of the invention is as follows:
the method for synthesizing the acrolein and the acrylic acid takes water vapor as a diluent and propylene reacts with an oxidant containing elemental oxygen in the presence of the catalyst in the technical scheme to obtain the acrolein and the acrylic acid.
Key to the present invention is the catalyst, and in the case of the catalyst disclosed herein, the skilled person can rationally select the oxidant and the process conditions without inventive step, such as but not limited to:
(1) in the above technical scheme, the oxidant is air.
(2) The reaction temperature is 330-400 ℃.
(3) The reaction raw materials comprise (by volume ratio) propylene, air and water vapor 1, (6-10) and (1-3).
(4) The volume space velocity of the reaction raw material is 800-1600 hours-1。
The catalyst of the present invention is used in the selective oxidation of propylene to prepare acrolein and acid at reaction temperature of 370 deg.c and reaction space velocity of 1400 hr-1Under the condition, after 1000 hours, the conversion rate of propylene can reach 99.1 percent, the total yield of acrolein and acrylic acid can reach 92.8 percent, the yield of the product acrolein can reach 78.1 percent, and a better technical effect is achieved.
In the examples given below, the evaluation conditions for the investigation of the catalyst were:
a reactor: fixed bed reactor, internal diameter 25.4 mm, reactor length 1200 mm
Catalyst loading: 200g
Reaction temperature: 380 deg.C
Reaction time: 4 hours
The volume ratio of raw materials is as follows: propylene air steam 1:7:2
Total volume space velocity of raw materials: 1000 hours-1
The reaction product was absorbed with dilute acid at 0 ℃ and the product was analyzed by gas chromatography. And calculating the carbon balance, wherein the carbon balance is effective data when the carbon balance is (95-105)%.
Propylene conversion, product yield and selectivity are defined as:
the invention adopts the carrier catalyst with a large number of macroporous structures, has excellent catalytic performance and heat dissipation effect, and particularly adopts the method of the technical scheme of the second technical problem to prepare the catalyst, so that the catalyst obtains excellent effects on the total yield of aldehyde and acid and the conversion rate of propylene, and can be used in the industrial production of acrolein.
The invention is further illustrated by the following examples:
Detailed Description
Example 1
In a batch tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 200g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 46.2 g of ferric nitrate (Fe (NO)3)3·9H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) was dissolved and vigorously stirred, and the pH of the solution was adjusted to 5 with aqueous ammonia to obtain an aqueous dispersion. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous dispersion, the mixture is transferred to a rotary evaporator until the water content is evaporated to dryness, the mixture is transferred to an oven for overnight drying, and finally the mixture is roasted for 2 hours at 500 ℃ to obtain the required catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 2
In a compounding tank equipped with a stirring motor, 100ml of deionized water (100 ℃ C.) was added, and 46.2 g of iron nitrate (Fe (NO) was added3)3·9H2O) and 10.1g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) (molar ratio Mo: Fe ═ 0.5) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia water to give aqueous solution I. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous solution, and poured into a rotary evaporator until the aqueous solution I is completely evaporated to dryness, transferred into an oven for overnight drying, and then roasted in a muffle furnace at 500 ℃ for 2 hours to obtain a catalyst precursor.
To a compounding tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 189.9 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia to give an aqueous dispersion II, all the catalyst precursor was added and transferred to a rotary evaporator, the water was evaporated, transferred to an oven for overnight drying, and finally calcined at 500 ℃ for 2 hours to give the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 3
Adding 100ml into a mixing tank equipped with a stirring motorIonized water (100 ℃), 46.2 g ferric nitrate (Fe (NO)3)3·9H2O) and 20.2g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) (molar ratio Mo: Fe ═ 1) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia water to give aqueous solution I. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous solution, and poured into a rotary evaporator until the aqueous solution I is completely evaporated to dryness, transferred into an oven for overnight drying, and then roasted in a muffle furnace at 500 ℃ for 2 hours to obtain a catalyst precursor.
To a compounding tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 179.8 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia to give an aqueous dispersion II, all the catalyst precursor was added and transferred to a rotary evaporator, the water was evaporated, transferred to an oven for overnight drying, and finally calcined at 500 ℃ for 2 hours to give the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 4
In a compounding tank equipped with a stirring motor, 100ml of deionized water (100 ℃ C.) was added, and 46.2 g of iron nitrate (Fe (NO) was added3)3·9H2O) and 28.3g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) (molar ratio Mo: Fe ═ 1.4) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia water to give aqueous solution I. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous solution I, the mixture is transferred to a rotary evaporator, the water is evaporated, the mixture is transferred to an oven for overnight drying, and the mixture is roasted for 2 hours at 500 ℃ in a muffle furnace to obtain a catalyst precursor.
To a compounding tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 171.7 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia to give an aqueous dispersion II, all the catalyst precursor was added and transferred to a rotary evaporator, the water was evaporated, transferred to an oven for overnight drying, and finally calcined at 500 ℃ for 2 hours to give the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 5
In a compounding tank equipped with a stirring motor, 100ml of deionized water (100 ℃ C.) was added, and 46.2 g of iron nitrate (Fe (NO) was added3)3·9H2O) and ammonium molybdate of 40.4 ((NH)4)6Mo7O24·4H2O) (molar ratio Mo: Fe ═ 2) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia water to give aqueous solution I. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous solution, and poured into a rotary evaporator until the aqueous solution I is completely evaporated to dryness, transferred into an oven for overnight drying, and then roasted in a muffle furnace at 500 ℃ for 2 hours to obtain a catalyst precursor.
To a batch tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 159.6 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia to give an aqueous dispersion II, all the catalyst precursor was added and transferred to a rotary evaporator, the water was evaporated, transferred to an oven for overnight drying, and finally calcined at 500 ℃ for 2 hours to give the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 6
In a compounding tank equipped with a stirring motor, 100ml of deionized water (100 ℃ C.) was added, and 46.2 g of iron nitrate (Fe (NO) was added3)3·9H2O) and 101g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) (molar ratio Mo: Fe ═ 5) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia water to give aqueous solution I. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous solution, and poured into a rotary evaporator until the aqueous solution I is completely evaporated to dryness, transferred into an oven for overnight drying, and then roasted in a muffle furnace at 500 ℃ for 2 hours to obtain a catalyst precursor.
In a batch tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 99 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia to give an aqueous dispersion II, all the catalyst precursor was added and transferred to a rotary evaporator, the water was evaporated, transferred to an oven for overnight drying, and finally calcined at 500 ℃ for 2 hours to give the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 7
In a compounding tank equipped with a stirring motor, 100ml of deionized water (100 ℃ C.) was added, and 46.2 g of iron nitrate (Fe (NO) was added3)3·9H2O) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia to give aqueous solution I. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous solution, and poured into a rotary evaporator until the aqueous solution I is completely evaporated to dryness, transferred into an oven for overnight drying, and then roasted in a muffle furnace at 500 ℃ for 2 hours to obtain a catalyst precursor.
In a batch tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 200g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia to give an aqueous dispersion II, all the catalyst precursor was added and transferred to a rotary evaporator, the water was evaporated, transferred to an oven for overnight drying, and finally calcined at 500 ℃ for 2 hours to give the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 8
In a compounding tank equipped with a stirring motor, 100ml of deionized water (100 ℃ C.) was added, and 200g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia to give aqueous solution I. 451.6g of macroporous Si-Al oxide carrier is added into the aqueous solution, and poured into a rotary evaporator until the aqueous solution I is completely evaporated to dryness, transferred into an oven for overnight drying, and then roasted in a muffle furnace at 500 ℃ for 2 hours to obtain a catalyst precursor.
In a compounding tank equipped with a stirring motor, 200ml of deionized water (100 ℃ C.) was added, and 46.2 g of iron nitrate (Fe (NO)3)3·9H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia to give an aqueous dispersion II, all the catalyst precursor was added and transferred to a rotary evaporator, the water was evaporated, transferred to an oven for overnight drying, and finally calcined at 500 ℃ for 2 hours to give the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
Example 9
200ml of deionized water (100 ℃) were added to a batching tank equipped with a stirring motor, and 171.7 g of molybdenum were addedAmmonium salt ((NH)4)6Mo7O24·4H2O), 36.6 g bismuth nitrate (Bi (NO)3)3·5H2O), 49.5 g cobalt nitrate (Co (NO)3)2·6H2O), 69.3 g of nickel nitrate (Ni (NO)3)2·6H2O), 0.51 g of potassium hydroxide (KOH) was dissolved and vigorously stirred, and the pH of the solution was adjusted to 5 with ammonia water to give an aqueous dispersion II, 451.6g of a macroporous Si — Al oxide support was added to the aqueous dispersion II, and transferred to a rotary evaporator, where the water was evaporated, transferred to an oven for overnight drying, and further calcined in a muffle furnace at 500 ℃ for 2 hours to give a catalyst precursor.
In a compounding tank equipped with a stirring motor, 100ml of deionized water (100 ℃ C.) was added, and 46.2 g of iron nitrate (Fe (NO) was added3)3·9H2O) and 28.3g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) (molar ratio Mo: Fe ═ 1.4) was dissolved in water, and the pH of the solution was adjusted to 5 with ammonia water to give aqueous solution I. And adding all the catalyst precursors, transferring the catalyst precursors to a rotary evaporator, evaporating water, transferring the catalyst precursors to an oven for overnight drying, and finally roasting the catalyst precursors for 2 hours at 500 ℃ to obtain the catalyst. The main preparation processes of the catalyst and the catalyst composition are shown in table 1, and the investigation results of the catalyst are shown in table 2.
TABLE 1 catalyst composition and preparation conditions
Table 2, catalyst examination results
Claims (4)
1. The catalyst for synthesizing the acrolein and the acrylic acid comprises the following components in parts by weight:
35-80 parts of macroporous Si-Al oxide carrier;
and active component carried thereon, 20-65 parts;
the active component is represented by Mo in atomic number12BiaFebNicXdYeZfOx；
Wherein X is selected from at least one of Mg, Co, Ca, Be, Cu, Zn, Pb and Mn; y is at least one selected from K, Rb, Na, Li or Cs; z is at least one of La, Ce or Sm; a is the number of Bi atoms; c is the number of Ni atoms; e is the number of Y atoms; f is the number of Z atoms; x is the total number of oxygen atoms required to satisfy the valences of other elements; the value range of b is 0.05-4.0; the preferable value range of d is 0.2-6.0, the value range of a is 0.05-6.0, the value range of c is 0.05-6.0, the value range of e is 0-0.5, and the value range of f is 0; the Si/Al molar ratio of the macroporous Si-Al oxide carrier is 0.5-3.
2. The catalyst of claim 1, wherein said macroporous Si-Al oxide support has an average pore size of 0.5 to 2.5 microns.
3. A method for synthesizing acrolein and acrylic acid, comprising the step of reacting propylene with an oxidant containing elemental oxygen in the presence of the catalyst according to any one of claims 1 to 2 by using water vapor as a diluent to obtain the acrolein and the acrylic acid.
4. The method of claim 3, wherein said oxidizing agent is air.
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| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN104275192A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrolein and acrylic acid and preparation method and application thereof |
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| CN104275192A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrolein and acrylic acid and preparation method and application thereof |
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