CN114425355B - Catalyst for preparing methacrolein by fixed bed, preparation method and application - Google Patents

Catalyst for preparing methacrolein by fixed bed, preparation method and application Download PDF

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CN114425355B
CN114425355B CN202011030869.2A CN202011030869A CN114425355B CN 114425355 B CN114425355 B CN 114425355B CN 202011030869 A CN202011030869 A CN 202011030869A CN 114425355 B CN114425355 B CN 114425355B
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catalyst
solution
bismuth
cobalt
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CN114425355A (en
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张作峰
师慧敏
张东顺
冯晔
安欣
袁滨
刘玉芬
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • C07C45/38—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 being a primary hydroxyl group
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Abstract

The invention discloses a catalyst for preparing methacrolein by a fixed bed, a preparation method and application thereof. The composition of the catalyst is as follows: mo (Mo) a Bi b Fe c Co d Cu e Mg f Cs g O x Wherein a-g are the atomic mole ratio of each element; a=12, 0<b<3.5,0<c<3,0<d<8,0<e<3,0<f<3,0<g<2; x is the number of oxygen atoms required to form the composite oxide. In the preparation process of the catalyst, the Mo, bi, fe, co, cu, mg, cs-containing salt or oxide is added to form a dispersion system, and meanwhile, the complexing agent, the polymer monomer and the cross-linking agent are added into the dispersion system step by step or directly, so that the purposes of controlling the morphology, granularity and uniformity of the catalyst and further improving the activity and selectivity of the catalyst are achieved.

Description

Catalyst for preparing methacrolein by fixed bed, preparation method and application
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, a preparation method and application thereof.
Background
Methyl Methacrylate (MMA) is an important organic chemical raw material, is mainly used for producing polymethyl methacrylate (organic glass), polyvinyl chloride auxiliary ARC and a second monomer used for producing acrylic fibers, can be copolymerized with other vinyl monomers to obtain products with different properties, and can be used as resins, adhesives, ion exchange resins, paper polishing agents, textile printing and dyeing auxiliary agents, leather treatment agents, lubricating oil additives, crude oil pour point depressants, insulating pouring materials, plasticizers of plastic emulsions and the like, and the application is quite wide.
The wide application and the excellent characteristics of the methyl methacrylate are very rapid in recent years. The acetone cyanohydrin method of the traditional route is greatly affected by the transportation or the production allocation of the acrylonitrile, the environmental protection pressure is gradually increased, and the ACH method is greatly restricted.
The isobutene method is a process with excellent MMA production with high added value at present, the raw materials are cheap and pollution-free, is a clean route, is increasingly valued, and is used for cracking C along with the project of tens of millions of tons of oil refining and millions of tons of ethylene in China to build up and build up coal chemical industry MTO 4 The resources are extremely rich, and the advantages of the isobutene oxidation method for producing MMA are gradually reflected.
The preparation of methacrolein from isobutylene is the first step in this route, and the catalyst used for the oxidation of isobutylene to methacrolein is critical to the development of this route.
The current catalysts for this stage of reaction have been studied for many years, and the most widely used composite oxides of molybdenum, bismuth, iron and cobalt have become the consensus of researchers. Alkali metal promoters are also typically added to the catalyst to act as acidic active sites of the catalyst, thereby increasing the selectivity of the reaction. The role of alkali metal in catalysts for the preparation of methacrolein by oxidation of isobutylene or t-butanol is more prominent and essentially indispensable, for example, alkali metals are used in higher proportions on the basis of molybdenum bismuth iron cobalt in the catalysts disclosed in US5892108, CN1143946A, CN103420820A, CN104549353A, CN101385978A, US5583086, CN1280036a and the like. Co, ni, sn and other elements are added into the report catalyst in China patent CN1647853A to increase the conversion rate and selectivity, the final isobutene conversion rate is more than 95%, and the MAL selectivity is more than 86%.
Japanese patent JP11179206 reports that the conversion of isobutene after adding Ni, W, mg and other elements on the basis of Mo, bi, fe, co is 97.1%, and the MAL selectivity is 88.2%. The catalyst is added with tungsten, and the tungsten can be considered to be stably combined with bismuth, so that the effect of molybdenum can be partially replaced within a certain range, but the solubility of tungstate in water is not large, and environmental pollution is easy to cause.
The catalyst described in chinese patent CN 109833881 improves the catalytic performance by co-doping Cu and Ce on the basis of the conventional Mo, bi, fe, co and alkali metal catalysts. Ce with heat resistance and reduction resistance is added to the catalyst in the patent and the patent CN1145946A, the patent CN1467032A, CN103934001 and the patent CN1280036A to inhibit the loss of Mo and improve the long-term stability of the catalyst. Ce is a rare earth element, however, which causes an increase in catalyst cost and an increase in price.
Patent WO2008013376 reports the selection of a Mo-Bi-Nb based composite metal oxide represented by the following general formula: mo (Mo) a Bi b Nb c A d B e C f D g E h F i O j Wherein A is at least one element of W, sb, as, P, sn and Pb; b is at least one element of Fe, zn, cr, mn, cu, pd, ag and Ru; c is at least one element of Co, cd, ta, pt and Ni; d is at least one element of Si, al, zr, V and Ce; e is at least one element of Se, ga, ti, ge, rh and Au; f is at least one element of Na, K, li, rb, cs, ca, mg, sr, ba and MgO; the catalyst is mainly based on molybdenum bismuth niobium, and the main product is acrylic acid, and the yield is not high.
The catalyst performance has more influencing factors, besides the physical and chemical properties, the microstructure of the catalyst has great influence, and particularly the nano-scale catalyst generally shows more excellent catalytic performance. The existing catalysts comprising the comparison are prepared by a coprecipitation method, the agglomeration phenomenon of powder is serious, the uniformity is poor, the repeatability is poor, the sintering activity is poor, and the catalyst is suitable for occasions with low requirements on products or occasions for laboratory small-batch preparation. Therefore, by improving the preparation method, the catalyst powder has high uniformity and fine particles, and is an important direction for regulating and controlling the element composition of the catalyst and simultaneously needing to be studied.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst for preparing methacrolein by a fixed bed, a preparation method and application. In the preparation process of the catalyst, the Mo, bi, fe, co, cu, mg, cs-containing salt or oxide is added to form a dispersion system, and meanwhile, the complexing agent, the polymer monomer and the cross-linking agent are added into the dispersion system step by step or directly, so that the purposes of controlling the morphology, granularity and uniformity of the catalyst and further improving the activity and selectivity of the catalyst are achieved.
It is an object of the present invention to provide a catalyst for the preparation of methacrolein for use in a fixed bed.
The composition of the catalyst is as follows: mo (Mo) a Bi b Fe c Co d Cu e Mg f Cs g O x
Wherein a-x are the atomic mole ratio of each element;
a＝12,0<b<3.5,0<c<3,0<d<8,0<e<3,0<f<3,0<g<2；
x is the number of oxygen atoms required to form the composite oxide.
It is a second object of the present invention to provide a process for preparing said catalyst.
The method comprises the following steps:
(1) The precursor compound of bismuth, iron, cobalt, copper, magnesium and cesium ions is weighed according to the molar ratio and dissolved in an acid solution, and after the solution is clear and transparent, a complexing agent is added to complex the solution with metal ions;
precursor compounds of bismuth, iron, cobalt, copper, magnesium, cesium ions are their oxides, acids, bases, organic salts, inorganic salts or complexes.
(2) After the complexing agent is completely dissolved, adding saccharide substances, and then adding a solution containing acrylamide monomers and methylene bisacrylamide;
(3) After the solution is uniformly mixed and clarified, adding a solution containing molybdenum salt;
(4) Heating the obtained mixed solution or adding an initiator to enable the mixed solution to perform polymerization reaction; and (3) obtaining gel, drying, crushing and roasting to obtain the catalyst.
In a preferred embodiment of the present invention,
the complexing agent is one or a combination of tartaric acid, citric acid and ethylenediamine tetraacetic acid;
the mole ratio of the complexing agent to the sum of bismuth, iron, cobalt, copper, magnesium and cesium ions is (0.1-10): 1.
in a more preferred embodiment of the present invention,
the mole ratio of the complexing agent to the sum of bismuth, iron, cobalt, copper, magnesium and cesium ions is (0.6-6): 1.
the acid solution can be nitric acid solution or hydrochloric acid solution, and the technical personnel can determine according to actual conditions.
In a preferred embodiment of the present invention,
step (2),
the saccharide is glucose and/or fructose; after the saccharide is added, the concentration of the saccharide in the system is 0.01-0.5 g/mL;
wherein, the concentration of the saccharide is: after adding the saccharide, the concentration of the saccharide in the system is not added before adding the solution containing the acrylamide monomer and the methylene bisacrylamide.
In a preferred embodiment of the present invention,
step (2),
the mole ratio of the acrylamide to the sum of bismuth, iron, cobalt, copper, magnesium and cesium ions is (0.1-50): 1; preferably (10 to 40): 1, a step of;
the molar ratio of the methylene bisacrylamide to the acrylamide is (0.01-0.5): 1.
in a preferred embodiment of the present invention,
in step (4), the initiator may be any initiator commonly used in the art, such as: persulfates, azobisisobutyronitrile, dibenzoyl peroxide, and the like, ammonium persulfate may be preferable in the present invention.
In a preferred embodiment of the present invention,
step (4),
the heating temperature is 65-100 ℃;
the roasting temperature is 400-600 ℃, and the roasting time is 2-10 hours.
It is a further object of the present invention to provide a catalyst prepared by the process.
The invention also provides an application of the catalyst or the catalyst obtained by the preparation method in preparing methacrolein by oxidizing tert-butyl isobutene.
The invention adopts the following technical scheme:
a catalyst for preparing methacrolein for a fixed bed, which comprises the following elements: mo (Mo) a Bi b Fe c Co d Cu e Mg f Cs g O x
Mo is molybdenum, bi is bismuth, fe is iron, co is cobalt, cu is copper, mg is magnesium, cs is cesium O is oxygen. a to g are the atomic mole ratios of the elements.
Wherein a=12, 0< b <3.5,0< c <3,0< d <8,0< e <3,0< f <3,0< g <2.
x is the number of oxygen atoms required to form the composite oxide.
The invention adds copper and magnesium on the basis of molybdenum, bismuth, iron, cobalt and alkali metal. Experiments prove that copper and magnesium have synergistic effect on improving the activity and selectivity of the catalyst. And the water solubility is good, the cost is low, the recovery is easy, and the environment is friendly.
The preparation method of the catalyst for preparing the methacrolein by oxidizing the isobutene/tertiary butanol comprises the following steps:
and weighing a proper amount of precursor compound of bismuth, iron, cobalt, copper, magnesium and cesium ions according to the molar ratio in the formula, dissolving the precursor compound in a nitric acid solution, and adding a complexing agent after the solution is clear and transparent to complex the precursor compound with metal ions. After the complexing agent is completely dissolved, a certain amount of saccharide is added, and then a solution containing acrylamide monomer and methylene bisacrylamide is added. Each of the above steps was accompanied by stirring to allow the additive to be sufficiently dissolved. After the solution is mixed uniformly and clarified, the solution containing molybdenum salt is added. Finally, the resulting mixed solution is heated or an initiator is added to cause polymerization. And (3) putting the obtained gel into a constant temperature drying box for drying to form xerogel. The xerogel is crushed and calcined at a certain temperature to obtain a catalyst sample.
The metal ion precursor compounds include oxides, acids, bases, organic salts, inorganic salts or complexes thereof as known in the art.
The complexing agent comprises one or more of tartaric acid, citric acid, ethylenediamine tetraacetic acid (EDTA) and other common complexing agents.
The adding proportion of the complexing agent is 1 (0.1-10) of the total mole ratio of the complexing agent to the metal ions.
The saccharide includes glucose, fructose and other saccharide known in the art.
The polymerization method comprises thermal polymerization or adding an initiator such as ammonium persulfate and the like which are well known in the industry.
The calcination temperature is 400-600 ℃ and the time is 2-10 hours.
The reticular polyacrylamide gel has very small nano cavities, and the size of the cavities can be changed by adjusting the proportion of acrylamide to methylene bisacrylamide in the solution, which is the physical basis for controlling the particle size of the catalyst. Micro-solution containing metal ions and crystals are formed in the nanometer cavity, and the metal ions are combined with-NH on the main chain and side chain of the polyacrylamide 2 Complexing, thereby being separated and fixed in the nano cavity, and the metal is separated by the existence of the complexing agentThe crystallization of the seed is more uniform and controllable. The amide bond is slowly hydrolyzed under the catalysis of copper ions and the like in the solution, so that the pH of a dispersion system is slowly increased, and meanwhile, the movement of an active component in the solution is effectively limited due to the increase of the viscosity of the solution due to the generation of polyacrylamide gel, so that the possibility of agglomeration of catalyst particles in the drying process is reduced.
The existence of the carbohydrate substance can lead the carbohydrate substance to provide a carbon skeleton to support the catalyst in the early stage of roasting, and simultaneously, a large amount of gas is generated during the roasting to lead the inside of the catalyst to form abundant micro-channels.
And drying and calcining the polyacrylamide gel at a proper temperature to obtain the catalyst powder. At higher temperature, the organic matters in the xerogel are burnt to generate a large amount of gas, and finally the catalyst nano powder is prepared. And (5) forming to obtain the formed catalyst.
The added polymer monomer, complexing agent, saccharide and cross-linking agent (methylene bisacrylamide) are decomposed in the roasting process, the element composition of the catalyst is not affected, but the most important function of the catalyst is to make the prepared catalyst more uniform. All the prior patents are prepared by a simple coprecipitation method, are extremely uneven in the steps of drying and later, can ensure the yield in small-batch preparation in a laboratory, and have serious uneven color visible to naked eyes in industrialization.
The invention has the following effects:
(1) Simple operation, low equipment requirement and no need of harsh physical environment in the preparation process. Low cost and cheap raw materials.
(2) The reactants can be uniformly mixed in the liquid phase to obtain a uniform multi-component dispersion system, which is convenient for controlling the chemical components of the powder.
(3) The agglomeration of the powder is effectively reduced, and the metal cations can be separated in the nanometer cavities by the high molecular structure of the gel, so that the agglomeration phenomenon of the powder in the calcination process of the gel is further reduced.
(4) The powder has fine particle size and controllable morphology, and can be used for preparing various nano materials such as spherical, diamond-shaped and porous particles.
(5) Pore formation is carried out in the roasting process, so that the specific surface area is increased.
The catalyst prepared by the method improves the conversion rate and the selectivity, ensures that the uniformity of the mixture in the preparation process is easier to control, and is beneficial to large-scale production.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the examples are all commercially available.
The catalyst is used or evaluated by mixing isobutene or tertiary butanol and a diluting gas containing oxygen (such as air, nitrogen, water vapor and the like according to any proportion required) and then reacting the mixture by a fixed bed filled with a formed catalyst under certain conditions: the temperature is 250-500 ℃, preferably 320-420 ℃; the pressure is 0.01-0.2MPa; the total airspeed of the mixed gas of the reaction raw materials is 500-3000h -1 Preferably 800-2000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume fraction of isobutene or tert-butanol is from 1 to 15%, preferably from 3 to 10%; the molar ratio of oxygen to isobutene or tert-butanol is from 1 to 10, preferably from 1.5 to 4; the molar ratio of water vapor to isobutene or tert-butanol is from 1 to 10, preferably from 2 to 6. And obtaining performance data through online gas chromatography analysis.
The raw material conversion and MAL selectivity during the reaction were calculated as follows:
example 1
12.6g of pentahydrate are added at 50 DEG CBismuth nitrate, 16.9g ferric nitrate nonahydrate, 12.2g cobalt nitrate hexahydrate, 12.4g copper nitrate hexahydrate, 5.38g magnesium nitrate hexahydrate and 2.72g cesium nitrate are dissolved in 100mL of 5% nitric acid solution, 25g tartaric acid is added after the solution is clear and transparent, 10g glucose is added after the tartaric acid is completely dissolved, the concentration of sugar in the added system is 0.1g/mL, then 350mL solution containing 278g acrylamide and 62g methylenebisacrylamide is added, stirring is carried out in each step so as to fully dissolve the additive, after the solution is uniformly mixed, 150mL solution containing 50g ammonium heptamolybdate tetrahydrate is added after the solution is clarified, finally, the obtained mixed solution is heated to 80 ℃ so as to enable the solution to be slowly converted into gel, the obtained gel is placed into a constant-temperature drying oven for drying, the xerogel is ground into fine powder, and calcination is carried out at 500 ℃ for 6 hours, thus obtaining a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 1.8 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Example 2
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added, the sugar concentration in the system after the addition was 0.1g/mL, then 350mL of a solution containing 278g of acrylamide and 62g of methylenebisacrylamide was added, each step was accompanied by stirring to sufficiently dissolve the additives, after the solution was uniformly mixed, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, the resulting mixed solution was heated to 80℃to cause polymerization reaction, after the solution was slowly converted into a gel, the obtained gel was dried in a constant temperature oven to form a xerogel, the xerogel was ground into fine powder, and calcined at 500℃for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 360 ℃, and the space velocity is 1000h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Example 3
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 12.4g of copper nitrate, 10.75g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added, the sugar concentration in the system after the addition was 0.1g/mL, then 350mL of a solution containing 278g of acrylamide and 124g of methylenebisacrylamide was added, each step was accompanied by stirring to sufficiently dissolve the additives, after the solution was uniformly mixed, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, the resulting mixed solution was heated to 80℃to cause polymerization reaction, after the solution was slowly converted into a gel, the obtained gel was dried in a constant temperature oven to form a xerogel, the xerogel was ground into fine powder, and calcined at 500℃for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 1.8 Mg 1.8 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Example 4
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and after the solution is clear and transparent, 32g of citric acid is added. After the citric acid was completely dissolved, 10g of glucose was added, the sugar concentration in the system after the addition was 0.1g/mL, then 350mL of a solution containing 278g of acrylamide and 124g of methylenebisacrylamide was added, each of which was stirred with sufficient dissolution of the additives, and after the solution was mixed well, 150m was added after clarificationL solution containing 50g of ammonium heptamolybdate, finally, heating the obtained mixed solution to 80 ℃ to cause polymerization reaction, slowly converting the solution into gel, placing the obtained gel into a constant temperature drying oven to be dried to form xerogel, grinding the xerogel into fine powder, and calcining at 500 ℃ for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Example 5
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and 48g of EDTA is added after the solution is clear and transparent. After complete dissolution of EDTA, 10g of glucose was added, the sugar concentration in the system after addition was 0.1g/mL, then 350mL of a solution containing 278g of acrylamide and 62g of methylenebisacrylamide was added, each step was accompanied by stirring to sufficiently dissolve the additives, after the solution was mixed well, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, the resulting mixed solution was heated to 80℃to cause polymerization reaction, after the solution was slowly converted into a gel, the obtained gel was dried in a thermostatic oven to form a xerogel, the xerogel was ground into fine powder, and calcined at 500℃for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Example 6
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate, 2.72g of cesium nitrate are dissolved in 100mL of 5% at 50 DEG CTo the nitric acid solution, 25g of tartaric acid was added after the solution was clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added, the sugar concentration of the system after the addition was 0.1g/mL, then 350mL of a solution containing 138g of acrylamide and 31g of methylenebisacrylamide was added, each of which was accompanied by stirring, to sufficiently dissolve the additives, after the solution was uniformly mixed, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, 3g of ammonium persulfate was added to the resulting mixed solution to cause polymerization reaction, after the solution was slowly converted into a gel, the obtained gel was dried in a constant temperature oven to form a xerogel, the xerogel was ground into fine powder, and calcined at 500℃for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Example 7
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 24.4g of cobalt nitrate, 6.2g of copper nitrate, 7.78g of magnesium acetate and 2.72g of cesium nitrate are dissolved in 100mL of a 5% nitric acid solution at 50 ℃, and 150g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 3g of glucose was added, after the addition, the sugar concentration of the system was 0.03g/mL, and then 100mL of a solution containing 14.75g of bismuth acrylamide and 16g of methylenebisacrylamide was added, each of which was accompanied by stirring, to sufficiently dissolve the additive, after the solution was uniformly mixed, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, the resulting mixed solution was heated to 70℃to cause polymerization, after the solution was slowly converted into a gel, the obtained gel was dried in a constant temperature drying oven to form a xerogel, the xerogel was ground into fine powder, and calcined at 450℃for 2.5 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1. 8 Co 3.6 Cu 1.8 Mg 0.9 Cs 0.6 O x 。
The catalyst is pressed into tablets and then is put into a fixed stateBed reactor, feeding isobutene/tert-butanol, oxygen, nitrogen, water=1:2:9:4, space velocity 1000h at 370 ℃ -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Example 8
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 24.4g of cobalt nitrate, 6.2g of copper nitrate, 7.78g of magnesium acetate and 2.72g of cesium nitrate are dissolved in 100mL of a 5% nitric acid solution at 50 ℃, and 150g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 50g of glucose was added, the sugar concentration of the system after the addition was 0.5g/mL, and then 700mL of a solution containing 556g of acrylamide and 12g of methylenebisacrylamide was added, each of which was accompanied by stirring, to sufficiently dissolve the additives, after the solution was uniformly mixed, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, 3g of ammonium persulfate was added to the resulting mixed solution to cause polymerization reaction, after the solution was slowly converted into a gel, the obtained gel was dried in a constant temperature oven to form a xerogel, the xerogel was ground into fine powder, and calcined at 600℃for 10 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 3.6 Cu 1.8 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 370 ℃ and the space velocity is 1000h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 1
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃ and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added, followed by the addition of 350mL of a solution containing 278g of acrylamide and 62g of methylenebisacrylamide, each with stirring, to allow the additive to dissolve well, after the solution was mixed well, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, the resulting mixed solution was heated to 80℃to allow polymerization to occur, after the solution was slowly converted to a gel, the gel obtained was dried in a constant temperature oven to form a xerogel, andgrinding xerogel into fine powder, calcining at 500 deg.C for 6 hr to obtain catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 2
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added, followed by the addition of 350mL of a solution containing 278g of acrylamide and 62g of methylenebisacrylamide, each with stirring, to allow the additive to be sufficiently dissolved, after the solution was mixed well, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, the resulting mixed solution was heated to 80℃to allow polymerization to occur, after the solution was slowly converted into a gel, the gel obtained was dried in a constant temperature oven to form a xerogel, the xerogel was ground into a fine powder, and calcined at 500℃for 6 hours to give a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 3
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate and 2.72g of cesium nitrate are dissolved in 100mL of a 5% nitric acid solution at 50 ℃, and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added followed by a 350mL solution containing 278g of acrylamide and 62g of methylenebisacrylamide, each with stirring to allow the additive to dissolve well, after the solution was mixed well, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarificationHeating the mixed solution to 80deg.C to polymerize, slowly converting into gel, drying in a constant temperature oven to obtain xerogel, grinding xerogel into fine powder, and calcining at 500deg.C for 6 hr to obtain catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 4
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, 150mL of solution containing 50g of ammonium heptamolybdate is added after the solution is clear and transparent, and finally the obtained mixed solution is heated to 80 ℃ with stirring in each step, and the mixture is uniformly mixed. Drying the slurry in a constant temperature drying oven, removing the solvent, grinding the solid into fine powder, and calcining at 500 ℃ for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 5
Dissolving 12.6g bismuth nitrate, 16.9g ferric nitrate, 12.2g cobalt nitrate, 6.2g copper nitrate, 5.38g magnesium nitrate and 2.72g cesium nitrate in 100mL5% nitric acid solution at 50 ℃, adding 278g acrylamide and 62g methylene bisacrylamide into the solution after the solution is clear and transparent, stirring each step to dissolve the additive fully, adding 150mL ammonium heptamolybdate solution after the solution is evenly mixed, finally, heating the obtained mixed solution to 80 ℃ to cause polymerization reaction, and obtainingThe solution is slowly converted into gel, the obtained gel is put into a constant temperature drying oven to be dried to form xerogel, the xerogel is ground into fine powder and calcined at 500 ℃ for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 360 ℃, and the space velocity is 1000h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 6
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, then 350mL of a solution containing 278g of acrylamide and 62g of methylenebisacrylamide was added, each with stirring, to allow the additive to be sufficiently dissolved, after the solution was uniformly mixed, 150mL of a solution containing 50g of ammonium heptamolybdate was added after clarification, finally, the resulting mixed solution was heated to 80℃to allow polymerization to occur, after the solution was slowly converted into a gel, the obtained gel was dried in a thermostatic oven to form a xerogel, the xerogel was ground into fine powder, and calcined at 500℃for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 7
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added followed by a 350mL solution containing 278g of acrylamideStirring to dissolve the additive, clarifying, adding 150mL of 50g ammonium heptamolybdate solution, heating to 80deg.C to polymerize, slowly converting into gel, drying in a constant temperature oven to obtain xerogel, grinding into fine powder, calcining at 500deg.C for 6 hr to obtain catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
Comparative example 8
12.6g of bismuth nitrate, 16.9g of ferric nitrate, 12.2g of cobalt nitrate, 6.2g of copper nitrate, 5.38g of magnesium nitrate and 2.72g of cesium nitrate are dissolved in 100mL of 5% nitric acid solution at 50 ℃, and 25g of tartaric acid is added after the solution is clear and transparent. After the tartaric acid was completely dissolved, 10g of glucose was added followed by 350mL of a solution containing 5% polyacrylamide. And (5) uniformly mixing the mixture. Placing the slurry into a constant temperature drying oven for drying, grinding into fine powder, and calcining at 500 ℃ for 6 hours to obtain a catalyst sample Mo 12 Bi 1.1 Fe 1.8 Co 1.8 Cu 0.9 Mg 0.9 Cs 0.6 O x 。
The catalyst is loaded into a fixed bed reactor after being pressed into tablets, and is fed according to the ratio of isobutene/tertiary butanol to oxygen to nitrogen to water=1:2:9:4 at 350 ℃, and the space velocity is 1200h -1 Analysis was performed by on-line chromatography. The results are shown in Table 1.
TABLE 1 catalytic Properties of catalysts for the Selective Oxidation of isobutylene/t-butanol to methacrolein
Experiments prove that copper and magnesium have synergistic effect on improving the activity and selectivity of the catalyst. The catalyst activity and yield can be improved even without changing the composition of the catalyst elements by a novel preparation method of adding complexing agent, saccharide, acrylamide and cross-linking agent in a certain proportion and polymerizing under proper conditions. And the preparation process is more stable, the uniformity is high, the repeatability is better, and the batch production is facilitated.

Claims (11)

1. A catalyst for the preparation of methacrolein in a fixed bed, characterized in that:
the composition of the catalyst is as follows: mo (Mo) a Bi b Fe c Co d Cu e Mg f Cs g O x
Wherein a-x are the atomic mole ratio of each element;
a＝12,0<b<3.5,0<c<3,0<d<8,0<e<3,0<f<3,0<g<2；
x is the number of oxygen atoms required to form the composite oxide;
the catalyst is prepared by a method comprising the following steps:
(1) Weighing a precursor compound of bismuth, iron, cobalt, copper, magnesium and cesium ions according to the molar ratio, dissolving the precursor compound in an acid solution, and adding a complexing agent to complex the solution with metal ions after the solution is clear and transparent;
(2) After the complexing agent is completely dissolved, adding saccharide substances, and then adding a solution containing acrylamide monomers and methylene bisacrylamide;
(3) After the solution is uniformly mixed and clarified, adding a solution containing molybdenum salt;
(4) Heating the obtained mixed solution or adding an initiator to perform polymerization reaction to obtain gel; drying, crushing and roasting to obtain the catalyst.
2. A process for preparing the catalyst of claim 1, said process comprising:
(1) Weighing a precursor compound of bismuth, iron, cobalt, copper, magnesium and cesium ions according to the molar ratio, dissolving the precursor compound in an acid solution, and adding a complexing agent to complex the solution with metal ions after the solution is clear and transparent;
(2) After the complexing agent is completely dissolved, adding saccharide substances, and then adding a solution containing acrylamide monomers and methylene bisacrylamide;
(3) After the solution is uniformly mixed and clarified, adding a solution containing molybdenum salt;
(4) Heating the obtained mixed solution or adding an initiator to perform polymerization reaction to obtain gel; drying, crushing and roasting to obtain the catalyst.
3. The method of manufacturing as claimed in claim 2, wherein:
step (1),
precursor compounds of bismuth, iron, cobalt, copper, magnesium, cesium ions are oxides, acids, bases, organic salts, inorganic salts or complexes thereof;
the complexing agent is one or a combination of tartaric acid, citric acid and ethylenediamine tetraacetic acid; and/or the number of the groups of groups,
the mole ratio of the complexing agent to the sum of bismuth, iron, cobalt, copper, magnesium and cesium ions is (0.1-10): 1.
4. a method of preparation as claimed in claim 3, wherein:
the mole ratio of the complexing agent to the sum of bismuth, iron, cobalt, copper, magnesium and cesium ions is (0.6-6): 1.
5. the method of manufacturing as claimed in claim 2, wherein:
step (2),
the saccharide is glucose and/or fructose; after the saccharide is added, the concentration of the saccharide in the system is 0.01-0.5 g/mL.
6. The method of manufacturing as claimed in claim 2, wherein:
step (2),
the mole ratio of the acrylamide to the sum of bismuth, iron, cobalt, copper, magnesium and cesium ions is (0.1-50): 1; and/or the number of the groups of groups,
the molar ratio of the methylene bisacrylamide to the acrylamide is (0.01-0.5): 1.
7. the method of manufacturing as claimed in claim 2, wherein:
the molar ratio of the acrylamide to the sum of bismuth, iron, cobalt, copper, magnesium and cesium ions is (10-40): 1.
8. the method of manufacturing as claimed in claim 2, wherein:
and (4) heating at 65-100 ℃.
9. The method of manufacturing as claimed in claim 2, wherein:
and (4) roasting at 400-600 ℃ for 2-10 hours.
10. A catalyst obtainable by the process of any one of claims 2 to 9.
11. Use of the catalyst according to claim 1 or the catalyst obtained by the process according to any one of claims 2 to 8 for the preparation of methacrolein by oxidation of isobutylene/t-butanol.
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