CN116237044A - Ammonia oxidation catalyst, preparation method and application thereof - Google Patents
Ammonia oxidation catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an ammoxidation catalyst and a preparation method and application thereof, wherein the ammoxidation catalyst belongs to a V-Rh system catalyst, and the stoichiometric ratio of V to Rh in an active component is precisely limited to 1.0 (0.05-5), and the stoichiometric ratio of B-class, C-class and D-class metal elements is limited, so that the ammoxidation catalyst not only can improve the selectivity of a product, reduce the deep oxidation degree of raw materials, improve the conversion rate of the raw materials and reduce the waste of the raw materials, but also has higher stability and mechanical strength, is suitable for large-scale industrial production and application, and is particularly suitable for application in the preparation of isophthalonitrile by m-xylene ammoxidation.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an ammonia oxidation catalyst, a preparation method and application thereof.
Background
The aromatic nitrile has high chemical activity, can be synthesized into various fine chemical products through hydrogenation and condensation reaction, and has been widely applied to various industries such as medicines, spices, pesticides, resins and the like. The aromatic nitrile is used as an important raw material source, and the demand at home and abroad has been growing in recent years, and the synthesis principle is that the aromatic nitrile cyano is obtained by oxidizing aromatic hydrocarbon ammonia under the conditions of ammonia and a catalyst. Because the manufacturing process has the advantages of simple operation, safe operation, high yield, small pollution and the like, a great deal of research is put into the process by a plurality of students at home and abroad so as to achieve wide application.
In the fifties of the twentieth century, allied corporation began to develop aromatic ammoxidation techniques. Meanwhile, there are also many companies, such as Distiller, bayer company, etc., and researches on related ammoxidation catalysts have been started. In 1969, japanese catalyst chemical industry company built a device for producing phthalonitrile and benzonitrile by mixed aromatic hydrocarbon ammoxidation method using its own developed technology. In 1970, a company in japan and a company in the united states co-operate to build an isophthalonitrile production plant. After that, mitsubishi gas chemistry in Japan has been successfully combined with Bagder company in U.S.A.to build an industrial apparatus for producing isophthalonitrile, so that aromatic hydrocarbon ammoxidation technology has been popularized and applied.
CN106268890A discloses an aromatic hydrocarbon ammoxidation mixed catalyst V 1.0 Cr a A b B c C d M e O x Wherein A is at least one selected from P, B, bi, sb, as elements; b is selected from at least one of Mn, ni, co, ti, sn, mo or rare earth elements; c is at least one selected from alkali metals or alkaline earth metals; m is selected from at least one of Zr and W. The attrition resistance of the catalyst described in this patent is optimized, with an attrition rate reduced by about 22% compared to the comparative catalyst in the literature.
CN106362760A discloses an ammoxidation mixed catalyst V 1.0 Cr a A b B c C d D e E f M g O x Wherein A is selected from at least one element of group IIIA of the periodic Table; b is at least one element selected from group VA of the periodic Table of elements; c is at least one element selected from alkali metals or alkaline earth metals; d is selected fromAt least one element of group VIII of the periodic Table of elements; e is at least one of Mo, ti and Nb; m is selected from at least one of Zr and W. The method effectively improves the wear resistance of the catalyst, and simultaneously maintains the high activity and selectivity of the catalyst, and the obtained catalyst can be applied to industrial production of aromatic hydrocarbon ammoxidation.
CN102218334B discloses an ammoxidation catalyst V containing antimony 1.0 Sb a A b B c C d O x Wherein A is at least one selected from lithium, sodium, potassium, rubidium or cesium; b is at least one selected from magnesium, calcium, barium, chromium, tungsten, molybdenum, manganese, iron, cobalt, nickel or tin; c is at least one selected from boron or phosphorus, and the catalyst well solves the problems that the catalyst is difficult to adapt to the requirements of a fluidized bed, the cost of raw materials is high and the like in the prior art, and can be used for industrial production.
In summary, the abrasion resistance and the raw material cost of the ammoxidation catalyst are optimized in the prior art, but the technical scheme of reducing the deep oxidation degree of the reaction raw material and the selectivity of small molecular products such as carbon dioxide and carbon monoxide is not mentioned, so that the development of a novel ammoxidation catalyst and a preparation method thereof are needed at present, which not only can improve the selectivity of the products, reduce the deep oxidation degree of the raw material, improve the conversion rate of the raw material and reduce the waste of the raw material, but also can improve the stability and the mechanical strength of the ammoxidation catalyst, and are suitable for large-scale industrial production and application.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ammonia oxidation catalyst, a preparation method and application thereof, and the ammonia oxidation catalyst belongs to a V-Rh system catalyst, can improve the selectivity of a product, reduce the deep oxidation degree of raw materials, improve the conversion rate of the raw materials and reduce the waste of the raw materials, has higher stability and mechanical strength, and is suitable for large-scale industrial production and application, in particular to application in the preparation of m-phthalonitrile by m-xylene ammonia oxidation.
It is an object of the present invention to provide an ammoxidation catalyst comprising a carrier and an active component in atomsThe ratio calculation satisfies the following structural formula: v (V) 1.0 Rh a B b C c D d O x ；
Wherein B is selected from any one or a combination of at least two of Sc, mn, ga or Mo, C is selected from any one or a combination of at least two of Zr, Y, tc or Ag, and D is selected from any one or a combination of at least two of As, bi, P or Sb;
a=0.05 to 5, b=0.01 to 2, c=0.001 to 1, d=0.001 to 1, x=2.0 to 9.0, and x is a value determined by the oxidation degree of other elements.
The ammonia oxidation catalyst belongs to a V-Rh system catalyst, and by accurately limiting the stoichiometric ratio of V to Rh in an active component to 1.0 (0.05-5) and limiting the stoichiometric ratio of B metal elements, an effective composite reaction active site can be formed, so that the active component and a carrier form a synergistic reaction active site, the activation energy of ammonia oxidation reaction is effectively reduced, the adsorption capacity of ammonia gas is improved, the deep oxidation degree of raw materials such as m-xylene is reduced, the generation of small molecular products is reduced, and the conversion rate and the product selectivity of the raw materials such as m-xylene are ensured.
Furthermore, the ammonia oxidation catalyst can effectively ensure the stability and mechanical strength of the ammonia oxidation catalyst and ensure the stability of the ammonia oxidation catalyst in the long-period running process by precisely limiting the stoichiometric ratio of the C-class metal element to the D-class metal element in the active component.
It is noted that in the above formula V 1.0 Rh a B b C c D d O x In a=0.05 to 5, for example, 0.05, 0.1, 0.3, 0.5, 0.7, 1, 1.5, 2, 3, 3.5, 4, or 5, etc., b=0.01 to 2, for example, 0.01, 0.03, 0.05, 0.08, 0.1, 0.3, 0.5, 0.7, 1, 1.3, 1.5, 1.7, or 2, etc., c=0.001 to 1, for example, 0.001, 0.003, 0.005, 0.008, 0.01, 0.03, 0.05, 0.08, 0.1, 0.3, 0.5, or 1, etc., d=0.001 to 1, for example, 0.001, 0.003, 0.005, 0.008, 0.01, 0.03, 0.05, 0.08, 0.1, 0.3, 0.5, or 1, etc., but the above numerical values are not limited to the above-mentioned ranges, and other numerical values are not applicable.
As a preferred embodiment of the present invention, in the structural formula V 1.0 Rh a B b C c D d O x In a=0.08 to 3, for example, 0.08, 0.15, 0.35, 0.65, 0.85, 1.2, 1.8, 2.3, 2.5, 2.8, or 3, etc., b=0.05 to 1, for example, 0.05, 0.07, 0.11, 0.15, 0.25, 0.45, 0.65, 0.85, 0.9, or 1, etc., c=0.05 to 0.8, for example, 0.05, 0.06, 0.07, 0.09, 0.12, 0.2, 0.4, 0.6, or 0.8, etc., d=0.01 to 0.5, for example, 0.01, 0.02, 0.04, 0.06, 0.09, 0.12, 0.15, 0.23, 0.35, 0.45, or 0.5, etc., but the present invention is not limited to the above-listed values, and other values not specifically stated in the above numerical ranges are equally applicable.
As a preferable technical scheme of the invention, the mass percentage of the active components is 20-70% based on the total mass of the ammoxidation catalyst, and the balance is the carrier.
It is to be noted that the active component of the present invention is present in an amount of 20 to 70% by mass, for example, 20%, 30%, 40%, 50%, 60% or 70% by mass, etc., but is not limited to the values recited, and other values not recited in the above-mentioned ranges are equally applicable.
Preferably, the carrier is MFI structure molecular sieve, belonging to the artificial synthesis of Al 2 O 3 /SiO 2 The molecular sieve has a double-ten-membered ring cross pore structure.
Preferably, the carrier is Al 2 O 3 /SiO 2 Molecular sieve, silica-alumina ratio (SiO 2 The molar ratio to Al) is 1 (0.001 to 0.1), for example, 1:0.001, 1:0.005, 1:0.01, 1:0.03, 1:0.05, 1:0.07, 1:0.1, etc., preferably 1 (0.005 to 0.07), for example, 1:0.005, 1:0.007, 1:0.009, 1:0.02, 1:0.04, 1:0.06, 1:0.07, etc., but the present invention is not limited to the recited values, and other non-recited values within the above-recited values are equally applicable.
It is a second object of the present invention to provide a method for producing the ammoxidation catalyst as one of the objects, comprising the steps of:
(1) Preparing an aqueous solution containing each metal element according to the structural formula of an active component in the ammoxidation catalyst, and mixing the aqueous solution with an oxalic acid aqueous solution to form a reaction solution A;
(2) Mixing the reaction solution A in the step (1) with a reaction solution B containing a carrier or a carrier-containing compound to form an impregnation mixed solution;
(3) And (3) sequentially evaporating, concentrating, drying and roasting the impregnating mixed solution in the step (2) to obtain the ammonia oxidation catalyst.
The preparation method of the ammonia oxidation catalyst comprises the steps of preparing a reaction liquid A according to a structural formula of an active component, mixing the reaction liquid A and the reaction liquid B, impregnating solid components in the reaction liquid A, and sequentially evaporating, concentrating, drying and roasting the obtained impregnating mixed liquid to obtain the ammonia oxidation catalyst.
As a preferable technical scheme of the invention, the preparation method of the reaction liquid B in the step (2) comprises the following steps:
and mixing an aluminum source and a silicon source to obtain a first mixed solution, mixing the first mixed solution with an auxiliary agent to obtain a second mixed solution, and aging to obtain the reaction solution B.
It is worth to say that the reaction solution B containing the carrier or the compound containing the carrier belongs to self-made slurry, and an auxiliary agent is added to control the size of the orifice in the carrier, so that the target raw material can enter the hole to combine with the reactive phase in the ammonia oxidation catalytic reaction process.
As a preferred embodiment of the present invention, the aluminum source comprises sodium metaaluminate and/or aluminum sulfate.
Preferably, the silicon source comprises ethyl orthosilicate and/or a silica sol.
Preferably, the silicon to aluminum ratio (SiO 2 Molar ratio to Al) is 1 (0.001-0.1), such as 1:0.001, 1:0.005, 1:0.008, 1:0.01, 1:0.03, 1:0.05, 1:0.07, 1:0.09, or 1:0.1, etc., preferably 1 (0.005-0.07), such as 1:0.005, 1:0.007, 1:0.009, 1:0.015, 1:0.02, 1:0.04, 1:0.06, or 1:0.07, etc., but is not limited to the listThe values recited above are equally applicable to other values not recited in the above ranges.
It is worth to say that the reaction liquid B containing the carrier or the compound containing the carrier belongs to self-made slurry, and Al in the carrier can be accurately regulated by accurately regulating the silicon-aluminum ratio of the reaction liquid B to 1 (0.001-0.1) 2 O 3 The content of the carrier is regulated, so that the acid amount of the carrier is regulated, and more ammonia adsorption sites are provided for subsequent ammonia oxidation reaction. If the silicon-aluminum ratio is higher than the selected range of the patent, the acid position is insufficient, the adsorption capacity to ammonia is insufficient, and the effect of reducing the oxidation degree of the dimethylbenzene cannot be achieved; if the silicon-aluminum ratio is lower than the range selected by the patent, the strong acid sites are increased, so that ammonia is excessively adsorbed, and ammonia oxidation reaction with dimethylbenzene is difficult to carry out, so that the degree of deep oxidation of added dimethylbenzene to generate carbon dioxide is increased.
Preferably, the auxiliary comprises any one of glycerol, an organic amine or a quaternary ammonium salt, preferably glycerol.
It is worth to say that the reaction liquid B containing carrier or carrier-containing compound of the invention belongs to self-made slurry, and by adding glycerol as an auxiliary agent, the reaction liquid B can be prepared for SiO by virtue of the advantages of stronger intermolecular hydrogen bonding force and stronger dipole moment of glycerol 2 The pore-enlarging modification and acid position increase have good auxiliary effects, the size of the pore opening in the carrier can be effectively controlled to be equivalent to the kinetic diameter (about 0.6 nm) of benzene molecules, namely, the shape selectivity is improved, the adsorptivity to ammonia gas is enhanced, the selectivity of aromatic products is improved, and the deep oxidation degree of raw materials is reduced.
Preferably, the molar ratio of the auxiliary agent to the silicon element in the silicon source is 0.1 to 30, for example 0.1, 0.5, 1, 3, 5, 8, 10, 15, 20, 25 or 30, etc., preferably 0.5 to 20, for example 0.5, 1.5, 2, 4, 7, 9, 11, 13, 16, 18 or 20, etc., but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the aging treatment is performed for a period of time ranging from 6 to 24 hours, for example, from 6 hours, 12 hours, 18 hours, or 24 hours, and the like, preferably from 8 to 20 hours, for example, from 8 hours, 9 hours, 10 hours, 11 hours, 13 hours, 14 hours, 15 hours, 17 hours, 19 hours, or 20 hours, and the like, but the aging treatment is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
The aging treatment is preferably carried out at a temperature of 40 to 120 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, or the like, preferably 50 to 100 ℃, for example, 50 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 95 ℃, or 100 ℃, or the like, but the aging treatment is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
In a preferred embodiment of the present invention, the temperature of the evaporation concentration in the step (3) is 40 to 100 ℃, for example 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or 100 ℃, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
Preferably, the concentration by evaporation in the step (3) yields a slurry liquid having a solid content of 35 to 75%, and the solid content may be 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%, etc., but is not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
As a preferred embodiment of the present invention, the drying in the step (3) is spray drying.
Preferably, the spray-drying has an inlet temperature of 180 to 280 ℃, for example 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 280 ℃, or the like, and an outlet temperature of 110 to 180 ℃, for example 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, or 180 ℃, or the like, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
In a preferred embodiment of the present invention, the temperature rising rate of the baking in the step (3) is 1 to 10 ℃/min, for example, 1 ℃/min, 3 ℃/min, 5 ℃/min, 7 ℃/min or 10 ℃/min, etc., preferably 2 to 6 ℃/min, for example, 2 ℃/min, 2.5 ℃/min, 3.5 ℃/min, 4.5 ℃/min, 5.5 ℃/min or 6 ℃/min, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are applicable.
Preferably, the firing of step (3) includes a primary firing and a secondary firing.
The primary baking temperature is preferably 120 to 170 ℃, for example 120 ℃ to 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, or the like, and preferably 120 to 150 ℃, for example 120 ℃, 125 ℃, 135 ℃, 145 ℃, 150 ℃, or the like, but is not limited to the recited values, and other values not recited in the above-mentioned numerical ranges are equally applicable.
Preferably, the primary roasting time is 3 to 12 hours, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc., but not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
The temperature of the secondary baking is preferably 600 to 750 ℃, for example 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃, 750 ℃, or the like, preferably 620 to 700 ℃, for example 620 ℃, 640 ℃, 660 ℃, 670 ℃, or 700 ℃, or the like, but is not limited to the recited values, and other values not recited in the above-mentioned numerical ranges are equally applicable.
Preferably, the secondary roasting time is 4 to 10 hours, for example, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, etc., but the secondary roasting time is not limited to the listed values, and other non-listed values in the above-mentioned value range are equally applicable.
It is a further object of the present invention to provide a process for producing isophthalonitrile, which comprises the following steps:
and (3) performing ammoxidation reaction on m-xylene ammonia and oxygen-containing gas under the action of the ammoxidation catalyst to obtain m-phthalonitrile by adopting the ammoxidation catalyst of one of the purposes or adopting the ammoxidation catalyst obtained by the two preparation methods of the two purposes.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The ammonia oxidation catalyst belongs to a V-Rh system catalyst, and is suitable for large-scale industrial production and application, in particular for the application in the preparation of isophthalonitrile by oxidizing m-xylene ammonia by accurately limiting the stoichiometric ratio of V to Rh in an active component to 1.0 (0.05-5) and limiting the stoichiometric ratio of B, C and D metal elements, so that the selectivity of a product can be improved, the deep oxidation degree of the raw material can be reduced, the conversion rate of the raw material can be improved, the waste of the raw material can be reduced, and the stability and the mechanical strength can be higher;
(2) The carrier in the ammoxidation catalyst is self-made micron Al 2 O 3 /SiO 2 The Al in the carrier can be accurately regulated by accurately regulating the silicon-aluminum ratio of the reaction liquid B to be 1 (0.001-0.1) in the preparation process of the type molecular sieve 2 O 3 The content is regulated, so that the acid amount of the carrier is regulated, and more ammonia adsorption sites are provided for the subsequent ammonia oxidation reaction;
(3) The carrier in the ammoxidation catalyst is self-made micron Al 2 O 3 /SiO 2 The molecular sieve can be used for SiO with the help of the advantages of stronger hydrogen bonding force between glycerol molecules and stronger dipole moment by adding glycerol and the like as auxiliary agents 2 The pore-enlarging modification and acid position increase have good auxiliary effects, the size of the pore opening in the carrier can be effectively controlled to be equivalent to the kinetic diameter (about 0.6 nm) of benzene molecules, namely, the shape selectivity is improved, the adsorptivity to ammonia gas is enhanced, the selectivity of aromatic products is improved, and the deep oxidation degree of raw materials is reduced.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The starting materials used in the examples were all conventional in the art and were AR grade in purity specification.
In the examples, the calculation formulas of the conversion of raw meta-xylene and the selectivity of target meta-phthalonitrile are as follows:
meta-xylene conversion (%) = (moles of meta-xylene reacted/moles of meta-xylene fed) ×100%;
isophthalonitrile selectivity (%) = (mole number of isophthalonitrile produced/mole number of m-xylene reacted) ×100%.
Example 1
The embodiment provides an ammoxidation catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) 66.04g of oxalic acid is added into 202g of hot water at 85 ℃ to form oxalic acid solution, 44.6g of vanadium pentoxide is slowly added into the oxalic acid solution according to the structural formula of active components in the ammoxidation catalyst, 6.354g of rhodium acetate, 4.8066g of ammonium molybdate, 10.528g of zirconium nitrate and 0.889g of arsenic chloride are respectively dissolved in 30g of water, 20g of water and 15g of water, and are added into the oxalic acid solution to be mixed to form reaction solution A;
(2) Adding a reaction solution B containing a carrier compound into the reaction solution A in the step (1) to form an impregnating mixed solution;
the preparation method of the reaction liquid B comprises the following steps: 2.49g NaAlO 2 Adding 95g of water, and stirring at normal temperature until the water is completely dissolved to form an aluminum source; adding an aluminum source into 303.4g of silica sol with the mass percentage content of 40%, mixing to obtain a first mixed solution, adding 53.176g of glycerol into the first mixed solution, mixing to obtain a second mixed solution, and aging at 80 ℃ for 12 hours to obtain a reaction solution B;
(3) Evaporating and concentrating the dipping mixed solution in the step (2) at the temperature of 85 ℃ until slurry feed liquid with the solid content of 60% is obtained; spray drying the obtained slurry feed liquid at the inlet temperature of 250 ℃ and the outlet temperature of 170 ℃ to obtain a catalyst precursor; and (3) placing the obtained catalyst precursor in a muffle furnace, heating to 140 ℃ at a heating rate of 2 ℃/min, preserving heat for 4 hours, performing primary roasting, heating to 630 ℃ at a heating rate of 2 ℃/min, preserving heat for 5 hours, performing secondary roasting, and finally cooling to room temperature to obtain the ammonia oxidation catalyst 1#.
The proportion of active components in the ammonia oxidation catalyst 1# is detected to be V 1.0 Rh 0.08 Mo 0.05 Zr 0.05 As 0.01 O 2.895 。
The ammoxidation catalyst 1# obtained above was charged into a laboratory ammoxidation fluidized-bed reactor to evaluate the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:3.1:12, and the reaction temperature of the ammoxidation reactor is 370 DEG CThe reaction pressure (gauge pressure) was 36kPa, and the catalyst weight loading in the reactor was 0.032h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 99.8%, and the selectivity to isophthalonitrile was 99.6%.
Example 2
The embodiment provides an ammoxidation catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) 66.04g of oxalic acid is added into 202g of hot water at 85 ℃ to form oxalic acid solution, 44.6g of vanadium pentoxide is slowly added into the oxalic acid solution according to the structural formula of active components in the ammoxidation catalyst, 79.426g of rhodium acetate, 48.066g of ammonium molybdate, 84.221g of zirconium nitrate and 44.453g of arsenic chloride are respectively dissolved into 300g, 160g and 150g of water, and are added into the oxalic acid solution to be mixed to form reaction solution A;
(2) Adding a reaction solution B containing a carrier compound into the reaction solution A in the step (1) to form an impregnating mixed solution;
the preparation method of the reaction liquid B comprises the following steps: 0.166g NaAlO 2 Adding 95g of water, and stirring at normal temperature until the water is completely dissolved to form an aluminum source; adding an aluminum source into 303.4g of silica sol with the mass percentage content of 40%, mixing to obtain a first mixed solution, adding 53.176g of glycerol into the first mixed solution, mixing to obtain a second mixed solution, and aging at 70 ℃ for 10 hours to obtain a reaction solution B;
(3) Evaporating and concentrating the dipping mixed solution in the step (2) at the temperature of 85 ℃ until slurry feed liquid with the solid content of 60% is obtained; spray drying the obtained slurry feed liquid at the inlet temperature of 230 ℃ and the outlet temperature of 130 ℃ to obtain a catalyst precursor; and (3) placing the obtained catalyst precursor in a muffle furnace, heating to 150 ℃ at a heating rate of 2 ℃/min for 6h, performing primary roasting, heating to 660 ℃ at a heating rate of 2 ℃/min for 7h, performing secondary roasting, and finally cooling to room temperature to obtain the ammonia oxidation catalyst No. 2.
The proportion of active components in the ammonia oxidation catalyst 2# is detected to be V 1.0 Rh 1.0 Mo 0.5 Zr 0.4 As 0.5 O 7.55 。
The ammoxidation catalyst 2# obtained above was charged into a laboratory ammoxidation fluidized-bed reactor to evaluate the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:3.5:11, the reaction temperature of the ammoxidation reactor is 365 ℃, the reaction pressure (gauge pressure) is 27kPa, and the weight load of the catalyst in the reactor is 0.04h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 99.3%, and the selectivity of m-phthalonitrile was 99.1%.
Example 3
The embodiment provides an ammoxidation catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) 66.04g of oxalic acid is added into 202g of hot water at 85 ℃ to form oxalic acid solution, 44.6g of vanadium pentoxide is slowly added into the oxalic acid solution according to the structural formula of active components in the ammoxidation catalyst, 39.713g of rhodium acetate, 24.033g of ammonium molybdate, 42.111g of zirconium nitrate and 22.227g of arsenic chloride are respectively dissolved into 150g, 80g and 75g of water, and are added into the oxalic acid solution to be mixed to form reaction solution A;
(2) Adding a reaction solution B containing a carrier compound into the reaction solution A in the step (1) to form an impregnating mixed solution;
the preparation method of the reaction liquid B comprises the following steps: will 1.656g NaAlO 2 Adding 95g of water, and stirring at normal temperature until the water is completely dissolved to form an aluminum source; adding an aluminum source into 303.4g of silica sol with the mass percentage content of 40%, mixing to obtain a first mixed solution, adding 53.176g of glycerol into the first mixed solution, mixing to obtain a second mixed solution, and aging at 80 ℃ for 12 hours to obtain a reaction solution B;
(3) Evaporating and concentrating the dipping mixed solution in the step (2) at the temperature of 85 ℃ until slurry feed liquid with the solid content of 60% is obtained; spray drying the obtained slurry feed liquid at the inlet temperature of 240 ℃ and the outlet temperature of 160 ℃ to obtain a catalyst precursor; and (3) placing the obtained catalyst precursor in a muffle furnace, heating to 140 ℃ at a heating rate of 2 ℃/min, preserving heat for 5 hours, performing primary roasting, heating to 650 ℃ at a heating rate of 2 ℃/min, preserving heat for 6 hours, performing secondary roasting, and finally cooling to room temperature to obtain the ammonia oxidation catalyst 3#.
The proportion of active components in the ammonia oxidation catalyst 3# is detected to be V 1.0 Rh 0.5 Mo 0.25 Zr 0.2 As 0.25 O 5.025 。
The ammoxidation catalyst 3# obtained above was charged into a laboratory ammoxidation fluidized-bed reactor to evaluate the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:2.1:10.1, the reaction temperature of the ammoxidation reactor is 360 ℃, the reaction pressure (gauge pressure) is 29kPa, and the weight load of the catalyst in the reactor is 0.037h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 99.9%, and the selectivity to isophthalonitrile was 99.8%.
Example 4
The embodiment provides an ammoxidation catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) 66.04g of oxalic acid is added into 202g of hot water at 85 ℃ to form oxalic acid solution, 44.6g of vanadium pentoxide is slowly added into the oxalic acid solution according to the structural formula of active components in the ammoxidation catalyst, 3.97g of rhodium acetate, 12.016g of ammonium molybdate, 21.055g of zirconium nitrate and 11.113g of arsenic chloride are respectively dissolved into 75g of water, 40g of water and 40g of water, and are added into the oxalic acid solution to be mixed to form reaction solution A;
(2) Adding a reaction solution B containing a carrier compound into the reaction solution A in the step (1) to form an impregnating mixed solution;
the preparation method of the reaction liquid B comprises the following steps: 16.557g NaAlO 2 Adding 95g of water, and stirring at normal temperature until the water is completely dissolved to form an aluminum source; adding an aluminum source into 303.4g of silica sol with the mass percentage content of 40%, mixing to obtain a first mixed solution, adding 53.176g of glycerol into the first mixed solution, mixing to obtain a second mixed solution, and aging at 80 ℃ for 12 hours to obtain a reaction solution B;
(3) Evaporating and concentrating the dipping mixed solution in the step (2) at the temperature of 85 ℃ until slurry feed liquid with the solid content of 60% is obtained; spray drying the obtained slurry feed liquid at the inlet temperature of 250 ℃ and the outlet temperature of 170 ℃ to obtain a catalyst precursor; and (3) placing the obtained catalyst precursor in a muffle furnace, heating to 170 ℃ at a heating rate of 2 ℃/min, preserving heat for 5 hours, performing primary roasting, heating to 650 ℃ at a heating rate of 2 ℃/min, preserving heat for 6 hours, performing secondary roasting, and finally cooling to room temperature to obtain the ammonia oxidation catalyst 4#.
The proportion of active components in the ammonia oxidation catalyst 4# is detected to be V 1.0 Rh 0.1 Mo 0.125 Zr 0.1 As 0.125 O 3.5375 。
The ammoxidation catalyst 4# obtained above was charged into a laboratory ammoxidation fluidized-bed reactor to evaluate the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:3.8:13, the reaction temperature of the ammoxidation reactor is 365 ℃, the reaction pressure (gauge pressure) is 40kPa, and the weight load of the catalyst in the reactor is 0.042h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 99.7%, and the selectivity to isophthalonitrile was 99.4%.
Example 5
The embodiment provides an ammoxidation catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) 66.04g of oxalic acid is added into 202g of hot water at 85 ℃ to form oxalic acid solution, 44.6g of vanadium pentoxide is slowly added into the oxalic acid solution according to the structural formula of active components in the ammoxidation catalyst, 6.87g of rhodium acetate, 0.3135g of gallium nitrate, 0.00042g of silver nitrate and 0.0000048g of bismuth nitrate are respectively dissolved in 140g, 20g, 10g and 10g of water, and are added into the oxalic acid solution to be mixed to form reaction solution A;
(2) Adding a reaction solution B containing a carrier compound into the reaction solution A in the step (1) to form an impregnating mixed solution;
the preparation method of the reaction liquid B comprises the following steps: will 1.656g NaAlO 2 Adding 95g of water, and stirring at normal temperature until the water is completely dissolved to form an aluminum source; adding an aluminum source into 303.4g of silica sol with the mass percentage content of 40%, mixing to obtain a first mixed solution, adding 53.176g of glycerol into the first mixed solution, mixing to obtain a second mixed solution, and aging at 80 ℃ for 12 hours to obtain a reaction solution B;
(3) Evaporating and concentrating the dipping mixed solution in the step (2) at the temperature of 85 ℃ until slurry feed liquid with the solid content of 60% is obtained; spray drying the obtained slurry feed liquid at the inlet temperature of 250 ℃ and the outlet temperature of 170 ℃ to obtain a catalyst precursor; and (3) placing the obtained catalyst precursor in a muffle furnace, heating to 140 ℃ at a heating rate of 2 ℃/min, preserving heat for 4 hours, performing primary roasting, heating to 630 ℃ at a heating rate of 2 ℃/min, preserving heat for 5 hours, performing secondary roasting, and finally cooling to room temperature to obtain the ammonia oxidation catalyst No. 5.
The proportion of active components in the ammonia oxidation catalyst 5# is detected to be V 1.0 Rh 0.1 Ga 0.05 Ag 0.002 Bi 0.05 O 2.0003 55 。
The ammoxidation catalyst 5# obtained above was charged into a laboratory ammoxidation fluidized-bed reactor to evaluate the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:3.1:12, the reaction temperature of the ammoxidation reactor is 370 ℃, the reaction pressure (gauge pressure) is 36kPa, and the weight load of the catalyst in the reactor is 0.032h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 99.3%, and the selectivity of m-phthalonitrile was 99.1%.
Example 6
The embodiment provides an ammoxidation catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) 66.04g of oxalic acid is added into 202g of hot water at 85 ℃ to form oxalic acid solution, 44.6g of vanadium pentoxide is slowly added into the oxalic acid solution according to the structural formula of active components in the ammoxidation catalyst, 3.43g of rhodium acetate, 0.283g of scandium nitrate, 0.0023g of yttrium nitrate and 0.0000071g of 85wt% phosphoric acid are respectively dissolved in 140g, 20g and 10g of water, and are added into the oxalic acid solution to be mixed to form reaction solution A;
(2) Adding a reaction solution B containing a carrier compound into the reaction solution A in the step (1) to form an impregnating mixed solution;
the preparation method of the reaction liquid B comprises the following steps: 16.56g NaAlO was added 2 Adding 95g of water, and stirring at normal temperature until the water is completely dissolved to form an aluminum source; adding an aluminum source into 303.4g of silica sol with the mass percentage content of 40%, mixing to obtain a first mixed solution, adding 53.176g of glycerol into the first mixed solution, mixing to obtain a second mixed solution, and aging at 80 ℃ for 12 hours to obtain a reaction solution B;
(3) Evaporating and concentrating the dipping mixed solution in the step (2) at the temperature of 85 ℃ until slurry feed liquid with the solid content of 60% is obtained; spray drying the obtained slurry feed liquid at the inlet temperature of 250 ℃ and the outlet temperature of 170 ℃ to obtain a catalyst precursor; and (3) placing the obtained catalyst precursor in a muffle furnace, heating to 140 ℃ at a heating rate of 2 ℃/min, preserving heat for 4 hours, performing primary roasting, heating to 630 ℃ at a heating rate of 2 ℃/min, preserving heat for 5 hours, performing secondary roasting, and finally cooling to room temperature to obtain the ammonia oxidation catalyst No. 5.
The proportion of active components in the ammonia oxidation catalyst 5# is detected to be V 1.0 Rh 0.05 Sc 0.1 Y 0.005 P 0.01 O 3.98 。
The ammoxidation catalyst 5# obtained above was charged into a laboratory ammoxidation fluidized-bed reactor to evaluate the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:3.1:12, the reaction temperature of the ammoxidation reactor is 370 ℃, the reaction pressure (gauge pressure) is 36kPa, and the weight load of the catalyst in the reactor is 0.032h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 99.3%, and the selectivity of m-phthalonitrile was 99.2%.
Example 7
The embodiment provides an ammoxidation catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) 66.04g of oxalic acid is added into 202g of hot water at 85 ℃ to form oxalic acid solution, 44.6g of vanadium pentoxide is slowly added into the oxalic acid solution according to the structural formula of active components in the ammoxidation catalyst, and 34.335g of rhodium acetate, 2.12g of manganese acetate, 0.208g of silver nitrate and 0.018g of antimony acetate are respectively dissolved into 200g, 50g, 10g and 10g of water and added into the oxalic acid solution to be mixed to form reaction solution A;
(2) Adding a reaction solution B containing a carrier compound into the reaction solution A in the step (1) to form an impregnating mixed solution;
the preparation method of the reaction liquid B comprises the following steps: 16.56g NaAlO was added 2 Adding 95g of water, and stirring at normal temperature until the water is completely dissolved to form an aluminum source; adding an aluminum source into 303.4g of silica sol with the mass percentage content of 40%, mixing to obtain a first mixed solution, adding 53.176g of glycerol into the first mixed solution, mixing to obtain a second mixed solution, and aging at 80 ℃ for 12 hours to obtain a reaction solution B;
(3) Evaporating and concentrating the dipping mixed solution in the step (2) at the temperature of 85 ℃ until slurry feed liquid with the solid content of 60% is obtained; spray drying the obtained slurry feed liquid at the inlet temperature of 250 ℃ and the outlet temperature of 170 ℃ to obtain a catalyst precursor; and (3) placing the obtained catalyst precursor in a muffle furnace, heating to 140 ℃ at a heating rate of 2 ℃/min, preserving heat for 4 hours, performing primary roasting, heating to 630 ℃ at a heating rate of 2 ℃/min, preserving heat for 5 hours, performing secondary roasting, and finally cooling to room temperature to obtain the ammonia oxidation catalyst No. 5.
The proportion of active components in the ammonia oxidation catalyst 5# is detected to be V 1.0 Rh 0.5 Mn 0.1 Ag 0.1 Sb 0.05 O 4.16 。
The ammoxidation catalyst 5# obtained above was charged into a laboratory ammoxidation fluidized-bed reactor to evaluate the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:3.1:12, the reaction temperature of the ammoxidation reactor is 370 ℃, the reaction pressure (gauge pressure) is 36kPa, and the weight load of the catalyst in the reactor is 0.032h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 99.5%, and the selectivity to isophthalonitrile was 99.4%.
Comparative example 1
This comparative example provides an ammoxidation catalyst prepared according to the procedure of example 1 of patent CN106268890A having a composition of V 1 Cr 1 P 1 B 0.5 Mo 0.1 Co 0.1 K 0.05 W 0.1 Zr 0.02 /50wt％SiO 2 Catalyst 1-1#.
The ammoxidation catalysts 1-1# obtained above were charged into a laboratory ammoxidation fluidized-bed reactor for evaluation of the reaction performance, and the reaction raw material feed ratio was in accordance with meta-xylene: ammonia gas: the molar ratio of oxygen is 1:3.1:12, the reaction temperature of the ammoxidation reactor is 370 ℃, the reaction pressure (gauge pressure) is 36kPa, and the weight load of the catalyst in the reactor is 0.032h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 98.1%, and the selectivity to isophthalonitrile was 84.3%.
Comparative example 2
This comparative example provides an ammoxidation catalyst prepared according to the procedure of example 1 of patent CN102218334B having a composition of V 1 Sb 1 B 0.5 P 0.05 Mo 0.3 Na 0.05 /SiO 2 Catalyst 2-1#.
The ammoxidation catalyst 2-1# obtained above is put into a laboratory ammoxidation fluidized bed reactor for reaction performance evaluation, and the reaction raw material feed ratio is as follows: ammonia gas: the molar ratio of oxygen is 1:3.5:11, the reaction temperature of the ammoxidation reactor is 365 ℃, the reaction pressure (gauge pressure) is 27kPa, and the weight load of the catalyst in the reactor is 0.04h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 98.5%, and the selectivity to isophthalonitrile was 82.0%.
Comparative example 3
This comparative example provides an ammoxidation catalyst prepared according to the procedure of example 1 of patent CN106362760A having a composition of V 1.0 Cr 1.1 B 0.5 P 0.8 Nb 0.15 Co 0.1 K 0.05 W 0.125 Zr 0.025 /50wt％SiO 2 Catalyst 3-1#.
The ammoxidation catalyst 3-1# obtained above is put into a laboratory ammoxidation fluidized bed reactor for reaction performance evaluation, and the reaction raw material feed ratio is as follows: ammonia gas: the molar ratio of oxygen is 1:2.1:10.1, the reaction temperature of the ammoxidation reactor is 360 ℃, the reaction pressure (gauge pressure) is 29kPa, and the weight load of the catalyst in the reactor is 0.037h -1 。
After 200 hours of operation of the reactor, the conversion of m-xylene was 98.5%, and the selectivity to isophthalonitrile was 87.8%.
TABLE 1
In summary, the ammoxidation catalyst belongs to a V-Rh system catalyst, and by accurately limiting the stoichiometric ratio of V to Rh in the active component to 1.0 (0.05-5) and limiting the stoichiometric ratio of B, C and D metal elements, the ammoxidation catalyst not only can improve the selectivity of the product, reduce the deep oxidation degree of the raw materials, improve the conversion rate of the raw materials and reduce the waste of the raw materials, but also has higher stability and mechanical strength, is suitable for large-scale industrial production and application, and is particularly suitable for the application in the preparation of isophthalonitrile by the ammoxidation of m-xylene.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. An ammoxidation catalyst, characterized in that the ammoxidation catalyst comprises a carrier and an active component, wherein the active component meets the following structural formula in terms of atomic ratio: v (V) 1.0 Rh a B b C c D d O x ；
Wherein B is selected from any one or a combination of at least two of Sc, mn, ga or Mo, C is selected from any one or a combination of at least two of Zr, Y, tc or Ag, and D is selected from any one or a combination of at least two of As, bi, P or Sb;
a＝0.05～5，b＝0.01～2，c＝0.001～1，d＝0.001～1，x＝2.0～9.0。
2. the ammoxidation catalyst of claim 1, wherein in said formula V 1.0 Rh a B b C c D d O x In a=0.08 to 3, b=0.05 to 1, c=0.05 to 0.8, and d=0.01 to 0.5.
3. The ammoxidation catalyst according to claim 1 or 2, wherein the mass percentage of the active component is 20 to 70% based on the total mass of the ammoxidation catalyst, and the balance is a carrier;
preferably, the carrier is an MFI structure molecular sieve;
preferably, the carrier has a silica-alumina ratio of 1 (0.001 to 0.1), preferably 1 (0.005 to 0.07).
4. A process for preparing an ammoxidation catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Preparing an aqueous solution containing each metal element according to the structural formula of an active component in the ammoxidation catalyst, and mixing the aqueous solution with an oxalic acid aqueous solution to form a reaction solution A;
(2) Mixing the reaction solution A in the step (1) with a reaction solution B containing a carrier or a carrier-containing compound to form an impregnation mixed solution;
(3) And (3) sequentially evaporating, concentrating, drying and roasting the impregnating mixed solution in the step (2) to obtain the ammonia oxidation catalyst.
5. The method according to claim 4, wherein the method for preparing the reaction liquid B in the step (2) comprises the steps of:
and mixing an aluminum source and a silicon source to obtain a first mixed solution, mixing the first mixed solution with an auxiliary agent to obtain a second mixed solution, and aging to obtain the reaction solution B.
6. The method of claim 5, wherein the aluminum source comprises sodium metaaluminate and/or aluminum sulfate;
preferably, the silicon source comprises ethyl orthosilicate and/or a silica sol;
preferably, the silicon to aluminum ratio of the aluminum source to the silicon source is 1 (0.001 to 0.1), preferably 1 (0.005 to 0.07);
preferably, the auxiliary comprises any one of glycerol, organic amine or quaternary ammonium salt, preferably glycerol;
preferably, the molar ratio of the auxiliary agent to the silicon element in the silicon source is 0.1-30, preferably 0.5-20;
preferably, the aging treatment is carried out for a period of time ranging from 6 to 24 hours, preferably from 8 to 20 hours;
preferably, the temperature of the aging treatment is 40 to 120 ℃, preferably 50 to 100 ℃.
7. The method according to any one of claims 4 to 6, wherein the temperature of the evaporation concentration in step (3) is 40 to 100 ℃;
preferably, the evaporation concentration in the step (3) is carried out to obtain slurry feed liquid with the solid content of 35-75%.
8. The method of any one of claims 4-7, wherein the drying of step (3) is spray drying;
preferably, the inlet temperature of the spray drying is 180-280 ℃ and the outlet temperature is 110-180 ℃.
9. The method of any one of claims 4-8, wherein the firing in step (3) has a heating rate of 1-10 ℃/min, preferably 2-6 ℃/min;
preferably, the firing of step (3) includes a primary firing and a secondary firing;
preferably, the temperature of the primary roasting is 120-170 ℃, preferably 120-150 ℃;
preferably, the primary roasting time is 3-12 hours;
preferably, the temperature of the secondary roasting is 600-750 ℃, preferably 620-700 ℃;
preferably, the secondary roasting time is 4-10 hours.
10. A process for producing isophthalonitrile, which comprises the following steps:
an ammoxidation catalyst as claimed in any one of claims 1 to 3, or an ammoxidation catalyst obtained by the production process as claimed in any one of claims 4 to 9, wherein m-xylene ammonia gas and an oxygen-containing gas are subjected to ammoxidation under the action of the ammoxidation catalyst to obtain isophthalonitrile.
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