CN111167485A - Sulfide coated ammonia oxidation catalyst and preparation method and application thereof - Google Patents
Sulfide coated ammonia oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN111167485A CN111167485A CN202010013063.6A CN202010013063A CN111167485A CN 111167485 A CN111167485 A CN 111167485A CN 202010013063 A CN202010013063 A CN 202010013063A CN 111167485 A CN111167485 A CN 111167485A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- 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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Abstract
The invention provides a sulfide coated ammonia oxidation catalyst, a preparation method and an application thereof, wherein the ammonia oxidation catalyst comprises an active component and a carrier, and the active component satisfies the following structure in atomic ratio calculation: (MoS)2)aAsbGecSedSieXfYgOxWherein X is selected from one or more of La, Pr, Pm or Sm, and Y is selected from one or more of Ir, Pt, Rh or Ru(ii) a a is 0.1 to 30, b is 0.2 to 20, c is 0 to 2.5, d is 0 to 2.5, e is 10 to 90, f is 0.01 to 8, and g is 0.001 to 2; and (a + b)/e is more than 0.2 and less than 1.8, c + d is more than 0.01 and less than 5, and f/(c + d + g) is more than 5 and less than or equal to 80; x is determined by the degree of oxidation of the other elements; the catalyst has high conversion rate and selectivity and good stability in the reaction of preparing phthalonitrile by ammoxidation of xylene, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a sulfide coated ammoxidation catalyst, a preparation method thereof, and application of the catalyst in preparation of phthalonitrile by ammoxidation of xylene.
Background
Aromatic nitriles are fine chemicals with wide application, can synthesize a series of fine chemical products by utilizing reactions of cyano hydrogenation, addition, condensation, polymerization, hydrolysis, halogenation and the like, are important raw materials for manufacturing pesticides, medicines, dyes, spices, oil products, fuel additives and the like, and are also commonly used for producing polyester resins and polyester fibers. For example, tetrachloroisophthalonitrile synthesized by chlorination of isophthalonitrile is a broad-spectrum bactericide with high efficiency and low toxicity; m-xylylenediamine prepared by hydrogenation of m-phthalonitrile is an epoxy resin curing agent with better performance, and isocyanate and a high-barrier nylon material can be further produced at the downstream.
The aromatic nitrile can be produced by chemical synthesis, gas phase ammoxidation and other processes, at present, the synthesis of m-phthalonitrile or an isomer thereof by using xylene, ammonia and air through ammoxidation in one step is the simplest and economic production method, and the process core technology is the development of a catalyst and the selection of a corresponding reactor.
The xylene ammoxidation catalyst mainly has four systems of V-Cr, V-P, V-Sb and Sb-Fe, wherein the V-Cr system catalyst is widely applied due to the characteristics of easy amplification production, good batch stability and higher reaction activity. However, the V-Cr-based catalyst also has problems of deep oxidation, many side reactions, and large consumption of ammonia, and generates a large amount of CO and CO2HCN and the target product isophthalonitrile have low selectivity and yield, and a large optimization space exists.
Patent CN1268399A discloses a fluidized bed catalyst V for preparing isophthalonitrile by m-xylene ammoxidation1.0CraAbBcCdOxWherein A is selected from P, B or an oxide of As; b is at least one oxide selected from Li, Na, K or Cs; c is selected from Mn, Mg, Sb, Pb, Fe, Mo, W or rare earth elements, and mainly solves the defects that the catalyst is difficult to adapt to the requirements of a fluidized bed or expensive raw materials are used or the reaction selectivity is poor. Japanese patent Japanese Kokoku publication Sho-61-4388 discloses a V-Cr-Ba/SiC catalyst in which the yield of phthalonitrile is 54%. Japanese patent Showa 45-19051 discloses a V-Cr-Mo/Al alloy2O3The yield of the catalyst, namely the isophthalonitrile, is 79.8%. Japanese patent No. Sho 47-34337 discloses a V-Cr-P/SiO2The yield of m-phthalonitrile as a catalyst was 54.0%. Japanese patent Showa 45-19050 discloses a V-Cr-Pb/Al alloy2O3The yield of the catalyst, namely the isophthalonitrile, is 79.3%. Japanese patent Showa 45-20893 discloses a V-Cr-Co/Al alloy2O3The yield of the catalyst, isophthalonitrile, was 78.6%.
U.S. Pat. No. 6,444,330 discloses an aromatic ammoxidation catalyst VaMobFecXdYeOfWherein X is selected from Mg, Ca, Ba, La, Ti, Zr, Cr, W, Co and Ni; y is selected from B, Al, Ge, Sn, Pb, P, Sb and Bi, and the catalyst has a preferred attrition index of about 2.1%. Patent CN103896807 discloses a fine particle fluidized bed catalyst V for producing terephthalonitrile1.0CraPbXcYdZeOmWherein X is selected from at least one of oxides of boron or arsenic; y is at least one of alkali metal or alkaline earth metal oxide; z is at least one of metal oxides of Ni, Co, Pb, Fe, Mo or W, and the catalyst optimizes the abrasion performance, and has an optimal abrasion index of about 1.5 percent.
Because aromatic hydrocarbon gas phase ammonia oxidation is an exothermic reaction, the prior xylene ammonia oxidation process mainly adopts a fine particle catalyst and a fluidized bed reaction process for industrial production. The applicant finds in research that the existing xylene fluidized bed ammoxidation technology generally has the disadvantages of low reaction efficiency caused by material back mixing, reduced product selectivity and yield, and increased raw material cost; in addition, the problem that fine catalyst powder is generated due to the abrasion of the fine catalyst particles of the fluidized bed inevitably exists in the prior art, so that the fluidized quality and the stability of the catalyst in the reactor are obviously reduced, the loss amount of the catalyst is large, and the process cost is increased; in addition, the fine powder catalyst is mixed in the outlet stream of the reactor, resulting in difficulty in separation and purification and three-waste treatment.
In summary, there is a need for an ammoxidation catalyst that is optimized by the existing xylene ammoxidation catalyst and reaction process, improves the conversion rate of xylene, selectivity and yield of target product phthalonitrile, and further optimizes the wear index of the catalyst.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a sulfide coated ammoxidation catalyst, a preparation method and application thereof, wherein the catalyst improves the conversion rate of dimethylbenzene, the selectivity and the yield of a target product phthalonitrile, and optimizes the wear index of the catalyst.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the invention provides a sulfide coated ammonia oxidation catalyst, which comprises an active component and a carrier, wherein the active component satisfies the following structure shown in the formula I in an atomic ratio:
(MoS2)aAsbGecSedSieXfYgOxformula I
In the formula I, X is selected from one or more of La, Pr, Pm or Sm, and Y is selected from one or more of Ir, Pt, Rh or Ru;
wherein a is 0.1-30, b is 0.2-20, c is 0-2.5, d is 0-2.5, e is 10-90, f is 0.01-8, and g is 0.001-2; and (a + b)/e is more than 0.2 and less than 1.8, c + d is more than 0.01 and less than 5, and f/(c + d + g) is more than 5 and less than or equal to 80; x is determined by the degree of oxidation of the other elements.
In some embodiments, in formula i, a is 5 to 20, b is 1 to 15, c is 0 to 1.5, d is 0 to 1.5, e is 20 to 80, f is 0.1 to 5, and g is 0.01 to 1.5.
In the sulfide coated ammonia oxidation catalyst provided by the invention, the active components are vulcanized by accurately adjusting the proportion among the active components to form high-efficiency multi-metal compound active sites, particularly introduced germanium, selenium and (MoS)2)aAsbThe double active centers are formed, the activation energy of the oxidation reaction of the dimethyl benzene ammonia can be obviously reduced in the ammoxidation reaction, and the reaction efficiency is greatly improved.
Meanwhile, the X-type element introduced into the catalyst of the sulfide coated ammonia oxidation catalyst provided by the invention is a promoter, which is in contact with (MoS)2)aAsbEffectively improves the selectivity in the ammoxidation process and reduces the mononitriles, CO and CO under the synergistic action2And the generation of deep oxidation byproducts such as HCN and the like, and Y-type elements are beneficial to protecting the redox cycle of active sites of the catalyst, improving the stability of the catalyst and ensuring long-period stable operation.
In a specific embodiment of the invention, the mass percentage of the active component is 18-80% of the total mass of the ammonia oxidation catalyst, and the balance is the carrier.
In a second aspect, the present invention provides a process for preparing the sulfided coated ammonia oxidation catalyst described above, using a process comprising the steps of:
1) mixing each substance containing active components and a solvent to obtain slurry;
2) aging and drying the slurry to obtain active component precursor powder, and coating the active component precursor powder and a binder on a carrier to obtain a molded catalyst;
3) carrying out vulcanization treatment and roasting on the molded catalyst to obtain a sulfide coated ammonia oxidation catalyst;
in step 1), each of the substances containing an active component comprises a molybdenum-containing compound, an arsenic-containing compound, a germanium-containing compound, a selenium-containing compound, a silicon-containing compound, a sulfur-containing compound, and a metal element represented by X, Y in the structure represented by formula i in claim 1; the dosage of each substance containing the active component meets the proportion of each element in the structure shown in the formula I in claim 1;
in the step 2), the thermal conductivity coefficient of the carrier is 2-20W/(m.K), preferably 5-16W/(m.K), and the carrier is preferably selected from inert ceramic balls and/or silicon carbide ceramic balls;
in the step 3), the vulcanization treatment is carried out by placing the formed catalyst in a vulcanization atmosphere, wherein the vulcanization atmosphere is a mixed gas of hydrogen sulfide and hydrogen according to a volume ratio of 0.2-10: 1, and preferably nitrogen is used as a carrier gas of the vulcanization atmosphere; the volume space velocity (GHSV) of the sulfuration atmosphere is 5-1000 h-1And the time of the vulcanization treatment is 2-16 h.
In a specific embodiment, the mixing form of each substance containing an active component and a solvent in step 1) is not particularly limited, and all the substances containing the active component may be mixed and then mixed with the solvent to obtain the slurry, or each substance may be mixed with the solvent in steps to obtain a plurality of mixed solutions, and then the mixed solutions are mixed together to obtain the slurry; the mixing process can be carried out under the conditions of stirring and heating, so that the aim of full dissolution is achieved; in some embodiments, the stirring speed is 50-800 rpm, preferably 300-500 rpm; the stirring time is 0.1-5 h, preferably 0.5-2 h; the stirring temperature is 35-90 ℃, preferably 65-85 ℃.
In step 1) of the preparation method of the present invention, the molybdenum-containing compound is selected from one or more of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, ammonium tetrathiomolybdate, molybdenum trioxide, ammonium paramolybdate, molybdic acid, phosphomolybdic acid, or phosphomolybdic acid; ammonium tetrathiomolybdate and/or ammonium heptamolybdate are preferred;
the arsenic-containing compound is selected from one or more of arsenic pentachloride, arsenic trichloride, arsenic pentoxide, arsenic trioxide, arsenic pentafluoride or arsenic trifluoride; preferably arsenic pentachloride and/or arsenic trichloride;
the germanium-containing compound is selected from one or more of germanium monoxide, germanium dioxide, germanium monosulfide, germanium disulfide, germanium tetraiodide or germanium tetrachloride; preferably germanium tetraiodide and/or germanium tetrachloride;
the selenium-containing compound is selected from one or more of selenium dioxide, selenic acid, selenium tetrachloride or selenium disulfide; preferably selenic acid and/or selenium tetrachloride;
the silicon-containing compound is selected from one or more of silica sol, nano silica or chromatographic silica gel;
the compounds of other metal elements in the active component are respectively selected from one or more of nitrate, chloride, carbonate or acetate of other metal elements.
In the step 1), the mass ratio of the added solvent to the active component-containing substances is (0.1-100): 1, and the solvent is selected from one or more of water, benzene, toluene, acetone, methanol and ethanol.
In the step 2), the aging is carried out for 0.5-10 h at the temperature of 60-125 ℃; the drying method can be selected from drying methods well known in the art, including spray drying, evaporation drying, flash drying, vacuum drying, rotary vacuum drying or drum drying, and more preferably centrifugal spray drying; for the purpose of scale-up molding, spray drying is preferably employed; in some embodiments, the aged slurry is preferably heated to an inlet temperature of 150 to 350 ℃, preferably 160 to 300 ℃; and (3) carrying out spray drying at the outlet temperature of 90-200 ℃, preferably at 120-180 ℃, and drying to obtain active component precursor powder with the particle size of 20-210 micrometers, preferably 30-180 micrometers.
In the step 2), the mass ratio of the active component precursor powder, the binder and the carrier is (0.01-20): 0.01-12): 1; the binder used in the invention is selected from one or more of glycerol, starch, polyvinyl alcohol, methylcellulose, hydroxypropyl methylcellulose, dextrin, curdlan, pullulan, gum arabic powder or polyethylene glycol; preferably one or more of starch, pullulan or gum arabic powder; the binder is preferably in the form of a binder aqueous solution, preferably a binder aqueous solution with the content of 5-60 wt%, and further preferably 15-45 wt%;
the support mentioned in the present invention is preferably selected from inert ceramic balls, which, as is well known to those skilled in the art, act as a covering support material for the catalyst in the reactor and can be divided according to their composition into inert ceramic balls of different alumina contents, for example, 82 wt.% Al2O3，80wt.％Al2O3(ii) a In some embodiments, the carrier has a porosity of 6 to 18%, a water absorption of 10 to 50%, and a pore size of 200 to 800 μm.
In the invention, the specific process of coating the active component precursor powder and the binding agent on the carrier can be finished in a centrifugal coating machine; specifically, the carrier is placed in a coating machine to roll, active component precursor powder and a binder aqueous solution are sprayed onto the surface of the carrier in a centrifugal coating machine through an automatic feeding machine, the rotating speed of the carrier away from the coating machine in the process is 15-180 revolutions per minute, preferably 25-165 revolutions per minute, the temperature in the centrifugal coating machine is 25-90 ℃, preferably 35-80 ℃, and the formed catalyst is obtained.
In the step 3), the molded catalyst is dried and then vulcanized, wherein the drying treatment is carried out for 2-10 h at 100-160 ℃, and preferably the temperature is increased to the drying treatment temperature at the speed of 1-10 ℃/min; the vulcanization treatment is carried out at 150-250 ℃, preferably 160-230 ℃; further preferably raising the temperature to the temperature of the vulcanization treatment at a rate of 1-8 ℃/min; and roasting the molded catalyst subjected to the vulcanization treatment at 450-650 ℃, and preferably raising the temperature to the roasting temperature at a rate of 1-5 ℃/min.
In some embodiments, the drying and baking apparatus is not particularly limited, and may be performed in a rotary kiln, a trolley kiln, or a mesh belt kiln, and preferably in a rotary kiln for improving uniformity.
In a third aspect of the present invention, there is provided a method for producing phthalonitrile, comprising subjecting xylene, ammonia gas and an oxygen-containing gas to ammoxidation reaction in the presence of a catalyst to obtain isophthalonitrile; the catalyst adopts the sulfide-coated ammonia oxidation catalyst or the sulfide-coated ammonia oxidation catalyst prepared by the method;
wherein the molar ratio of the xylene to the ammonia to the oxygen in the oxygen-containing gas is 1: 1-9: 4.2-13.6, preferably 1: 2-8: 5.2-12.5.
In the practice of the present invention, the oxygen-containing gas may be pure oxygen, or air with a volume fraction of about 21%, or a mixture of oxygen and other non-reactive gases.
In the specific method, the temperature of the ammoxidation reaction is 300-500 ℃, preferably 320-420 ℃; the gauge pressure of the ammoxidation reaction is 1-350 kPa; preferably 10 to 250 kPa. In some embodiments, the xylene as feedstock may be selected from ortho-xylene, meta-xylene, and para-xylene.
More preferably, the reaction raw materials are gasified, uniformly mixed and introduced into a reactor for carrying out the ammoxidation reaction, and the weight load of the catalyst in the reactor is 0.01-0.5 h-1Preferably 0.03 to 0.45h-1。
By adopting the technical scheme, the method has the following technical effects:
in the sulfide coated ammonia oxidation catalyst provided by the invention, the active components are vulcanized by accurately adjusting the proportion of the active components to form high-efficiency multi-metal compound active sites, and particularly, germanium and selenium elements are introduced into the catalyst, so that (MoS) is obtained2)aAsbForm double active centers, and can obviously reduce the oxidation of the dimethyl benzene during the ammoxidationThe reaction activation energy greatly improves the reaction efficiency.
Meanwhile, the X-type element introduced into the catalyst of the sulfide coated ammonia oxidation catalyst provided by the invention is used as an active auxiliary agent, and is (MoS)2)aAsbThe synergistic effect effectively improves the selectivity in the ammoxidation process and reduces the mononitriles, CO and CO2And the generation of deep oxidation byproducts such as HCN and the like, and Y-type elements are beneficial to protecting the redox cycle of active sites of the catalyst, improving the stability of the catalyst and ensuring long-period stable operation.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The following examples are given for raw material information:
inert ceramic ball 1: alumina porcelain ball (18 wt.% SiO)2And 82 wt.% Al2O3) (ii) a The outer diameter is 2.5mm, the water absorption is 18 wt%, and the pore diameter is 450 mu m; calculated by the total pore volume of the carrier, the pore volume occupied by the pore channels with the internal diameter of 300-450 mu m is 35%, the porosity is 10%, and the heat conductivity is 9W/(m.K);
inert ceramic ball 2: alumina porcelain ball (20 wt.% SiO)2And 80 wt.% Al2O3) (ii) a The outer diameter is 2.6mm, the water absorption is 19 wt%, and the pore diameter is 437 mu m; calculated by the total pore volume of the carrier, the pore volume occupied by the pore channels with the internal diameter of 300-450 mu m is 33%, the porosity is 12%, and the thermal conductivity is 8.5W/(m.K);
silicon carbide ceramic ball: the outer diameter of the porcelain ball is 2.1mm, the water absorption is 12 wt%, and the aperture is 413 mu m; calculated by the total pore volume of the carrier, the pore volume occupied by the pore channels with the internal diameter of 300-450 mu m is 29%, the porosity is 11%, and the thermal conductivity is 7.5W/(m.K).
Other raw materials used in the examples are conventional in the art, and the purity specification used is industrial grade purity.
The calculation formula of the conversion rate of the raw material dimethylbenzene and the selectivity of the target product isophthalonitrile (ortho, meta and para) is as follows:
xylene conversion (%). times.100% (moles of xylene reacted/moles of xylene fed)
Phthalonitrile selectivity (%) - (moles of phthalonitrile produced/moles of xylene reacted) × 100%
Example 1
1) 6620.7g of ammonium heptamolybdate (H)24Mo7N6O24·4H2O) and 2719.2g of arsenic chloride AsCl3Adding the mixture into 15000g of deionized water at 75 ℃, stirring the mixture at 350 r/min until the mixture is dissolved, and then adding 7510.5g of 40 wt.% silica sol solution to obtain a first mixed solution;
1236.4g of praseodymium chloride (PrCl)3) 16.1g of germanium tetrachloride (GeCl)4) And 130g of rhodium nitrate (Rh (NO)3)3·nH2O) is added into 1450g of deionized water at the temperature of 80 ℃ and is stirred at 350 r/min until the deionized water is dissolved, and a mixed solution II is obtained;
adding the mixed solution II into the mixed solution I under the stirring condition of 350 revolutions per minute, and stirring for 1.5 hours to obtain slurry;
2) standing and aging the slurry at 70 ℃ for 3.5h, and performing spray drying at an inlet temperature of 290 ℃ and an outlet temperature of 135 ℃ to obtain active component precursor powder with the average particle size of 68 mu m;
23800g of inert ceramic balls 1 are placed in a roller of a coating machine to roll, the revolution is 130 r/min, and the temperature in the coating machine is kept at 60 ℃; 6600g of catalyst precursor powder and 660g of an aqueous solution containing 45 wt.% of gum arabic powder were spray coated on the surface of the carrier to form a shaped catalyst;
3) placing the obtained molded catalyst in a rotary kiln, heating to 150 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and drying; then, the temperature is raised to 200 ℃ at the speed of 2 ℃/min, the temperature is kept for 8 hours, hydrogen sulfide and hydrogen gas (the volume concentration of the hydrogen sulfide is 8 percent, the volume concentration of the hydrogen gas is 1.5 percent, the rest is nitrogen gas) which take nitrogen gas as carrier gas are introduced, and the total gas space velocity is 150h-1) Carrying out vulcanization treatment; then roasting the mixture in nitrogen atmosphere, and heating the nitrogen at the temperature of 2.5 ℃/minCalcining at 600 deg.C for 6 hours to obtain a sulfide-coated ammoxidation catalyst 1 having an active component composition of (MoS)2)15As6Ge0.03Si50Pr2Rh0.18Ox。
Filling the obtained sulfide coated ammonia oxidation catalyst 1 into a fused salt tubular fixed bed reactor for ammonia oxidation reaction, wherein the molar ratio of m-xylene, ammonia gas and oxygen in the reaction raw materials is 1:7:10, the temperature of the ammonia oxidation reaction is 390 ℃, the reaction pressure (gauge pressure) is 25kPa, and the weight load of the catalyst in the reactor is 0.08h-1。
After the reactor was operated for 950 hours, the conversion of m-xylene was 99.9%, the selectivity for m-phthalonitrile was 99.8%, and the selectivity for m-methylbenzonitrile was 0.05%.
Example 2
1) 4237.3g of ammonium heptamolybdate (H)24Mo7N6O24·4H2O) and 2537.9g of arsenic chloride AsCl3Adding the mixture into 16500g of deionized water at the temperature of 81 ℃, stirring the mixture at 320 revolutions per minute until the mixture is dissolved, and adding 5407.6g of 40 wt.% silica sol solution to obtain a first mixed solution;
66.2g of selenium tetrachloride (SeCl)4) 1732g lanthanum nitrate (La (NO)3)3·6H2O) and 13.5g of platinum chloride (PtCl)4) Adding the mixture into 1600g of deionized water at the temperature of 81 ℃, and stirring the mixture at the speed of 320 revolutions per minute until the mixture is dissolved to obtain a mixed solution II;
adding the mixed solution II into the mixed solution I under the stirring condition of 320 revolutions per minute, and stirring for 2.8 hours to obtain slurry;
2) standing and aging the slurry at 80 ℃ for 6.5h, and performing spray drying at inlet temperature of 293 ℃ and outlet temperature of 126 ℃ to obtain active component precursor powder with average particle size of 67 mu m;
placing 22600g of silicon carbide ceramic balls in a roller of a coating machine to roll at the speed of 135 revolutions per minute, and keeping the temperature in the coating machine at 62 ℃; 6300g of catalyst precursor powder and 580g of an aqueous solution containing 45 wt.% of gum arabic powder were spray-coated on the surface of the carrier to form a shaped catalyst;
3) placing the obtained molded catalyst in a rotary kiln, heating to 155 ℃ at a heating rate of 3.5 ℃/min in a nitrogen atmosphere, and drying; then, the temperature is raised to 210 ℃ at the speed of 3 ℃/min, the temperature is kept for 8.5 hours, hydrogen sulfide and hydrogen gas (the volume concentration of the hydrogen sulfide is 8.1 percent, the volume concentration of the hydrogen gas is 1.5 percent, the rest is nitrogen gas) which take nitrogen gas as carrier gas are introduced, and the total gas space velocity is 260h-1) Carrying out vulcanization treatment; then roasting the mixture in nitrogen atmosphere, heating the nitrogen to 630 ℃ at the speed of 2.5 ℃/min, and roasting the mixture for 6.5 hours to obtain the sulfide coated ammonia oxidation catalyst 2, wherein the active component of the sulfide coated ammonia oxidation catalyst 2 is (MoS)2)12As7Se0.15Si45La2Pt0.02Ox。
Filling the obtained sulfide-coated ammonia oxidation catalyst 2 into a fused salt tubular fixed bed reactor for ammonia oxidation reaction, wherein the molar ratio of o-xylene, ammonia gas and oxygen in the reaction raw materials is 1:7:11.5, the temperature of the ammonia oxidation reaction is 377 ℃, the reaction pressure (gauge pressure) is 20kPa, and the weight load of the catalyst in the reactor is 0.08h-1。
After the reactor is operated for 950 hours, the conversion rate of the o-xylene is 99.9 percent, the selectivity of the phthalonitrile is 99.9 percent, and the selectivity of the o-tolunitrile is 0.04 percent.
Example 3
1) 5738g of ammonium heptamolybdate (H)24Mo7N6O24·4H2O) and 2266g of arsenic chloride AsCl3Adding the mixture into 15500g of deionized water at 78 ℃, stirring the mixture at 330 revolutions per minute until the mixture is dissolved, and adding 8261.6g of 40 wt.% silica sol solution to obtain a first mixed solution;
80.4g of germanium tetrachloride (GeCl)4) 115.9g of selenium tetrachloride (SeCl)4) 1669.1g of praseodymium chloride (PrCl)3) And 13.2g of iridium nitrate (IrCl)3·3H2O) is added into 1550g of deionized water at the temperature of 80 ℃, and the mixture is stirred at 330 revolutions per minute until the mixture is dissolved, so that a mixed solution II is obtained;
adding the mixed solution II into the mixed solution I under the stirring condition of 330 revolutions per minute, and stirring for 2.5 hours to obtain slurry;
2) standing and aging the slurry at 70 ℃ for 4.5h, and performing spray drying at inlet temperature of 285 ℃ and outlet temperature of 125 ℃ to obtain active component precursor powder with average particle size of 65 μm;
placing 22000g of inert ceramic balls 2 in a roller of a coating machine to roll, wherein the rotation speed is 115 revolutions per minute, and the temperature in the coating machine is kept at 65 ℃; spraying 6200g of catalyst precursor powder and 630g of an aqueous solution containing 45 wt.% of arabic gum powder on the surface of the carrier to form a shaped catalyst;
3) placing the obtained molded catalyst in a rotary kiln, heating to 145 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere, and drying; then, the temperature is raised to 200 ℃ at the speed of 2.5 ℃/min, the temperature is kept for 7.5 hours, hydrogen sulfide and hydrogen gas (the volume concentration of the hydrogen sulfide is 7.6 percent, the volume concentration of the hydrogen gas is 1.3 percent, the rest is nitrogen gas) which take nitrogen gas as carrier gas are introduced, and the total gas space velocity is 130h-1) Carrying out vulcanization treatment; then roasting the mixture in nitrogen atmosphere, heating the nitrogen to 610 ℃ at the temperature of 3 ℃/min, and roasting the mixture for 5.5 hours to obtain the sulfide coated ammonia oxidation catalyst 3, wherein the active component of the catalyst is (MoS)2)13As5Ge0.15Se0.21Si55Pr2.7Ir0.015Ox。
Filling the obtained sulfide-coated ammonia oxidation catalyst 3 into a fused salt tubular fixed bed reactor for ammonia oxidation reaction, wherein the molar ratio of p-xylene, ammonia gas and oxygen in the reaction raw materials is 1:7:12, the temperature of the ammonia oxidation reaction is 385 ℃, the reaction pressure (gauge pressure) is 23kPa, and the weight load of the catalyst in the reactor is 0.07h-1。
After the reactor was operated for 950 hours, the conversion of p-xylene was 99.8%, the selectivity to phthalonitrile was 99.9%, and the selectivity to methylbenzonitrile was 0.03%.
Comparative example 1
Comparative example 1 differs from example 1 in that: germanium tetrachloride (GeCl) is not added in the preparation process of the catalyst4) To obtain an ammoxidation catalyst1-1, the active component of which is (MoS)2)15As6Si50Pr2Rh0.18Ox。
The ammoxidation catalyst 1-1 obtained above was charged in a molten salt tubular fixed bed reactor, and an ammoxidation reaction was carried out by the method of example 1, and after the reactor was operated for 950 hours, the conversion of m-xylene was 89.7% and the selectivity of m-phthalonitrile was 85.9%.
Comparative example 2
Comparative example 2 differs from example 2 in that: arsenic chloride (SeCl) is not added in the preparation process of the catalyst4) To obtain an ammonia oxidation catalyst 2-2 having an active component composition of (MoS)2)12Se0.15Si45La2Pt0.02Ox。
The ammoxidation catalyst 2-2 obtained above was packed in a molten salt tubular fixed bed reactor, and an ammoxidation reaction was carried out by the method of example 2, and after the reactor was operated for 950 hours, the conversion of o-xylene was 85.3% and the selectivity of phthalonitrile was 86.1%.
Comparative example 3
Comparative example 3 differs from example 3 in that: in the preparation process of the catalyst, the sulfuration is carried out without adopting the mixed gas of hydrogen sulfide and hydrogen (the volume concentration of the hydrogen sulfide is 0 percent, the volume concentration of the hydrogen is 0 percent, all the hydrogen is nitrogen, and the space velocity of the total gas is 130h-1) To obtain an ammoxidation catalyst 3-3 whose active component is Mo13As5Ge0.15Se0.21Si55Pr2.7Ir0.015Ox。
The ammoxidation catalyst 3-3 obtained above was packed in a molten salt tubular fixed bed reactor, and an ammoxidation reaction was carried out by the method of example 3, and after the reactor was operated for 950 hours, the conversion of p-xylene was 81.9% and the selectivity for terephthalonitrile was 83.5%.
Comparative example 4
Preparation of composition V according to example 11 of patent CN1268399A1.0Cr1.0B0.5P0.2K0.05Cs0.025/SiO2The catalyst abrasion index of the ammoxidation catalyst is 8.3 percent, the catalyst is filled in a fused salt tube type fixed bed reactor, and the ratio of p-xylene: ammonia: the oxygen molar ratio is 1:6:9.4, the temperature is 420 ℃, the pressure is 0.03MPa, and the weight load of the catalyst is 0.07h-1The reaction was carried out with a conversion of p-xylene of 86.5%, selectivity to terephthalonitrile of 78.5% and selectivity to methylbenzonitrile of 6.5%.
Comparative example 5
Preparation of composition V according to example 1 of patent CN1500775A1.0Cr0.9B0.5Ti0.1P0.05Mo0.1Na0.05/SiO2The ammoxidation catalyst has a catalyst abrasion index of 9.1 percent, and the catalyst is filled in a fused salt tube type fixed bed reactor and the molar ratio of m-xylene: ammonia: oxygen is 1:5:10.5, the temperature is 430 ℃, the pressure is 0.02MPa, and the weight load of the catalyst is 0.05h-1The reaction was carried out with a conversion of m-xylene of 87.1%, selectivity of m-phthalonitrile of 73.2% and selectivity of m-methylbenzonitrile of 8.9%.
Comparative example 6
The preparation of Mo of composition is carried out according to the method of example 1 in patent application No. 2007100478691V0.31Nb0.22Te0.23Sn0.03OxThe ammoxidation catalyst has a catalyst abrasion index of 8.5 percent, and the catalyst is filled in a fused salt tube type fixed bed reactor and the molar ratio of m-xylene: ammonia: oxygen of 1:5.5:10, temperature of 435 ℃, pressure of 0.03MPa and catalyst weight load of 0.05h-1The reaction was carried out with a conversion of m-xylene of 73.5%, selectivity to m-phthalonitrile of 62.1% and selectivity to m-methylbenzonitrile of 7.5%.
Claims (10)
1. A sulfide-coated ammonia oxidation catalyst, which is characterized by comprising an active component and a carrier, wherein the active component satisfies the following structure shown in formula I in terms of atomic ratio:
(MoS2)aAsbGecSedSieXfYgOxformula I
In the formula I, X is selected from one or more of La, Pr, Pm or Sm, and Y is selected from one or more of Ir, Pt, Rh or Ru;
wherein a is 0.1-30, b is 0.2-20, c is 0-2.5, d is 0-2.5, e is 10-90, f is 0.01-8, and g is 0.001-2; and (a + b)/e is more than 0.2 and less than 1.8, c + d is more than 0.01 and less than 5, and f/(c + d + g) is more than 5 and less than or equal to 80; x is determined by the degree of oxidation of the other elements; preferably, a is 5 to 20, b is 1 to 15, c is 0 to 1.5, d is 0 to 1.5, e is 20 to 80, f is 0.1 to 5, and g is 0.01 to 1.5.
2. The sulfide-coated ammonia oxidation catalyst according to claim 1, wherein the mass percentage of the active component is 18 to 80% based on the total mass of the ammonia oxidation catalyst, and the balance is the carrier.
3. A process for the preparation of a sulphided, coated ammonia oxidation catalyst according to claim 1 or 2, wherein a process is used which comprises the steps of:
1) mixing each substance containing active components and a solvent to obtain slurry;
2) aging and drying the slurry to obtain active component precursor powder, and coating the active component precursor powder and a binder on a carrier to obtain a molded catalyst;
3) carrying out vulcanization treatment and roasting on the molded catalyst to obtain a sulfide coated ammonia oxidation catalyst;
in step 1), each of the substances containing an active component comprises a molybdenum-containing compound, an arsenic-containing compound, a germanium-containing compound, a selenium-containing compound, a silicon-containing compound, a sulfur-containing compound, and a metal element represented by X, Y in the structure represented by formula i in claim 1; the dosage of each substance containing the active component meets the proportion of each element in the structure shown in the formula I in claim 1;
in the step 2), the thermal conductivity coefficient of the carrier is 2-20W/(m.K), preferably 5-16W/(m.K), and the carrier is preferably selected from inert ceramic balls and/or silicon carbide ceramic balls;
in the step 3), the vulcanization treatment is carried out by placing the formed catalyst in a vulcanization atmosphere, wherein the vulcanization atmosphere is a mixed gas of hydrogen sulfide and hydrogen according to a volume ratio of 0.2-10: 1, and preferably nitrogen is used as a carrier gas of the vulcanization atmosphere; the volume airspeed of the vulcanization atmosphere is 5-1000 h-1And the time of the vulcanization treatment is 2-16 h.
4. The method according to claim 3, wherein in step 1), the molybdenum-containing compound is selected from one or more of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, ammonium tetrathiomolybdate, molybdenum trioxide, ammonium paramolybdate, molybdic acid, phosphomolybdic acid, or phosphomolybdic acid;
the arsenic-containing compound is selected from one or more of arsenic pentachloride, arsenic trichloride, arsenic pentoxide, arsenic trioxide, arsenic pentafluoride or arsenic trifluoride;
the germanium-containing compound is selected from one or more of germanium monoxide, germanium dioxide, germanium monosulfide, germanium disulfide, germanium tetraiodide or germanium tetrachloride;
the selenium-containing compound is selected from one or more of selenium dioxide, selenic acid, selenium tetrachloride or selenium disulfide;
the silicon-containing compound is selected from one or more of silica sol, nano silica or chromatographic silica gel;
the compounds of other metal elements in the active component are respectively selected from one or more of nitrate, chloride, carbonate or acetate of other metal elements.
5. The method according to claim 4, wherein in the step 1), the mass ratio of the added solvent to the substances containing the active components is (0.1-100): 1, and the solvent is selected from one or more of water, benzene, toluene, acetone, methanol and ethanol.
6. The method according to claim 5, wherein in the step 2), the aging is performed for 0.5-10 hours at 60-125 ℃; the drying is preferably to spray-dry the aged slurry at the inlet temperature of 150-350 ℃ and the outlet temperature of 90-200 ℃;
the particle size of the active component precursor powder is 20-210 μm, and preferably 30-180 μm.
7. The method according to claim 6, wherein in the step 2), the mass ratio of the active component precursor powder, the binder and the carrier is (0.01-20): 1;
the binder is selected from one or more of glycerol, starch, polyvinyl alcohol, methylcellulose, hydroxypropyl methylcellulose, dextrin, curdlan, pullulan, gum arabic powder or polyethylene glycol; the binder is preferably an aqueous solution with the content of 5-60 wt%, and is further preferably 15-45 wt%;
the carrier preferably has a porosity of 6-18%, a water absorption of 10-50% and a pore diameter of 200-800 μm.
8. The method according to claim 7, wherein in step 3), the formed catalyst is dried and then subjected to the sulfidation treatment, and the drying treatment is carried out at 100-160 ℃ for 2-10 h, preferably at a rate of 1-10 ℃/min until reaching the temperature of the drying treatment;
the vulcanization treatment is carried out at 150-250 ℃, preferably 160-230 ℃; further preferably raising the temperature to the temperature of the vulcanization treatment at a rate of 1-8 ℃/min;
and roasting the molded catalyst subjected to the vulcanization treatment at 450-650 ℃, and preferably raising the temperature to the roasting temperature at a rate of 1-5 ℃/min.
9. A process for producing phthalonitrile, which comprises the following steps: in the presence of a catalyst, carrying out ammoxidation reaction on dimethylbenzene, ammonia gas and oxygen-containing gas to obtain phthalonitrile; the catalyst adopts the sulfide coated ammonia oxidation catalyst as described in claims 1-2, or the sulfide coated ammonia oxidation catalyst prepared by the method described in claims 3-8;
wherein the molar ratio of the xylene to the ammonia to the oxygen in the oxygen-containing gas is 1: 1-9: 4.2-13.6, preferably 1: 2-8: 5.2-12.5.
10. The method according to claim 9, wherein the temperature of the ammoxidation reaction is 300 to 500 ℃, preferably 320 to 420 ℃; the gauge pressure of the ammoxidation reaction is 1-350 kPa; preferably 10 to 250 kPa;
more preferably, the reaction raw materials are gasified, uniformly mixed and introduced into a reactor for carrying out the ammoxidation reaction, and the weight load of the catalyst in the reactor is 0.01-0.5 h-1Preferably 0.03 to 0.45h-1。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112675848A (en) * | 2021-01-12 | 2021-04-20 | 万华化学集团股份有限公司 | Catalyst for producing isophthalonitrile, preparation method and method for preparing isophthalonitrile by using catalyst |
| CN114367302A (en) * | 2021-12-29 | 2022-04-19 | 万华化学集团股份有限公司 | Preparation method and application of catalyst for preparing hydrocyanic acid by ammoxidation of methanol |
| CN114950462A (en) * | 2022-06-23 | 2022-08-30 | 万华化学集团股份有限公司 | Catalyst for preparing HCN by methanol ammoxidation and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821172A (en) * | 1997-01-06 | 1998-10-13 | Advanced Micro Devices, Inc. | Oxynitride GTE dielectrics using NH3 gas |
| US20040102643A1 (en) * | 2002-11-27 | 2004-05-27 | Tway Cathy L. | Process for preparing a catalyst for the oxidation and ammoxidation of olefins |
| CN104998694A (en) * | 2015-05-29 | 2015-10-28 | 万华化学集团股份有限公司 | Cladding type catalyst carrier, preparation method thereof and cladding type catalyst |
| CN107469833A (en) * | 2017-08-11 | 2017-12-15 | 中国科学院东北地理与农业生态研究所 | A kind of preparation method and applications of the titanium dioxide hollow core shell structure composite photo-catalyst of molybdenum disulfide cladding |
| CN107847922A (en) * | 2015-07-20 | 2018-03-27 | 赢创德固赛有限公司 | The method for preparing the mixed oxide catalyst containing molybdenum and bismuth |
| CN107999070A (en) * | 2017-11-29 | 2018-05-08 | 万华化学集团股份有限公司 | A kind of coated catalyst and its preparation method and application |
| CN109174110A (en) * | 2018-11-15 | 2019-01-11 | 新地能源工程技术有限公司 | A kind of presulfurization catalyst for methanation in presence of sulfur and preparation method |
| CN109821564A (en) * | 2019-01-23 | 2019-05-31 | 湘潭大学 | A kind of preparation method and catalyst of coated catalyst |
| CN109847744A (en) * | 2018-12-26 | 2019-06-07 | 万华化学集团股份有限公司 | Ammoxidation catalyst, and preparation method thereof and the method for preparing isophthalodinitrile |
-
2020
- 2020-01-07 CN CN202010013063.6A patent/CN111167485B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821172A (en) * | 1997-01-06 | 1998-10-13 | Advanced Micro Devices, Inc. | Oxynitride GTE dielectrics using NH3 gas |
| US20040102643A1 (en) * | 2002-11-27 | 2004-05-27 | Tway Cathy L. | Process for preparing a catalyst for the oxidation and ammoxidation of olefins |
| CN104998694A (en) * | 2015-05-29 | 2015-10-28 | 万华化学集团股份有限公司 | Cladding type catalyst carrier, preparation method thereof and cladding type catalyst |
| CN107847922A (en) * | 2015-07-20 | 2018-03-27 | 赢创德固赛有限公司 | The method for preparing the mixed oxide catalyst containing molybdenum and bismuth |
| CN107469833A (en) * | 2017-08-11 | 2017-12-15 | 中国科学院东北地理与农业生态研究所 | A kind of preparation method and applications of the titanium dioxide hollow core shell structure composite photo-catalyst of molybdenum disulfide cladding |
| CN107999070A (en) * | 2017-11-29 | 2018-05-08 | 万华化学集团股份有限公司 | A kind of coated catalyst and its preparation method and application |
| CN109174110A (en) * | 2018-11-15 | 2019-01-11 | 新地能源工程技术有限公司 | A kind of presulfurization catalyst for methanation in presence of sulfur and preparation method |
| CN109847744A (en) * | 2018-12-26 | 2019-06-07 | 万华化学集团股份有限公司 | Ammoxidation catalyst, and preparation method thereof and the method for preparing isophthalodinitrile |
| CN109821564A (en) * | 2019-01-23 | 2019-05-31 | 湘潭大学 | A kind of preparation method and catalyst of coated catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112675848A (en) * | 2021-01-12 | 2021-04-20 | 万华化学集团股份有限公司 | Catalyst for producing isophthalonitrile, preparation method and method for preparing isophthalonitrile by using catalyst |
| CN114367302A (en) * | 2021-12-29 | 2022-04-19 | 万华化学集团股份有限公司 | Preparation method and application of catalyst for preparing hydrocyanic acid by ammoxidation of methanol |
| CN114367302B (en) * | 2021-12-29 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation method and application of methanol ammoxidation hydrogen production cyanic acid catalyst |
| CN114950462A (en) * | 2022-06-23 | 2022-08-30 | 万华化学集团股份有限公司 | Catalyst for preparing HCN by methanol ammoxidation and preparation method thereof |
| CN114950462B (en) * | 2022-06-23 | 2024-04-09 | 万华化学集团股份有限公司 | Catalyst for preparing HCN (hydrogen cyanide) by methanol ammoxidation and preparation method thereof |
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