CN113996322A - Catalyst for preparing dinitrile compound from alicyclic hydrocarbon and synthesis method of dinitrile - Google Patents

Catalyst for preparing dinitrile compound from alicyclic hydrocarbon and synthesis method of dinitrile Download PDF

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CN113996322A
CN113996322A CN202111342501.4A CN202111342501A CN113996322A CN 113996322 A CN113996322 A CN 113996322A CN 202111342501 A CN202111342501 A CN 202111342501A CN 113996322 A CN113996322 A CN 113996322A
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catalyst
alicyclic hydrocarbon
adiponitrile
molar ratio
alicyclic
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权于
王贤丰
高振聪
张亮
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ANSHAN HIFICHEM CO LTD
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ANSHAN HIFICHEM CO LTD
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention provides a catalyst for preparing dinitrile compounds from alicyclic hydrocarbon, which can open the ring of alicyclic alcohol, alicyclic ketone, cycloolefin and cycloalkane and simultaneously complete ammoxidation reaction to obtain the dinitrile compounds. The catalyst has high reaction activity and good selectivity, can prepare high-quality dinitrile compounds, is easy to control the process and is beneficial to industrial production.

Description

Catalyst for preparing dinitrile compound from alicyclic hydrocarbon and synthesis method of dinitrile
Technical Field
The invention belongs to the technical field of catalytic organic synthesis, and particularly relates to a catalyst for preparing dinitrile by catalyzing alicyclic hydrocarbon and a method for catalytically synthesizing dinitrile by the catalyst.
Background
With the development and application of chemical products, the demand of aliphatic dinitrile as an important chemical raw material is gradually increased. The adiponitrile can be used for producing monomer hexamethylene diamine of nylon 66, adipic acid can be prepared after hydrolysis, and the adiponitrile has multiple purposes. Glutaronitrile is a raw material for preparing chemical products such as diethyl glutarate, glutaric acid, 1, 5-diaminopentane and the like.
At present, the method for preparing aliphatic dinitriles mainly comprises the methods of preparing dinitrile by diacid, such as preparing adiponitrile by taking adipic acid as a starting material, preparing glutaronitrile and the like by glutaric acid, obtaining dinitrile products by reacting chlorohydrocarbon with cyanide, preparing adiponitrile by an acrylonitrile electrolytic dimerization method, preparing adiponitrile by a butadiene hydrocyanation method and the like.
The method for preparing the aliphatic dinitrile by using the alicyclic alcohol, the alicyclic ketone, the cycloolefin and the like as the raw materials has the problems that the selective oxidative ring-opening ammoxidation process and the like are required to be completed in the reaction process, the activation of the reaction raw materials is difficult, the activity and the selectivity of the catalyst are required to be improved, the occurrence of side reactions is reduced and the like.
Therefore, how to obtain a catalyst with good selection and high activity, catalytically synthesize dinitrile compounds, optimize the preparation process, reduce the generation of byproducts, and obtain high-quality dinitrile products, needs to further develop a preparation method for preparing aliphatic dinitrile.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for catalytically synthesizing aliphatic dinitrile, which has high reaction activity, good selectivity and long service life, and can catalyze alicyclic hydrocarbons such as cycloolefin, alicyclic alcohol, alicyclic ketone and the like to carry out ammoxidation reaction to synthesize dinitrile products. The synthesis process is easy to control, the process is simple, and side reactions can be effectively controlled to obtain high-quality products, so that the invention is completed.
The first aspect of the invention aims to provide a catalyst for preparing dinitrile compounds from alicyclic hydrocarbon. The alicyclic hydrocarbon is selected from one or more of alicyclic alcohol, alicyclic ketone, cycloolefin and cycloalkane, preferably alicyclic alcohol, alicyclic ketone or cycloolefin, and is a five-membered ring, a six-membered ring or a seven-membered ring, preferably a five-membered ring or a six-membered ring; the dinitrile compound is glutaronitrile, adiponitrile or pimelonitrile, preferably glutaronitrile or adiponitrile. For example, adiponitrile prepared using cyclohexanol, cyclohexanone or cyclohexene; cyclopentanol, cyclopentanone and cyclohexanone are used to prepare glutaronitrile.
The catalyst is a V-Ti-P-Mo-Cs catalyst which takes vanadium, titanium, phosphorus, molybdenum and cesium as basic active elements.
Preferably, the catalyst further comprises auxiliary elements including one or more of sodium, potassium, nickel, tin and chromium, preferably including one of the following groups:
(1) combinations of sodium, nickel, tin;
(2) a combination of nickel and tin;
(3) a combination of potassium and tin;
(4) a combination of nickel and chromium.
The second aspect of the present invention is to provide a method for preparing the catalyst for preparing the dinitrile compound from the alicyclic hydrocarbon, wherein the method comprises the steps of taking a compound containing vanadium-based catalyst component elements as a raw material, dissolving or dispersing the raw material in a solution to obtain a mixed solution, removing the solvent, and drying to obtain a catalyst precursor. And roasting the catalyst precursor in an oxygen atmosphere to obtain the catalyst.
The third aspect of the invention aims to provide a method for synthesizing dinitrile compounds. The method takes alicyclic hydrocarbon as a starting material, and the alicyclic hydrocarbon and ammonia react in the presence of a catalyst to synthesize the dinitrile compound, and preferably, the reaction is carried out in a carrier gas environment. Preferably, the method comprises in particular the steps of:
step 1, respectively preheating alicyclic hydrocarbon, ammonia and carrier gas;
step 2, mixing preheated alicyclic hydrocarbon, ammonia and carrier gas, and heating for reaction in the presence of a catalyst to obtain mixed gas;
and 3, post-treating the mixed gas to obtain the dinitrile compound.
The catalyst for preparing dinitrile compounds from alicyclic hydrocarbon and the synthesis method of nitrile compounds provided by the invention have the following beneficial effects:
(1) the catalyst has high reaction activity and good selectivity, can prepare high-quality dinitrile compounds, is easy to control the process and is beneficial to industrial production.
(2) The existing process mainly adopts a liquid-phase batch synthesis process route, and has long reaction route and low reaction efficiency. The synthesis process has high atom economy, directly obtains glutaronitrile and adiponitrile by using gas-phase continuous reaction, solves the problem of long reaction route, improves the reaction efficiency and reduces the production cost.
(3) The process for preparing adiponitrile by adopting cyclohexanol, cyclohexanone or cyclohexene does not relate to a process containing a highly toxic raw material or an intermediate product cyanide, the raw materials used by the novel process are relatively cheap and easily available, the production cost is reduced, the main reaction raw materials are all liquid, the difficulty of production engineering is reduced in a gas-solid phase continuous reaction system, and the process is successfully developed to solve the technical monopoly problem of adiponitrile for solving the similar problem of no adipic acid high-temperature coking of production equipment.
(4) The raw materials used in the process for preparing the glutaronitrile from the cyclopentanol, the cyclopentanone and the cyclohexanone are relatively cheap and easily available, the production cost is reduced, the main reaction raw materials are all liquid, and the difficulty of production engineering is reduced in a gas-solid phase continuous reaction system.
Drawings
FIG. 1 shows a gas chromatogram of adiponitrile prepared in example 1 of the present invention;
FIG. 2 shows a gas chromatogram of glutaronitrile produced in example 5 of the present invention.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The invention provides a catalyst for preparing dinitrile compounds from alicyclic hydrocarbon in a first aspect. The alicyclic hydrocarbon is selected from one or more of alicyclic alcohol, alicyclic ketone, cycloolefin and cycloalkane, preferably alicyclic alcohol, alicyclic ketone or cycloolefin, and is a five-membered ring, a six-membered ring or a seven-membered ring, preferably a five-membered ring or a six-membered ring; the dinitrile compound is glutaronitrile, adiponitrile or pimelonitrile, preferably glutaronitrile or adiponitrile. For example, adiponitrile prepared using cyclohexanol, cyclohexanone or cyclohexene; cyclopentanol, cyclopentanone and cyclohexanone are used to prepare glutaronitrile.
The catalyst is a V-Ti-P-Mo-Cs catalyst which takes vanadium, titanium, phosphorus, molybdenum and cesium as basic active elements. The catalyst is prepared by dissolving or dispersing a compound containing component elements in a solution to obtain a mixed solution, removing the solvent, and drying to obtain a catalyst precursor. Preferably, the carrier raw material is added to the mixed solution, taken out and dried to obtain the catalyst precursor. And roasting the catalyst precursor in an air atmosphere to obtain the V-Ti-P-Mo-Cs catalyst.
The molar ratio of the vanadium source to the titanium source to the phosphorus source to the molybdenum source to the cesium source is 1 (0.1-1.5): (0.1-1.90): 0.15-0.22): 0.17-0.4), preferably 1 (0.2-1.3): 0.5-1.60): 0.1-0.17): 0.12-0.3, more preferably 1 (0.36-1.1): 0.9-1.30): 0.05-0.12): 0.07-0.22. Wherein the molar amounts of the vanadium source, the titanium source, the phosphorus source, the molybdenum source and the cesium source are based on the molar amount of the component elements contained therein.
Preferably, the catalyst further comprises auxiliary elements including one or more of sodium, potassium, nickel, tin and chromium, preferably including one of the following groups:
(1) combinations of sodium, nickel, tin; the molar ratio is (0.03-0.20): (0.04-0.20): 0.02-0.09), preferably (0.06-0.10): 0.08-0.10): 0.05-0.07.
(2) A combination of nickel and tin; the molar weight ratio is (0.03-0.05): 0.01-0.1, preferably (0.03-0.05): 0.03-0.06).
(3) A combination of potassium and tin; the molar weight ratio is (0.04-0.2): 0.05-0.07, preferably (0.08-0.15): 0.05-0.07.
(4) A combination of nickel and chromium; the molar weight ratio is (0.03-0.05): 0.15-0.45, preferably (0.03-0.05): 0.25-0.35.
The molar ratio of the vanadium source to the total amount of the auxiliary element source is 1 (0.03-0.55), preferably 1 (0.05-0.45), and more preferably 1 (0.07-0.35). Wherein the molar amounts of the vanadium source and the auxiliary element source are based on the molar amount of the component elements contained therein.
In a preferred embodiment of the present invention, when adiponitrile is prepared from cyclohexanol or glutaronitrile is prepared from cyclopentanol, the catalyst is a V-Ti-P-Mo-Cs-Na-Ni-Sn catalyst, and the molar ratio of the above-mentioned component element raw materials is 1 (0.1-1.5), (0.1-1.90), (0.15-0.22), (0.17-0.4), (0.03-0.20), (0.04-0.20), (0.02-0.09), preferably 1 (0.36-1.1), (0.9-1.30), (0.05-0.12), (0.07-0.22): (0.06-0.10):(0.08-0.10):(0.05-0.07).
A catalyst for preparing adiponitrile by using cyclohexanol as a catalyst I (V-Ti-P-Mo-Cs-Na-Ni-Sn catalyst) comprises the following raw materials in a molar ratio of V, Ti, P, Mo, Cs, Na, Ni and Sn of 1:0.83:0.92:0.12:0.11:0.10:0.08: 0.06.
When cyclopentanol is used for preparing glutaronitrile, the catalyst is a catalyst V, and the molar ratio of the raw materials is V, Ti, P, Mo, Cs, Na, Ni and Sn is 1:0.45:1.12:0.08:0.07:0.06:0.10: 0.06.
In a preferred embodiment of the present invention, when adiponitrile is prepared from cyclohexanone or glutaronitrile is prepared from cyclopentanone, the catalyst is a V-Ti-P-Mo-Cs-Ni-Sn catalyst, and when the catalyst is prepared, the molar ratio of the raw materials of the above components is 1 (0.1-1.5), (0.1-1.90), (0.15-0.22), (0.17-0.4), (0.03-0.05), (0.01-0.1), preferably 1 (0.36-1.1), (0.9-1.30), (0.05-0.12), (0.07-0.22): (0.03-0.05):(0.03-0.06).
When the cyclohexanone is used for preparing adiponitrile, the catalyst is a catalyst II (V-Ti-P-Mo-Cs-Ni-Sn catalyst), and the molar ratio of the raw materials is V, Ti, P, Mo, Cs, Ni and Sn is 1:0.71:1.12:0.10:0.16:0.04: 0.06.
When cyclopentanone is used for preparing glutaronitrile, the catalyst is a catalyst VI (V-Ti-P-Mo-Cs-Ni-Sn catalyst), and the molar ratio of the raw materials is V, Ti, P, Mo, Cs, Ni and Sn is 1:0.36:1.18:0.08:0.13:0.04: 0.03.
In a preferred embodiment of the present invention, when adiponitrile is prepared from cyclohexene, the catalyst is a V-Ti-P-Mo-Cs-K-Sn catalyst, and when the adiponitrile is prepared, the molar ratio of the raw materials of the components elements is 1 (0.1-1.5): 0.1-1.90): 0.15-0.22): 0.17-0.4): 0.04-0.2): 0.05-0.07, preferably 1 (0.36-1.1): 0.9-1.30): 0.05-0.12): 0.07-0.22): (0.08-0.15):(0.05-0.07).
When the adiponitrile is prepared from the cyclohexene, the catalyst is a catalyst III (V-Ti-P-Mo-Cs-K-Sn catalyst), and the molar ratio of the raw materials is (V: Ti: P: Mo: Cs: K: Sn) 1:1.00:1.12:0.05:0.08:0.11: 0.06.
In a preferred embodiment of the present invention, the catalyst is a V-Ti-P-Mo-Cs-Ni-Cr catalyst when preparing glutaronitrile from cyclohexanone, and the molar ratio of the above component element raw materials when preparing the glutaronitrile is 1 (0.1-1.5): 0.1-1.90): 0.15-0.22): 0.17-0.4): 0.03-0.05): 0.15-0.45, preferably 1 (0.36-1.1): 0.9-1.30): 0.05-0.12): 0.07-0.22): (0.03-0.05):(0.25-0.35).
When the cyclohexanone is used for preparing the glutaronitrile, the catalyst is a catalyst VII (V-Ti-P-Mo-Cs-Ni-Cr catalyst), and the molar ratio of the raw materials is V, Ti, P, Mo, Cs, Ni and Cr is 1:1.07:1.30:0.11:0.22:0.04: 0.31.
The molar amount of each of the above-mentioned component element raw materials is based on the molar amount of the component element contained therein.
The second aspect of the invention provides a preparation method of the catalyst for preparing the dinitrile compound from the alicyclic hydrocarbon, which comprises the steps of taking a compound containing catalyst component elements as a raw material, dissolving or dispersing the raw material in a solution to obtain a mixed solution, removing the solvent, and drying to obtain a catalyst precursor. And roasting the catalyst precursor in an oxygen atmosphere to obtain the catalyst.
The compound of the metal component element of the catalyst is salt, metal oxide or acid dissolved in water or acidic solution. Wherein the content of the first and second substances,
the vanadium source is a vanadium compound, preferably an oxide of vanadium, such as vanadium pentoxide, vanadium trioxide.
The titanium source is a titanium-containing compound, such as titanium dioxide.
The source of phosphorus is a phosphorus compound, preferably a soluble phosphate or phosphoric acid, more preferably phosphoric acid.
The molybdenum source is a molybdenum compound, preferably molybdic acid or molybdate, such as ammonium molybdate, sodium molybdate, preferably ammonium molybdate.
The cesium source is a cesium-containing compound, preferably a cesium salt, such as cesium chloride, cesium sulfate or cesium nitrate.
The auxiliary metal element source is salt or oxide containing sodium, potassium, nickel, tin and chromium, such as nickel chloride, manganese oxide, ferric oxide, ferrous oxide, ferric chloride, ferrous chloride, cobalt oxide, etc.
The sodium source is sodium salt, such as sodium chloride, sodium nitrate, sodium sulfate, etc.
The potassium source is potassium salt, such as potassium chloride, potassium nitrate, potassium sulfate, etc.
The nickel source is nickel salt, such as nickel chloride, nickel nitrate, nickel sulfate, etc.
The tin source is a tin salt, such as tin chloride, tin nitrate, tin sulfate, and the like.
The chromium source is a chromium salt or chromium oxide, such as chromium chloride or chromium trioxide.
The molar amount of each of the above-mentioned component element raw materials is based on the molar amount of the metal component element contained therein.
Preferably, the compound of the element of the catalyst component is dissolved in an acidic solution, such as an oxalic acid solution, the mass concentration of the acidic substance being 10 to 30%, preferably 15 to 25%.
The molar ratio of the vanadium element to the acid is (0.2-1.4):2, preferably (0.3-1):2, more preferably (0.4-0.6): 2.
The molar mass ratio of the vanadium source to the carrier raw material is 1mol of (1500) -2100 g, preferably 1mol of (1600) -2000 g, and more preferably 1mol of (1700) -1900 g. The molar amount of the vanadium source is based on the molar amount of the vanadium-containing element contained therein.
The carrier raw material is selected from one of silica sol, silica and aluminum trioxide, preferably silica sol or silica, and more preferably silica sol. Preferably, the silica sol has a mass concentration of 25% to 65%, preferably 35% to 55%.
The roasting is carried out in two sections: the first section is calcined for 1.5 to 6.5 hours at the temperature of 200-400 ℃ and calcined for 2.5 to 4.5 hours at the temperature of 250-350 ℃; the second-stage calcination temperature is 500-800 ℃, preferably 600-700 ℃, such as 650 ℃; the roasting time is 6-14h, and 8-10h is preferred. The first stage of calcination mainly decomposes metallic oxalate generated in the preparation of the catalyst at the temperature, the calcination time is to ensure that the oxalate in the catalyst can be fully decomposed, the second stage of calcination mainly carries out the adjustment stage of the valence state of different metal oxides under the high temperature condition, and the calcination time is to adjust the valence state of the metal element to a stable valence state.
In a third aspect, the invention provides a method for catalytically preparing dinitrile compounds. The method takes alicyclic hydrocarbon as a starting material, and the alicyclic hydrocarbon and ammonia react in the presence of a catalyst to synthesize the dinitrile compound, and preferably, the reaction is carried out in a carrier gas environment.
The dinitrile compound is glutaronitrile, adiponitrile or pimelonitrile, preferably glutaronitrile or adiponitrile; the alicyclic hydrocarbon is selected from one or more of alicyclic alcohol, alicyclic ketone, cycloolefin and cycloalkane, preferably alicyclic alcohol, alicyclic ketone or cycloolefin, and is a five-membered ring, a six-membered ring or a seven-membered ring, preferably a five-membered ring or a six-membered ring.
The method specifically comprises the following steps:
step 1, respectively preheating alicyclic hydrocarbon, ammonia and carrier gas.
The alicyclic hydrocarbon, ammonia and carrier gas are preheated separately. The preheating temperature is 130-240 ℃, preferably 140-220 ℃, and more preferably 150-200 ℃.
In a preferred embodiment of the present invention, the preheating temperature of the alicyclic hydrocarbon is 130-200 ℃, preferably 140-190 ℃, and more preferably 150-180 ℃; the preheating temperature of the ammonia and the carrier gas is 140-240 ℃, preferably 160-220 ℃, and more preferably 180-200 ℃.
According to the invention, the alicyclic hydrocarbon, ammonia gas and carrier gas are preheated and mixed into the reaction gas, so that the rapid temperature rise of the system is facilitated, the overall temperature of the reaction gas is accurately controlled, the reaction state is rapidly entered, the problem of increased side reactions caused by overhigh reaction temperature is solved, and meanwhile, the conditions that the reaction temperature is too low, the reaction state cannot be rapidly entered under the process condition, and the reaction is insufficient are avoided.
Preferably, when the cyclohexanol and the cyclohexanone are used for preparing the adiponitrile, the preheating temperature is 180-220 ℃; preheating the carrier gas and the ammonia gas at the temperature of 190 ℃ and 210 ℃, such as 200 ℃;
when the adiponitrile is prepared from the cyclohexene, the preheating temperature is 100-160 ℃; preheating the carrier gas and the ammonia gas at the temperature of 190 ℃ and 210 ℃, such as 200 ℃;
preheating cyclopentanol, cyclopentanone and cyclohexanone at 160 ℃ and 180 ℃; preheating the carrier gas and the ammonia gas at the temperature of 170-190 ℃, such as 180 ℃;
the preheating ensures that main raw materials (alicyclic hydrocarbon and ammonia) participate in the reaction in a gas form, and mainly promotes the reaction, particularly, after the main raw materials are preheated, the main raw materials can enter a reaction system in a gas form and can be fully mixed with other gases, and the mixed gases can quickly react after contacting with a catalyst at a reaction temperature.
And 2, introducing preheated alicyclic hydrocarbon, ammonia and carrier gas into the reactor, and heating and reacting in the presence of a catalyst to obtain mixed gas.
The carrier gas is selected from one or more of air, oxygen-containing nitrogen, oxygen-containing argon and oxygen-containing xenon, and is preferably air, oxygen-containing nitrogen or oxygen. The carrier gas can enable the reverse alicyclic hydrocarbon, the ammonia gas and the catalyst to reach a fluidized state or a state close to a fluidized state, so that the reaction materials are well dispersed in the reaction device, the reverse alicyclic hydrocarbon and the ammonia gas are fully contacted with the catalyst, and the reaction efficiency and the effect are improved.
The invention does not specially limit the reactor, and can lead the reaction to be smoothly carried out, such as a fixed bed reactor and a fluidized bed reactor.
The flow rate of the alicyclic hydrocarbon introduced into the reactor is 1 to 10g/h, preferably 2 to 8g/h, and more preferably 3 to 6 g/h. The flow rate of the alicyclic hydrocarbon is related to the catalyst load, and the amount of the charged alicyclic hydrocarbon is close to the upper limit in the range of the catalyst treatment load, firstly, the reaction efficiency is improved, and secondly, the decomposition amount of the alicyclic hydrocarbon with relatively high concentration in the high-temperature catalyst system is relatively low. Within a reasonable feeding range, the reaction yield and the product quality are increased.
The molar ratio of the ammonia gas to the alicyclic hydrocarbon is (10-22):1, preferably (12-20):1, and more preferably (14-18): 1. The ammonia gas and the carrier gas are matched for use, firstly, the ammonia gas is required to be higher than the theoretical reaction amount (the molar ratio of 2: 1), secondly, after the using amount of the ammonia gas is properly increased, the trend of completely oxidizing and decomposing the alicyclic hydrocarbon is reduced, and simultaneously, the ammoxidation reaction of the terminal carbon of the linear alkane after ring opening is accelerated to generate the cyano group.
The oxidation of oxygen in the carrier gas mainly opens the ring of the alicyclic hydrocarbon and breaks the bond at the active methylene, and if the oxygen in the reaction system is excessive, the oxidation in the system is strong, so that the alicyclic hydrocarbon in the reaction system continues to be oxidized and decomposed after the bond breaking ring opening reaction. The residence time of the carrier is also a means of adjusting the reaction, too long a residence time promotes oxidative decomposition, and short a residence time may not cause bond breaking or ammoxidation.
The molar ratio of the carrier gas to the alicyclic hydrocarbon is (10-35):1, preferably (15-30):1, and more preferably (20-25): 1. The carrier gas can control the residence time of the materials in the catalyst layer by the flow rate of the carrier gas while the alicyclic hydrocarbon, the ammonia gas and the catalyst are fluidized or nearly fluidized, and the residence time is generally controlled to be 1-60s, preferably 3-30s, and more preferably 5-25 s. Too long residence time can cause excessive oxidation of the reaction, produce byproducts, reduce the utilization rate of raw materials, have short residence time, possibly have no bond breaking or ammoxidation reaction, and cannot obtain target products.
The reaction temperature is 305-415 ℃, preferably 320-400 ℃, and more preferably 335-385 ℃. Too high a reaction temperature also leads to excessive oxidation reaction, too low a reaction temperature, incomplete reaction, or failure to obtain the target product.
The catalyst has a catalytic treatment capacity of 1 to 10g of alicyclic hydrocarbon per 100g of catalyst per hour, preferably 2 to 8g of alicyclic hydrocarbon, and more preferably 3 to 6g of alicyclic hydrocarbon. The catalyst used in the invention has high catalytic activity, good reaction selectivity and stable performance, and can stably catalyze the reaction process for a long time.
The reaction pressure is 0.01-0.15MPa, preferably 0.04-0.08 MPa.
And 3, post-treating the mixed gas to obtain the dinitrile compound.
And cooling the reaction gas to be treated to obtain the dinitrile compound in a collecting device. The tail gas mainly contains carrier gas, excessive ammonia and water vapor, and alicyclic hydrocarbon basically completely reacts. The excessive ammonia gas and carrier gas can be recycled after absorbing water vapor. Or the absorption device can be used for absorbing the excessive ammonia gas and then discharging the tail gas. The whole production process generates less three wastes and is environment-friendly.
The collecting device and the tail gas absorption device can be completed by adopting the prior art, for example, a catcher is used for collecting dinitrile compounds, and the acid absorption liquid is used for absorbing excessive ammonia in the tail gas.
The catalyst for preparing the dinitrile compound from the alicyclic hydrocarbon can open the ring of the alicyclic hydrocarbon and complete ammoxidation reaction, so that the dinitrile compound is obtained, the reaction activity of the catalyst is further improved, the selectivity is good, the occurrence of side reactions can be effectively inhibited, and the high-quality dinitrile compound is prepared.
Examples
Example 1
Adding 48g of vanadium pentoxide into 800g of oxalic acid solution with the mass concentration of 22.5 wt%, and stirring for 2 hours to dissolve the vanadium pentoxide to obtain a mixed solution. To the above mixed solution were added 35g of titanium dioxide, 12.8g of ammonium orthomolybdate ((NH)4)2MoO4) 56g of 85.54% strength by weight phosphoric acid solution, stirred for 2 hours and then slowly added technical nickel chloride NiCl containing crystal water2·6H2O9.80 g, 3.2g sodium chloride, stirred for 1 hour, then added SnCl slowly2·2H2O7.60 g and cesium sulfate 10.5g were stirred for 1 hour, and 980g of a 40 wt% silica sol (Shandonghao, silica hydrosol type s 40) was added to obtain a catalyst slurry. And heating the catalyst slurry to evaporate water until the solid content of the system is 45%. And spray-drying and forming the slurry in a spray dryer to obtain the catalyst precursor. The molar ratio of the added metal elements is V, Ti, P, Mo, Cs, Na, Ni and Sn is 1:0.83:0.92:0.12:0.11:0.10:0.08: 0.06.
And (3) roasting the catalyst precursor in a muffle furnace at 300 ℃ for 6 hours, then gradually heating to 650 ℃, preserving heat for 10 hours, and cooling to room temperature to obtain the catalyst I.
100g of catalyst I are charged
Figure BDA0003352612830000121
In a fluidized bed reactor with the height of 600mm, ammonia gas and air are respectively preheated at 200 ℃ and then enter the fluidized bed reactor, cyclohexanol enters the fluidized bed reactor after being gasified at the temperature of 180 ℃, the flow of the gasified cyclohexanol entering the reactor is 4.5g/h, the system pressure in the reactor is 0.05MPa, the reaction temperature is 360 +/-5 ℃, the reaction is carried out in the presence of a catalyst I, wherein the molar ratio of the ammonia gas to the cyclohexanol is about 14:1,the molar ratio of air to cyclohexanol was about 25:1, the catalytic treatment capacity of the catalyst was such that 5.6g of cyclohexanol could be catalytically treated per 100g of catalyst per hour, the residence time of cyclohexanol was 8.3 s. And (3) directly enabling a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, collecting the adiponitrile crude product obtained by trapping, weighing, and detecting the content and the moisture. Through gas chromatography tests, the conversion rate of cyclohexanol is 99.3%, the selectivity of adiponitrile is 97.8%, and a gas chromatogram is shown in fig. 1, wherein after test solvent methanol is removed, the content of adiponitrile in the product is 98.794%.
The service life of the catalyst I is 2932h after being tested.
Example 2
Adding 48g of vanadium pentoxide into 800g of oxalic acid solution with the mass concentration of 22.5 wt%, and stirring for 2 hours to dissolve the vanadium pentoxide to obtain a mixed solution. To the above mixed solution were added 30g of titanium dioxide, 10.3g of ammonium orthomolybdate ((NH)4)2MoO4) 68.3g of 85.54% strength by weight phosphoric acid solution, stirred for 2 hours and slowly added to the technical nickel chloride NiCl containing crystal water2·6H2O4.80 g, stirred for 1 hour, and then SnCl was slowly added2·2H2O7.60 g and cesium sulfate 15.3g were stirred for 1 hour, and 980g of silica sol having a mass concentration of 40 wt% was further added to obtain a catalyst slurry. And heating the catalyst slurry to evaporate water until the solid content of the system is 45%. And spray-drying and forming the slurry in a spray dryer to obtain the catalyst precursor. The molar ratio of the added metal elements is V, Ti, P, Mo, Cs, Ni and Sn is 1:0.71:1.12:0.10:0.16:0.04: 0.06.
And (3) roasting the catalyst precursor in a muffle furnace at 300 ℃ for 3 hours, gradually heating to 650 ℃, preserving heat for 8 hours, and cooling to room temperature to obtain a catalyst II.
100g of catalyst II are charged
Figure BDA0003352612830000131
In a fluidized bed reactor with the height of 600mm, ammonia gas and air enter the fluidized bed reactor after being preheated at 200 ℃, cyclohexanone enters the fluidized bed reactor after being gasified at the temperature of 180 ℃, and the cyclohexanone enters the fluidized bed reactor after being gasifiedThe flow of the cyclohexanone into the reactor is 4.2g/h, the system pressure in the reactor is 0.05MPa, the reaction temperature is 380 +/-5 ℃, the reaction is carried out in the presence of a catalyst II, wherein the molar ratio of ammonia to the cyclohexanone is about 18:1, the molar ratio of air to the cyclohexanone is about 20:1, the catalytic treatment capacity of the catalyst is that 5.3g of cyclohexanone can be catalytically treated per 100g of the catalyst per hour, and the retention time of the cyclohexanone is 7.5 s. And (3) directly enabling a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, collecting the adiponitrile crude product obtained by trapping, weighing, and detecting the content and the moisture. Through gas chromatography test, the conversion rate of cyclohexanone is 98.9%, and the selectivity of adiponitrile is 94.7%.
The service life of the catalyst II is 3038h through testing.
Example 3
Adding 48g of vanadium pentoxide into 800g of oxalic acid solution with the mass concentration of 22.5 wt%, and stirring for 2 hours to dissolve the vanadium pentoxide to obtain a mixed solution. To the above mixed solution were added 42.2g of titanium dioxide, 5.2g of ammonium orthomolybdate ((NH)4)2MoO4) 67.7g of 85.54 wt% phosphoric acid solution, stirring for 2 hours, slowly adding 4.3g of potassium chloride, stirring for 1 hour, and slowly adding SnCl2·2H2O7.60 g and cesium sulfate 7.6g were stirred for 1 hour, and 980g of silica sol having a mass concentration of 40 wt% was further added to obtain a catalyst slurry. And heating the catalyst slurry to evaporate water until the solid content of the system is 45%. And spray-drying and forming the slurry in a spray dryer to obtain the catalyst precursor. The molar ratio of the added metal elements is V: Ti: P: Mo: Cs: K: Sn ═ 1:1.00:1.12:0.05:0.08:0.11: 0.06.
And (3) roasting the catalyst precursor in a muffle furnace at 300 ℃ for 3 hours, then gradually heating to 650 ℃, preserving heat for 10 hours, and cooling to room temperature to obtain a catalyst III.
100g of catalyst III are charged
Figure BDA0003352612830000141
In a fluidized bed reactor with the height of 600mm, ammonia gas and air enter the fluidized bed reactor after being preheated at 200 ℃, and cyclohexene is gasified at the temperature of 150 DEG CThen the mixture enters a fluidized bed reactor, the flow of the gasified cyclohexene entering the reactor is 4.6g/h, the system pressure in the reactor is 0.05MPa, the mixture reacts at the reaction temperature of 360 +/-5 ℃ in the presence of a catalyst III, wherein the molar ratio of ammonia to cyclohexene is about 16:1, the molar ratio of air to cyclohexene is about 20:1, the catalytic treatment capacity of the catalyst is that 6.0g of cyclohexene can be catalytically treated per 100g of catalyst per hour, and the residence time of the cyclohexene is 7.8 s. And (3) directly enabling a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, collecting the adiponitrile crude product obtained by trapping, weighing, and detecting the content and the moisture. Through gas chromatography tests, the conversion rate of cyclohexene is 99.2%, and the selectivity of adiponitrile is 94.2%.
The service life of the catalyst III is 2881 h.
Example 4
100g of catalyst III are charged
Figure BDA0003352612830000151
In a fluidized bed reactor with the height of 600mm, ammonia gas and oxygen gas are respectively preheated at 200 ℃ and then enter the fluidized bed reactor, cyclohexene is gasified at the temperature of 150 ℃ and then enters the fluidized bed reactor, the flow of the gasified cyclohexene entering the reactor is 4.6g/h, the system pressure in the reactor is 0.05MPa, the reaction is carried out in the presence of a catalyst III at the reaction temperature of 340 +/-5 ℃, wherein the molar ratio of the ammonia gas to the cyclohexene is about 16:1, the molar ratio of the oxygen gas to the cyclohexene is about 20:1, the catalytic treatment capacity of the catalyst is that 6.0g of cyclohexene can be catalytically treated per 100g of the catalyst per hour, and the retention time of the cyclohexene is 7.8 s. And (3) directly enabling a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, collecting the adiponitrile crude product obtained by trapping, weighing, and detecting the content and the moisture. Through gas chromatography tests, the conversion rate of cyclohexene is 99.8%, and the selectivity of adiponitrile is 97.8%.
The service life of the catalyst III is 3213h after the test.
Example 5
Adding 48g of vanadium pentoxide into 800g of oxalic acid solution with the mass concentration of 22.5 wt%, stirring for 2 hours to dissolve the vanadium pentoxide to obtainThe solution was mixed. To the above mixed solution were added 19g of titanium dioxide, 8.3g of ammonium orthomolybdate ((NH)4)2MoO4) 67.7g of 85.54% strength by weight phosphoric acid solution, stirred for 2 hours and slowly added with 1.8g of sodium chloride and technical nickel chloride NiCl containing crystal water2·6H2O12.6 g, stirred for 1 hour, then SnCl was slowly added2·2H2O7.60 g and cesium sulfate 6.7g were stirred for 1 hour, and 980g of silica sol having a mass concentration of 40 wt% was further added to obtain a catalyst slurry. And heating the catalyst slurry to evaporate water until the solid content of the system is 45%. And spray-drying and forming the slurry in a spray dryer to obtain the catalyst precursor. The molar ratio of the added metal elements is V, Ti, P, Mo, Cs, Na, Ni and Sn is 1:0.45:1.12:0.08:0.07:0.06:0.10: 0.06.
And (3) roasting the catalyst precursor in a muffle furnace at 300 ℃ for 3 hours, then gradually heating to 650 ℃, preserving heat for 10 hours, and cooling to room temperature to obtain a catalyst V.
100g of catalyst V were charged
Figure BDA0003352612830000161
In a fluidized bed reactor with the height of 600mm, ammonia gas and air enter the fluidized bed reactor after being preheated at 180 ℃ respectively, cyclopentanol enters the fluidized bed reactor after being gasified at the temperature of 160 ℃, the flow of the gasified cyclopentanol entering the reactor is 4.8g/h, the system pressure in the reactor is 0.05MPa, the mixture reacts at the reaction temperature of 340 +/-5 ℃ in the presence of a catalyst V, wherein the molar ratio of the ammonia gas to the cyclopentanol is about 15:1, the molar ratio of the air to the cyclopentanol is about 20:1, the catalytic treatment capacity of the catalyst is 6.1g of cyclopentanol per 100g of the catalyst per hour, and the retention time of the cyclopentanol is 8.1 s. And (3) directly enabling a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, collecting a crude glutaronitrile product obtained by trapping, weighing, and detecting the content and the moisture. Through gas chromatography tests, the conversion rate of the cyclopentanol is 99.5 percent, and the selectivity of the glutaronitrile is 97.9 percent. The gas chromatogram is shown in FIG. 2, and the product glutaronitrile content is 98.428% after the removal of the test solvent methanol.
The service life of the tested catalyst V was 2917 h.
Example 6
Adding 48g of vanadium pentoxide into 800g of oxalic acid solution with the mass concentration of 22.5 wt%, and stirring for 2 hours to dissolve the vanadium pentoxide to obtain a mixed solution. To the above mixed solution were added 15.2g of titanium dioxide, 8.3g of ammonium orthomolybdate ((NH)4)2MoO4) 72g of 85.54% strength by weight phosphoric acid solution, stirred for 2 hours and slowly added to the technical nickel chloride NiCl containing crystal water2·6H2O4.81 g, stirred for 1 hour and then added SnCl slowly2·2H2O3.62 g and cesium sulfate 12.5g were stirred for 1 hour, and 980g of silica sol having a mass concentration of 40 wt% was further added to obtain a catalyst slurry. And heating the catalyst slurry to evaporate water until the solid content of the system is 45%. And spray-drying and forming the slurry in a spray dryer to obtain the catalyst precursor. The molar ratio of the added metal elements is V, Ti, P, Mo, Cs, Ni and Sn is 1:0.36:1.18:0.08:0.13:0.04: 0.03.
And (3) roasting the catalyst precursor in a muffle furnace at 300 ℃ for 3 hours, gradually heating to 650 ℃, preserving heat for 8 hours, and cooling to room temperature to obtain a catalyst VI.
100g of catalyst VI are charged
Figure BDA0003352612830000171
In a fluidized bed reactor with the height of 600mm, ammonia gas and air are preheated at 180 ℃ respectively and then enter the fluidized bed reactor, cyclopentanone is gasified at the temperature of 150 ℃ and then enters the fluidized bed reactor, the flow of the gasified cyclopentanone entering the reactor is 4.6g/h, the system pressure in the reactor is 0.05MPa, the mixture reacts at the reaction temperature of 360 +/-5 ℃ in the presence of a catalyst VI, wherein the molar ratio of the ammonia gas to the cyclopentanone is about 16:1, the molar ratio of the air to the cyclopentanone is about 20:1, the catalytic treatment capacity of the catalyst is 5.9g of cyclopentanone per hour per 100g of the catalyst, and the retention time of the cyclopentanone is 8.3 s. And (3) directly enabling a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, collecting a crude glutaronitrile product obtained by trapping, weighing, and detecting the content and the moisture. Through the gas phaseAccording to a chromatographic test, the conversion rate of cyclopentanone is 97.2 percent, and the selectivity of glutaronitrile is 95.6 percent.
The service life of the catalyst VI is 2723 h.
Example 7
Adding 48g of vanadium pentoxide into 800g of oxalic acid solution with the mass concentration of 22.5 wt%, and stirring for 2 hours to dissolve the vanadium pentoxide to obtain a mixed solution. To the above mixed solution were added 45.2g of titanium dioxide, 11.4g of ammonium orthomolybdate ((NH)4)2MoO4) 78.6g of 85.54% strength by weight phosphoric acid solution, stirred for 2 hours and slowly added to the technical nickel chloride NiCl containing crystal water2·6H2O5.22 g, stirred for 1 hour, then 16.4g of chromium trioxide and 21.0g of cesium sulfate were slowly added thereto, stirred for 1 hour, and 980g of silica sol having a mass concentration of 40 wt% was further added to obtain a catalyst slurry. And heating the catalyst slurry to evaporate water until the solid content of the system is 45%. And spray-drying and forming the slurry in a spray dryer to obtain the catalyst precursor. The molar ratio of the added metal elements is V, Ti, P, Mo, Cs, Ni and Cr is 1:1.07:1.30:0.11:0.22:0.04: 0.31.
And (3) roasting the catalyst precursor in a muffle furnace at 300 ℃ for 3 hours, gradually heating to 650 ℃, preserving heat for 8 hours, and cooling to room temperature to obtain the catalyst VII.
100g of catalyst VII was charged
Figure BDA0003352612830000181
In a fluidized bed reactor with the height of 600mm, ammonia gas and air are respectively preheated at 180 ℃ and then enter the fluidized bed reactor, cyclohexanone is gasified at the temperature of 150 ℃ and then enters the fluidized bed reactor, the flow of the gasified cyclohexanone entering the reactor is 4.8g/h, the system pressure in the reactor is 0.05MPa, the mixture reacts at the reaction temperature of 340 +/-5 ℃ in the presence of a catalyst VII, wherein the molar ratio of the ammonia gas to the cyclohexanone is about 16:1, the molar ratio of the air to the cyclohexanone is about 20:1, the catalytic treatment capacity of the catalyst is that 5.6g of cyclohexanone can be catalytically treated per 100g of the catalyst per hour, and the retention time of the cyclohexanone is 8.5 s. The products desorbed from the surface of the catalyst directly enter and are trapped along with the reaction gasAnd collecting the obtained crude glutaronitrile product in the device, weighing, and detecting the content and the moisture. Through gas chromatography test, the conversion rate of cyclohexanone is 98.2%, and the selectivity of glutaronitrile is 96.9%.
The service life of the tested catalyst VII is 2710 h.
Comparative example
Comparative example 1
Mixing 1mmol cyclohexanol with 0.050g Rh/MnO2(Rh-supporting amount: 0.01mol) was charged into a 20mL lined reactor, 10mL acetonitrile was added, and 3MPa NH was charged3And 0.1MPa air, heating to 30 ℃ by a program, reacting for 48 hours, cooling, and carrying out qualitative analysis on the obtained sample by gas chromatography-mass spectrometry, wherein quantitative analysis is realized by gas chromatography. The conversion of cyclohexanol was tested to 73.0% and selectivity to adipic acid 95.2%. The isolation yield of adiponitrile was 50.5%, and the purity thereof was 99.1% by gas chromatography.
Comparative example 2
Adding 100mL of cyclohexene, 450mL of concentrated ammonia water (industrial ammonia water, the mass concentration is about 25-28%), 3mmol of 3, 5-bis (trifluoromethyl) -4-n-butylbenzene suntan acid, heating and reacting at 130 ℃ in 1MPa of pure oxygen for 24 hours, and analyzing the yield of the adiponitrile product by gas chromatography to be 87%.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A catalyst for preparing dinitrile compounds from alicyclic hydrocarbon is a V-Ti-P-Mo-Cs catalyst which takes vanadium, titanium, phosphorus, molybdenum and cesium as basic active elements.
2. The catalyst according to claim 1,
the alicyclic hydrocarbon is selected from one or more of alicyclic alcohol, alicyclic ketone, cycloolefine and cycloparaffin, preferably alicyclic alcohol, alicyclic ketone or cycloolefine; the dinitrile compound is glutaronitrile, adiponitrile or pimelonitrile, preferably glutaronitrile or adiponitrile;
the catalyst is prepared by dissolving or dispersing a compound containing component elements in a solution to obtain a mixed solution, removing the solvent, drying to obtain a catalyst precursor, and roasting the catalyst precursor in an air atmosphere to obtain the V-Ti-P-Mo-Cs catalyst.
3. The catalyst of claim 2, further comprising an auxiliary element comprising one or more of sodium, potassium, nickel, tin, and chromium.
4. The catalyst according to claim 3, wherein the auxiliary element is selected from one of the following groups:
(1) combinations of sodium, nickel, tin; the molar weight ratio is (0.03-0.20): (0.04-0.20): 0.02-0.09), preferably (0.06-0.10): 0.08-0.10): 0.05-0.07;
(2) a combination of nickel and tin; the molar weight ratio is (0.03-0.05): 0.01-0.1, preferably (0.03-0.05): 0.03-0.06);
(3) a combination of potassium and tin; the molar weight ratio is (0.04-0.2): (0.05-0.07), preferably (0.08-0.15): 0.05-0.07);
(4) a combination of nickel and chromium; the molar weight ratio is (0.03-0.05): 0.15-0.45, preferably (0.03-0.05): 0.25-0.35);
the molar ratio of the vanadium source to the total amount of the auxiliary element source is 1 (0.03-0.55), preferably 1 (0.05-0.45); wherein the molar amounts of the vanadium source and the auxiliary element source are based on the molar amount of the component elements contained therein.
5. A method for preparing dinitrile compounds by catalysis of the catalyst according to any one of claims 1 to 4, wherein the method comprises the step of synthesizing dinitrile compounds by reacting alicyclic hydrocarbons as starting materials with ammonia in the presence of the catalyst, preferably in a carrier gas environment.
6. The method according to claim 5, characterized in that it comprises in particular the steps of:
step 1, respectively preheating alicyclic hydrocarbon, ammonia and carrier gas;
step 2, introducing preheated alicyclic hydrocarbon, ammonia and carrier gas into a reactor, and heating and reacting in the presence of a catalyst to obtain mixed gas;
and 3, post-treating the mixed gas to obtain the dinitrile compound.
7. The method as claimed in claim 6, wherein the alicyclic hydrocarbon, ammonia and carrier gas are preheated at a temperature of 130-240 ℃, preferably 140-220 ℃, and more preferably 150-200 ℃ in step 1.
8. The method according to claim 6, wherein, in step 2,
the carrier gas is selected from one or more of air, oxygen-containing nitrogen, oxygen-containing argon and oxygen-containing xenon, and is preferably air, oxygen-containing nitrogen or oxygen;
the flow rate of the alicyclic hydrocarbon introduced into the reactor is 1 to 10g/h, preferably 2 to 8g/h, and more preferably 3 to 6 g/h.
9. The method according to claim 6, wherein, in step 2,
the molar ratio of the ammonia gas to the alicyclic hydrocarbon is (10-22):1, preferably (12-20):1, more preferably (14-18): 1;
the molar ratio of the carrier gas to the alicyclic hydrocarbon is (10-35):1, preferably (15-30):1, more preferably (20-25): 1;
the reaction temperature is 305-415 ℃, preferably 320-400 ℃, and more preferably 335-385 ℃.
10. The method according to claim 6, wherein, in step 2,
when the cyclohexanol is used for preparing adiponitrile or the cyclopentanol is used for preparing glutaronitrile, the catalyst is a V-Ti-P-Mo-Cs-Na-Ni-Sn catalyst, and the molar ratio of the raw materials of the components is 1 (0.1-1.5), 0.1-1.90, (0.15-0.22), 0.17-0.4, (0.03-0.20), 0.04-0.20 and 0.02-0.09;
when the adiponitrile is prepared from cyclohexanone or the glutaronitrile is prepared from cyclopentanone, the catalyst is a V-Ti-P-Mo-Cs-Ni-Sn catalyst, and the molar ratio of the raw materials of the components is 1 (0.1-1.5), (0.1-1.90), (0.15-0.22), (0.17-0.4), (0.03-0.05), (0.01-0.1);
when the adiponitrile is prepared from cyclohexene, the catalyst is a V-Ti-P-Mo-Cs-K-Sn catalyst, and when the adiponitrile is prepared, the molar ratio of the raw materials of the components is 1 (0.1-1.5): (0.1-1.90): 0.15-0.22): 0.17-0.4): 0.04-0.2): 0.05-0.07;
when the glutaronitrile is prepared from cyclohexanone, the catalyst is a V-Ti-P-Mo-Cs-Ni-Cr catalyst, and when the glutaronitrile is prepared, the molar ratio of the raw materials of the components is 1 (0.1-1.5) (0.1-1.90) (0.15-0.22) (0.17-0.4) (0.03-0.05) (0.15-0.45).
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CN115093346A (en) * 2022-07-15 2022-09-23 西安交通大学 Method for preparing nitrile compounds from different substituted cycloalkanones in one step
CN117431276A (en) * 2023-09-27 2024-01-23 江苏维尤纳特精细化工有限公司 Dinitrile refining method

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US4070393A (en) * 1975-03-18 1978-01-24 Sun Ventures, Inc. Ammoxidation process
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CN115093346A (en) * 2022-07-15 2022-09-23 西安交通大学 Method for preparing nitrile compounds from different substituted cycloalkanones in one step
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