CN117399059B - Preparation method of hydrocyanic acid - Google Patents

Preparation method of hydrocyanic acid Download PDF

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CN117399059B
CN117399059B CN202311353883.XA CN202311353883A CN117399059B CN 117399059 B CN117399059 B CN 117399059B CN 202311353883 A CN202311353883 A CN 202311353883A CN 117399059 B CN117399059 B CN 117399059B
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耿海涛
耿铭芮
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Beijing Daosike Energy Equipment Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/02—Preparation, separation or purification of hydrogen cyanide
    • C01C3/0208—Preparation in gaseous phase
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a preparation method of hydrocyanic acid, which comprises the following steps: s1, preparing a porous magnetic SiO2 nanosphere; s2, surface modification of the wrinkled graphene oxide; s3, fixing the beta-zeolite molecular sieve nanocrystalline; s4, modifying polydopamine; s5, depositing Co/V doped Fe-Mo oxide. Under the action of the prepared catalyst for preparing hydrocyanic acid by methanol ammoxidation, the method for preparing hydrocyanic acid by preparing hydrocyanic acid through catalytic oxidation reaction of methanol, ammonia and oxygen can greatly improve the efficiency of the preparation reaction by adopting a proper catalyst, so that the yield of hydrocyanic acid is obviously improved, the selectivity is greatly improved, the methanol conversion rate is high, the catalyst can be repeatedly used, the production cost is reduced, and the reaction process is simple and mild, thereby having wide application prospect.

Description

Preparation method of hydrocyanic acid
Technical Field
The invention relates to the technical field of catalytic chemistry, in particular to a preparation method of hydrocyanic acid.
Background
Hydrocyanic acid (HCN) has many applications as a reactant or as a synthetic intermediate in different synthetic pathways. In particular, it is a key reactant for the preparation of acetone cyanohydrin, a synthetic intermediate for the production of methyl methacrylate MAM (base monomer of thermoplastic polymers such as PMMA (Altuglas, plexiglas)). Hydrocyanic acid is also used in the synthesis of methionine, or adiponitrile, which is a synthetic intermediate for the preparation of polyamide 6.6 (Nylon) and many chelating agents. Sodium cyanide, derivatives of hydrocyanic acid, also have many applications in the chemical industry.
The production method of hydrocyanic acid is mainly divided into two types of direct synthesis method and acrylonitrile byproduct method, and the direct synthesis method is divided into four types of method of Anshi, BMA, light oil cracking method and methanol ammoxidation method. Among them, the Ann method, BMA method and light oil cracking method are carried out at high temperature by using natural gas or petroleum as raw materials. The acrylonitrile byproduct method is byproduct HCN obtained by the process of preparing acrylonitrile by propylene ammoxidation with propylene as raw material. With the progressive progress of the propylene ammoxidation process level, the amount of hydrocyanic acid, a corresponding byproduct, gradually decreases. The methanol ammoxidation method using coal chemical industry as the source has the advantages of low cost and easy obtaining of raw materials, low reaction temperature, high yield and the like, and has wide development prospect.
At present, catalysts reported by foreign patents for preparing hydrogen cyanide by methanol ammoxidation are mainly divided into four types of Mo, sb, mn and B-P oxides. Wherein the patent report of the Mo series catalyst is mainly Fe/Mo two metal oxide catalyst (US 4425260) of Monsanto company and Bi-rare earth-Mo-SiO of The standard oil company company 2 Catalysts (US 4485079), moBiFeXYZO catalyst (US 3911089) from Sumitomo Chemical Company. In addition, the national institute of vinca strain also researches two metal oxide catalysts of methanol ammoxidation to prepare hydrogen cyanate Mo-Fe at the end of 80 th century.
The methanol ammoxidation to prepare the hydrocyanic acid is a strong exothermic reaction, and a fluidized bed reactor which is easy to remove heat is preferably adopted. Since the catalyst in the fluidized bed reactor requires high attrition resistance, the catalyst needs to contain a sufficient amount of support (binder) to ensure good mechanical properties of the catalyst. After a certain amount of carrier (adhesive) is added into Mo-Fe two metal oxide catalyst, the activity and selectivity of the catalyst can be greatly reduced, and by-product CO 2 The selectivity and yield of the product HCN are greatly reduced. In order to obtain high conversion of methanol, the reaction temperature has to be increased (generally above 420 ℃). The ammonia oxidation reaction is carried out at high temperature, so that the loss of active component Mo in the catalyst is easy to cause the stability of the catalyst to be reduced, thereby reducing the industrial application value of the catalyst and being unfavorable for the popularization of the technology.
CN1112243 is a research on a catalyst moabibmectectedqerfxgyhhoz, in which the catalyst contains 10% or more of molybdenum, bismuth and at least one element selected from iron and cerium, and when tellurium is incorporated into the catalyst, the catalyst is calcined at around 700 ℃ for about 3 hours, so that the activity of the catalyst can be maintained for a prolonged period of time while preventing the loss of molybdenum and tellurium. The catalyst activity experiment is carried out under the conditions that the methanol ammonia-oxygen ratio is 1:1:1.2, the reaction temperature is 420 ℃, the contact time is 0.3s, the catalyst stability is good, the yield is 88.5% after 50 hours, and the yield is 88.3% after 500 hours, and the reduction is not great. However, the overall yield of the catalyst is not ideal at low ammonia to oxygen ratios.
The catalyst component used in US4461752 is Fe a Cu b Sb c Mo d Me e Te f Q g O h (SiO 2 ) l The reaction condition is that the ratio of methanol to ammonia and oxygen is 1:1.1:2, when the contact time is 2-3s, the yield of hydrocyanic acid can reach 91%, and when the contact time is 4s, the yield of hydrocyanic acid is obviously reduced and can only reach 76%.
Catalyst Fe in CN1097556 a Sb b P c V d Mo e Cu f W g X h Y i Z j O k (SiO 2 ) 1 When the ratio of methanol to ammonia and oxygen is 1:1:1.5, the yield of hydrocyanic acid is 94.5%. The catalyst control experiment was performed to increase the reaction contact time of the catalyst and a significant decrease in yield was observed with increasing reaction time. In addition, the catalyst has a complex structure, and the performance of the catalyst is degraded when the preparation composition deviates slightly from an empirical formula, so that the yield of hydrocyanic acid is reduced.
US5158787 discloses a catalyst Fe a Cu b Sb c V d Mo e W f P g Q h R i S j O k (SiO 2 ) l In experiments for verifying the catalyst in the literature, the oxygen ratio and the ammonia ratio are only in a rough range, and detailed researches are not carried out, so that the final hydrocyanic acid yield is 80.4-90.1%.
Thus, the performance of the current catalysts for preparing hydrocyanic acid is still to be further improved.
Disclosure of Invention
The invention aims to provide a preparation method of hydrocyanic acid, which can greatly improve the efficiency of the preparation reaction by adopting a proper catalyst, so that the yield of hydrocyanic acid is obviously improved, the selectivity is greatly improved, the methanol conversion rate is high, the catalyst can be reused, the production cost is reduced, and the reaction process is simple and mild, thereby having wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a catalyst for preparing hydrocyanic acid by methanol ammoxidation, which comprises the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: dissolving ferric salt and ferrous salt in water, adding an emulsifying agent and a pore-forming agent, and uniformly mixing to obtain a water phase; dissolving alkyl orthosilicate in an organic solvent to obtain an oil phase; dropwise adding the water phase into the oil phase, emulsifying, dropwise adding ammonia water, heating and stirring for reaction, centrifuging, washing, drying, calcining to obtain porous magnetic SiO 2 A nanosphere;
s2, surface modification of the wrinkled graphene oxide: dissolving graphene oxide in water, and adding the porous magnetic SiO prepared in the step S1 2 Nanospheres are stirred and mixed uniformly, and spray-dried to prepare the pleated graphene oxide modified porous magnetic SiO 2 A nanosphere;
s3, fixing beta-zeolite molecular sieve nanocrystals: dissolving pseudo-boehmite in water, adding tetraethyl ammonium hydroxide, white carbon black and the pleated graphene oxide modified porous magnetic SiO prepared in the step S2 2 Nanospheres, heating and stirring to react to prepare the beta-zeolite molecular sieve nanocrystalline fixed fold porous magnetic SiO 2 A nanosphere;
s4, modifying polydopamine: the beta-zeolite molecular sieve nanocrystalline prepared in the step S3 is fixed to form the wrinkled porous magnetic SiO 2 Adding nanospheres into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, centrifuging, washing and drying to obtain modified SiO 2 A nanosphere;
s5, depositing Co/V doped Fe-Mo oxide: dissolving molybdate in water to obtain solution A; dissolving ferric salt, cobalt salt and vanadium salt in water to obtain solution B; adding the liquid A into the liquid B, and adding the modified SiO prepared in the step S4 2 And (3) dropwise adding ammonia water into the nanospheres, heating and stirring for reaction, centrifuging, washing and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
As a further improvement of the invention, the molar ratio of the ferric salt to the ferrous salt in the step S1 is 2:1, the ferric salt is at least one of ferric chloride and ferric nitrate, the ferrous salt is at least one of ferrous chloride and ferrous nitrate, the emulsifying agent is at least one of span-20, span-40, span-60, span-80, tween-20, tween-40, tween-60 and Tween-80, the pore-forming agent is at least one of hexadecyl trimethyl ammonium bromide and ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO106, the mass ratio of the alkyl orthosilicate, the ferric salt, the emulsifying agent and the pore-forming agent is 25-35:12-15:1-2:0.5-1, the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, the dropwise adding ammonia water to the solution pH value is 8.5-9, the temperature of the heating and stirring reaction is 65-75 ℃ for 3-5h.
As a further improvement of the present invention, the graphene oxide, porous magnetic SiO, described in step S2 2 The mass ratio of the nanospheres is 12-15:25-30, the spray drying condition is that the air inlet temperature is 85-100 ℃, the air outlet temperature is 40-70 ℃, and the evaporation water amount is 1700-2200mL/h.
As a further improvement of the present invention, the pseudo-boehmite, tetraethylammonium hydroxide, white carbon black and pleated graphene oxide modified porous magnetic SiO in step S3 2 The mass ratio of the nanospheres is 2-3:4.5-6.5:7-10:12-15, and in the heating and stirring reaction, the temperature of a heater is 110-130 ℃, and the reaction time is 18-20h.
As a further improvement of the present invention, the beta zeolite molecular sieve nanocrystalline immobilized pleated porous magnetic SiO in step S4 2 The mass ratio of the nanospheres to the dopamine hydrochloride to the catalyst is 15-20:7-10:0.5-1, the catalyst is Tris-HCl solution with pH=8.5-9, the temperature of the heating and stirring reaction is 40-50 ℃, and the time is 2-4h.
As a further improvement of the present invention, the molybdate in step S5 is (NH) 4 ） 6 Mo 7 O 24 The ferric salt is ferric nitrate, ferric sulfate or ferric chloride, the cobalt salt is cobalt chloride or cobalt nitrate, the vanadium salt is vanadium chloride, and the molybdate, ferric salt, cobalt salt, vanadium salt and modified SiO 2 The mass ratio of the nanospheres is 25-30:98-105:3-5:2-4:100-120, dropwise adding ammonia water until the pH value of the solution is 2-2.5, heating and stirring to react at 90-100 ℃ for a period of time2-4h.
The invention further protects the catalyst for preparing hydrocyanic acid by methanol ammoxidation, which is prepared by the preparation method.
The invention further provides a preparation method of hydrocyanic acid, which enables methanol, ammonia and oxygen to undergo catalytic oxidation reaction under the action of the catalyst to obtain the hydrocyanic acid.
As a further improvement of the present invention, the process uses a fixed bed reactor or a fluidized bed reactor for the reaction.
As a further improvement of the invention, the molar ratio of methanol, ammonia and oxygen is 1: (0.95-1.25): (9.5-13), wherein the pressure of the catalytic oxidation reaction is 0.2-0.4MPa, the weight space velocity is 0.05-0.45/h, and the reaction temperature is 395-405 ℃.
The invention has the following beneficial effects:
the Fe-Mo catalyst prepared by the common coprecipitation method has the problems of large loss and high cost, and the surface coating of the catalyst obtained by the impregnation method is unstable and easy to fall off, so that the catalytic life is greatly shortened.
Firstly, after water-in-oil emulsification, dropwise adding ammonia water to perform sol-gel reaction, forming a shell layer on an oil-water interface by using alkyl orthosilicate, and wrapping magnetic ferroferric oxide in a nano microsphere, so that the nano microsphere has magnetism, separation after later reaction and repeated use of the catalyst are facilitated, and meanwhile, the magnetic ferroferric oxide is also beneficial to improving the catalytic activity of the catalyst; meanwhile, under the action of a pore-forming agent, the prepared porous magnetic SiO 2 The nanospheres contain rich pores, the specific surface area is increased, and active catalytic sites are improved.
Further, the prepared porous magnetic SiO 2 The nanospheres are added into graphene oxide solution, and the liquid drop volume is rapidly contracted under the action of spray drying, so that the graphene oxide is wrapped on the porous magnetic SiO 2 The nanosphere surface and the fold structure are formed, so that the specific surface area of the carrier is further increased, the catalytic active site is greatly improved, and a larger sedimentation is provided for the subsequent catalyst depositionSites of deposition.
The beta zeolite has proper acidity catalysis, unique topological structure and higher silicon/aluminum mole ratio, has good heat stability, acid resistance, coking resistance and catalytic energy in catalytic reaction, and the beta zeolite active molecular sieve nanocrystalline prepared by the invention has microstructure similar to the beta zeolite, has smaller geometric dimension, can be used as an active center of oxidation catalytic reaction, and is used for preparing the pleated graphene oxide modified porous magnetic SiO before 2 The folded pore canal of the nanosphere is subjected to microscopic modification, after the surface is subjected to polydopamine modification, active groups such as rich hydroxyl, amino, carboxyl and the like can be reacted with subsequent hydrothermal precipitation of ammonium molybdate and ferric salt to provide reaction sites, and cobalt ions and vanadium ions can be stabilized through chelation, so that uniform Co and V doping and Fe-Mo oxide deposition are achieved, under the doping action of Co and V, the activity of Fe-Mo oxide on methanol ammoxidation catalysis can be promoted, and the doping catalysis of the two has a synergistic action;
due to the effects of hydrogen bonding and complexation, the catalyst is not easy to fall off, and the catalyst molding operation is not needed, so that the specific surface area of the prepared catalyst is increased, the selectivity and the catalytic efficiency of hydrocyanic acid reaction are greatly improved, the efficiency of preparation reaction is greatly improved, the catalyst can be recycled after being used, the reaction cost is greatly reduced, and wide industrial application can be realized.
The preparation method of hydrocyanic acid can greatly improve the efficiency of the preparation reaction by adopting a proper catalyst, so that the yield of hydrocyanic acid is obviously improved, the selectivity is greatly improved, the methanol conversion rate is high, the catalyst can be reused, the production cost is reduced, and the reaction process is simple and mild, thereby having wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The graphene oxide is industrial-grade graphene oxide purchased from Jiangsu Xianfeng nano materials science and technology Co.
Example 1
The embodiment provides a preparation method of a catalyst for preparing hydrocyanic acid by methanol ammoxidation, which comprises the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: dissolving 12 parts by weight of ferric chloride and ferrous chloride in 200 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 1 part by weight of an emulsifier and 0.5 part by weight of an ethylene oxide-propylene oxide triblock copolymer PEO106-PPO70-PEO106, and uniformly stirring for 10 minutes to prepare a water phase; dissolving 25 parts by weight of methyl orthosilicate in 200 parts by weight of methylene dichloride to obtain an oil phase; dropwise adding the water phase into the oil phase under the protection of nitrogen, emulsifying for 15min at 10000r/min, dropwise adding 22wt% ammonia water until the pH value of the solution is 8.5, heating to 65 ℃, stirring for reaction for 3h, centrifuging, washing with deionized water, drying, calcining for 2h at 400 ℃ under the protection of nitrogen, and obtaining the porous magnetic SiO 2 A nanosphere;
the emulsifier is a mixture of tween-80 and span-80 according to a mass ratio of 1:1;
s2, surface modification of the wrinkled graphene oxide: 12 parts by weight of graphene oxide is dissolved in 200 parts by weight of water, and 25 parts by weight of porous magnetic SiO prepared in the step S1 is added 2 Nanospheres are stirred and mixed for 20min, and spray-dried to prepare the pleated graphene oxide modified porous magnetic SiO 2 A nanosphere;
the spray drying condition is that the air inlet temperature is 85 ℃, the air outlet temperature is 40 ℃ and the evaporation water quantity is 1700mL/h;
s3, fixing beta-zeolite molecular sieve nanocrystals: 2 parts by weight of pseudo-boehmite is dissolved in water, and 4.5 parts by weight of tetraethylammonium hydroxide, 7 parts by weight of white carbon black and 12 parts by weight of the pleated graphene oxide modified porous magnetic SiO prepared in the step S2 are added 2 The nanospheres are heated, stirred and reacted, the temperature of a heater is 110 ℃, the reaction time is 18 hours, the nanospheres are centrifuged, washed by deionized water and dried, and the beta is preparedPleated porous magnetic SiO immobilized by zeolite molecular sieve nanocrystals 2 A nanosphere;
s4, modifying polydopamine: 15 parts by weight of beta-zeolite molecular sieve nanocrystalline immobilized pleated porous magnetic SiO prepared in step S3 2 Adding the nanospheres into water, adding 7 parts by weight of dopamine hydrochloride and 0.5 part by weight of catalyst, heating to 40 ℃, stirring and reacting for 2 hours, centrifuging, washing with deionized water, and drying to obtain modified SiO 2 A nanosphere;
the catalyst is Tris-HCl solution with pH=8.5;
s5, depositing Co/V doped Fe-Mo oxide: 25 parts by weight (NH 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 98 parts by weight of ferric chloride, 3 parts by weight of cobalt chloride and 2 parts by weight of vanadium chloride in 200 parts by weight of water to obtain a solution B; dripping A liquid into B liquid, adding 100 parts by weight of modified SiO prepared in the step S4 2 Dropwise adding ammonia water to the nanospheres until the pH value of the solution is 2, heating to 90 ℃, stirring and reacting for 2 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Example 2
The embodiment provides a preparation method of a catalyst for preparing hydrocyanic acid by methanol ammoxidation, which comprises the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: 15 parts by weight of ferric nitrate and ferrous nitrate are dissolved in 200 parts by weight of water, the molar ratio of the ferric nitrate to the ferrous nitrate is 2:1, 2 parts by weight of emulsifying agent and 1 part by weight of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 are added, and the mixture is stirred uniformly for 10 minutes to prepare a water phase; dissolving 35 parts by weight of ethyl orthosilicate in 200 parts by weight of dichloromethane to obtain an oil phase; dropwise adding the water phase into the oil phase under the protection of nitrogen, emulsifying for 15min at 10000r/min, dropwise adding 22wt% ammonia water until the pH value of the solution is 9, heating to 75 ℃, stirring for reacting for 5h, centrifuging, washing with deionized water, drying, calcining for 2h at 400 ℃ under the protection of nitrogen, and obtaining the porous magnetic SiO 2 A nanosphere;
the emulsifier is a mixture of tween-80 and span-80 according to a mass ratio of 1:1;
s2, surface modification of the wrinkled graphene oxide: 15 parts by weight of graphene oxide is dissolved in 200 parts by weight of water, and 30 parts by weight of porous magnetic SiO prepared in the step S1 is added 2 Nanospheres are stirred and mixed for 20min, and spray-dried to prepare the pleated graphene oxide modified porous magnetic SiO 2 A nanosphere;
the spray drying condition is that the air inlet temperature is 100 ℃, the air outlet temperature is 70 ℃ and the evaporation water quantity is 2200mL/h;
s3, fixing beta-zeolite molecular sieve nanocrystals: 3 parts by weight of pseudo-boehmite is dissolved in water, and 6.5 parts by weight of tetraethylammonium hydroxide, 10 parts by weight of white carbon black and 15 parts by weight of the pleated graphene oxide modified porous magnetic SiO prepared in the step S2 are added 2 Nanosphere, heating and stirring to react, wherein the temperature of a heater is 130 ℃, the reaction time is 20 hours, centrifuging, washing with deionized water, and drying to obtain the pleated porous magnetic SiO with the beta-zeolite molecular sieve nanocrystalline fixed 2 A nanosphere;
s4, modifying polydopamine: 20 parts by weight of beta-zeolite molecular sieve nanocrystalline immobilized pleated porous magnetic SiO prepared in step S3 2 Adding the nanospheres into water, adding 10 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging, washing with deionized water, and drying to obtain modified SiO 2 A nanosphere;
the catalyst is Tris-HCl solution with pH=9;
s5, depositing Co/V doped Fe-Mo oxide: 30 parts by weight (NH 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 105 parts by weight of ferric nitrate, 5 parts by weight of cobalt nitrate and 4 parts by weight of vanadium chloride in 200 parts by weight of water to obtain a solution B; dripping A liquid into B liquid, adding 120 parts by weight of modified SiO prepared in the step S4 2 Dropwise adding ammonia water into the nanospheres until the pH value of the solution is 2.5, heating to 100 ℃, stirring and reacting for 4 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Example 3
The embodiment provides a preparation method of a catalyst for preparing hydrocyanic acid by methanol ammoxidation, which comprises the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: dissolving 12.6 parts by weight of ferric chloride and ferrous chloride in 200 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 1.5 parts by weight of an emulsifier and 0.7 part by weight of cetyl trimethyl ammonium bromide, and uniformly stirring for 10min to obtain a water phase; dissolving 30 parts by weight of ethyl orthosilicate in 200 parts by weight of dichloromethane to obtain an oil phase; dropwise adding the water phase into the oil phase under the protection of nitrogen, emulsifying for 15min at 10000r/min, dropwise adding 22wt% ammonia water until the pH value of the solution is 8.7, heating to 70 ℃, stirring for reacting for 4h, centrifuging, washing with deionized water, drying, calcining for 2h at 400 ℃ under the protection of nitrogen, and obtaining the porous magnetic SiO 2 A nanosphere;
the emulsifier is a mixture of tween-80 and span-80 according to a mass ratio of 1:1;
s2, surface modification of the wrinkled graphene oxide: 13.5 parts by weight of graphene oxide is dissolved in 200 parts by weight of water, and 27 parts by weight of the porous magnetic SiO prepared in the step S1 is added 2 Nanospheres are stirred and mixed for 20min, and spray-dried to prepare the pleated graphene oxide modified porous magnetic SiO 2 A nanosphere;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 50 ℃ and the evaporation water quantity is 2000mL/h;
s3, fixing beta-zeolite molecular sieve nanocrystals: 2.5 parts by weight of pseudo-boehmite is dissolved in water, and 5 parts by weight of tetraethylammonium hydroxide, 8 parts by weight of white carbon black and 13.5 parts by weight of the pleated graphene oxide modified porous magnetic SiO prepared in the step S2 are added 2 Nanosphere, heating and stirring to react, wherein the temperature of a heater is 120 ℃, the reaction time is 19h, centrifuging, washing with deionized water, and drying to obtain the pleated porous magnetic SiO with the beta-zeolite molecular sieve nanocrystalline fixed 2 A nanosphere;
s4, modifying polydopamine: 17 parts by weight of beta-zeolite molecular sieve nanocrystalline immobilized pleated porous magnetic SiO prepared in step S3 2 Adding nanospheres into water, adding 8.5 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 45 ℃, stirringStirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain modified SiO 2 A nanosphere;
the catalyst is Tris-HCl solution with pH=8.7;
s5, depositing Co/V doped Fe-Mo oxide: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate, 4 parts by weight of cobalt nitrate and 3 parts by weight of vanadium chloride in 200 parts by weight of water to obtain a solution B; dropwise adding the solution A into the solution B, and adding 110 parts by weight of the modified SiO prepared in the step S4 2 Dropwise adding ammonia water into the nanospheres until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 1
In comparison with example 3, the difference is that ferric chloride and ferrous chloride are not added in step S1.
The method comprises the following steps:
s1, porous SiO 2 Preparation of nanospheres: dissolving 1.5 parts by weight of an emulsifier and 0.7 part by weight of cetyl trimethyl ammonium bromide in 200 parts by weight of water, and uniformly stirring for 10 minutes to prepare a water phase; dissolving 30 parts by weight of ethyl orthosilicate in 200 parts by weight of dichloromethane to obtain an oil phase; dropwise adding water phase into oil phase, emulsifying for 15min at 10000r/min, dropwise adding 22wt% ammonia water until pH value of solution is 8.7, heating to 70deg.C, stirring for reacting for 4 hr, centrifuging, washing with deionized water, drying, calcining at 400deg.C for 2 hr to obtain porous SiO 2 A nanosphere.
Comparative example 2
The difference compared to example 3 is that no porogen is added in step S1.
The method comprises the following steps:
s1, magnetic SiO 2 Preparation of nanospheres: dissolving 12.6 parts by weight of ferric chloride and ferrous chloride in 200 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 1.5 parts by weight of an emulsifier, and uniformly stirring for 10min to obtain a water phase; dissolving 30 parts by weight of ethyl orthosilicate in 200 parts by weight of dichloromethane to obtain an oil phase; under the protection of nitrogen, the water phase is treatedDropwise adding into oil phase, emulsifying at 10000r/min for 15min, dropwise adding 22wt% ammonia water until pH value of solution is 8.7, heating to 70deg.C, stirring for reacting for 4 hr, centrifuging, washing with deionized water, drying, calcining at 400deg.C under nitrogen protection for 2 hr to obtain magnetic SiO 2 A nanosphere.
Comparative example 3
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: dissolving 12.6 parts by weight of ferric chloride and ferrous chloride in 200 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 1.5 parts by weight of an emulsifier and 0.7 part by weight of cetyl trimethyl ammonium bromide, and uniformly stirring for 10min to obtain a water phase; dissolving 30 parts by weight of ethyl orthosilicate in 200 parts by weight of dichloromethane to obtain an oil phase; dropwise adding the water phase into the oil phase under the protection of nitrogen, emulsifying for 15min at 10000r/min, dropwise adding 22wt% ammonia water until the pH value of the solution is 8.7, heating to 70 ℃, stirring for reacting for 4h, centrifuging, washing with deionized water, drying, calcining for 2h at 400 ℃ under the protection of nitrogen, and obtaining the porous magnetic SiO 2 A nanosphere;
the emulsifier is a mixture of tween-80 and span-80 according to a mass ratio of 1:1;
s2, fixing beta-zeolite molecular sieve nanocrystals: 2.5 parts by weight of pseudo-boehmite is dissolved in water, and 5 parts by weight of tetraethylammonium hydroxide, 8 parts by weight of white carbon black and 13.5 parts by weight of porous magnetic SiO prepared in the step S1 are added 2 Nanosphere, heating and stirring to react, wherein the temperature of a heater is 120 ℃, the reaction time is 19h, centrifuging, washing with deionized water, and drying to obtain the porous magnetic SiO with the immobilized beta-zeolite molecular sieve nanocrystals 2 A nanosphere;
s3, modifying polydopamine: 17 parts by weight of the porous magnetic SiO with the fixed beta-zeolite molecular sieve nanocrystalline prepared in the step S2 2 Adding the nanospheres into water, adding 8.5 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 45 ℃, stirring for reaction for 3 hours, centrifuging, washing with deionized water, and drying to obtain modified SiO 2 A nanosphere;
the catalyst is Tris-HCl solution with pH=8.7;
s4, depositing Co/V doped Fe-Mo oxide: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate, 4 parts by weight of cobalt nitrate and 3 parts by weight of vanadium chloride in 200 parts by weight of water to obtain a solution B; dropwise adding the solution A into the solution B, and adding 110 parts by weight of the modified SiO prepared in the step S3 2 Dropwise adding ammonia water into the nanospheres until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 4
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: dissolving 12.6 parts by weight of ferric chloride and ferrous chloride in 200 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 1.5 parts by weight of an emulsifier and 0.7 part by weight of cetyl trimethyl ammonium bromide, and uniformly stirring for 10min to obtain a water phase; dissolving 30 parts by weight of ethyl orthosilicate in 200 parts by weight of dichloromethane to obtain an oil phase; dropwise adding the water phase into the oil phase under the protection of nitrogen, emulsifying for 15min at 10000r/min, dropwise adding 22wt% ammonia water until the pH value of the solution is 8.7, heating to 70 ℃, stirring for reacting for 4h, centrifuging, washing with deionized water, drying, calcining for 2h at 400 ℃ under the protection of nitrogen, and obtaining the porous magnetic SiO 2 A nanosphere;
the emulsifier is a mixture of tween-80 and span-80 according to a mass ratio of 1:1;
s2, surface modification of the wrinkled graphene oxide: 13.5 parts by weight of graphene oxide is dissolved in 200 parts by weight of water, and 27 parts by weight of the porous magnetic SiO prepared in the step S1 is added 2 Nanospheres are stirred and mixed for 20min, and spray-dried to prepare the pleated graphene oxide modified porous magnetic SiO 2 A nanosphere;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 50 ℃ and the evaporation water quantity is 2000mL/h;
s3, modifying polydopamine: 17 parts by weight of the wrinkled graphene oxide modified porous magnetic SiO prepared in the step S2 2 Adding the nanospheres into water, adding 8.5 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 45 ℃, stirring for reaction for 3 hours, centrifuging, washing with deionized water, and drying to obtain modified SiO 2 A nanosphere;
the catalyst is Tris-HCl solution with pH=8.7;
s4, depositing Co/V doped Fe-Mo oxide: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate, 4 parts by weight of cobalt nitrate and 3 parts by weight of vanadium chloride in 200 parts by weight of water to obtain a solution B; dropwise adding the solution A into the solution B, and adding 110 parts by weight of the modified SiO prepared in the step S3 2 Dropwise adding ammonia water into the nanospheres until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 5
In comparison with example 3, the difference is that step S4 is not performed.
The method comprises the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: dissolving 12.6 parts by weight of ferric chloride and ferrous chloride in 200 parts by weight of water, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adding 1.5 parts by weight of an emulsifier and 0.7 part by weight of cetyl trimethyl ammonium bromide, and uniformly stirring for 10min to obtain a water phase; dissolving 30 parts by weight of ethyl orthosilicate in 200 parts by weight of dichloromethane to obtain an oil phase; dropwise adding the water phase into the oil phase under the protection of nitrogen, emulsifying for 15min at 10000r/min, dropwise adding 22wt% ammonia water until the pH value of the solution is 8.7, heating to 70 ℃, stirring for reacting for 4h, centrifuging, washing with deionized water, drying, calcining for 2h at 400 ℃ under the protection of nitrogen, and obtaining the porous magnetic SiO 2 A nanosphere;
the emulsifier is a mixture of tween-80 and span-80 according to a mass ratio of 1:1;
s2, surface modification of the wrinkled graphene oxide: 13.5 parts by weight of graphene oxide was dissolved in 200 parts by weightAdding 27 parts by weight of porous magnetic SiO prepared in the step S1 into water 2 Nanospheres are stirred and mixed for 20min, and spray-dried to prepare the pleated graphene oxide modified porous magnetic SiO 2 A nanosphere;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 50 ℃ and the evaporation water quantity is 2000mL/h;
s3, fixing beta-zeolite molecular sieve nanocrystals: 2.5 parts by weight of pseudo-boehmite is dissolved in water, and 5 parts by weight of tetraethylammonium hydroxide, 8 parts by weight of white carbon black and 13.5 parts by weight of the pleated graphene oxide modified porous magnetic SiO prepared in the step S2 are added 2 Nanosphere, heating and stirring to react, wherein the temperature of a heater is 120 ℃, the reaction time is 19h, centrifuging, washing with deionized water, and drying to obtain the pleated porous magnetic SiO with the beta-zeolite molecular sieve nanocrystalline fixed 2 A nanosphere;
s4, depositing Co/V doped Fe-Mo oxide: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate, 4 parts by weight of cobalt nitrate and 3 parts by weight of vanadium chloride in 200 parts by weight of water to obtain a solution B; dropwise adding the solution A into the solution B, and adding 110 parts by weight of the beta-zeolite molecular sieve nanocrystalline immobilized pleated porous magnetic SiO prepared in the step S3 2 Dropwise adding ammonia water into the nanospheres until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 6
The difference from example 3 is that cobalt nitrate was not added in step S5.
The method comprises the following steps:
s5, depositing Co/V doped Fe-Mo oxide: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; 102.2 parts by weight of ferric nitrate and 7 parts by weight of vanadium chloride are dissolved in 200 parts by weight of water to obtain a solution B; dropwise adding the solution A into the solution B, and adding 110 parts by weight of the modified SiO prepared in the step S4 2 Dropwise adding ammonia water into nanospheres until the pH value of the solution is 2.2, and heating to 95 DEG CStirring and reacting for 3h, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 7
In comparison with example 3, the difference is that vanadium chloride is not added in step S5.
The method comprises the following steps:
s5, depositing Co/V doped Fe-Mo oxide: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate and 7 parts by weight of cobalt nitrate in 200 parts by weight of water to obtain solution B; dropwise adding the solution A into the solution B, and adding 110 parts by weight of the modified SiO prepared in the step S4 2 Dropwise adding ammonia water into the nanospheres until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 8
In comparison with example 3, the difference is that vanadium chloride and cobalt nitrate are not added in step S5.
The method comprises the following steps:
s5, depositing Co/V doped Fe-Mo oxide: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate in 200 parts by weight of water to obtain a solution B; dropwise adding the solution A into the solution B, and adding 110 parts by weight of the modified SiO prepared in the step S4 2 Dropwise adding ammonia water into the nanospheres until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 9
27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate in 200 parts by weight of water to obtain a solution B; and (3) dropwise adding the solution A into the solution B, dropwise adding ammonia water until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Comparative example 10
The method comprises the following steps:
S1.SiO 2 preparation of sol: dissolving 30 parts by weight of ethyl orthosilicate in 200 parts by weight of ethanol, adding 70 parts by weight of water, dropwise adding 16wt% hydrochloric acid until the pH value of the solution is 4, heating to 70 ℃, stirring for reaction for 4 hours, centrifuging, washing with deionized water, and drying to obtain SiO 2 A sol carrier;
s2, preparing a catalyst: 27 parts by weight (NH) 4 ） 6 Mo 7 O 24 Dissolving in 200 parts by weight of water to obtain solution A; dissolving 102.2 parts by weight of ferric nitrate in 200 parts by weight of water to obtain a solution B; dropwise adding the solution A into the solution B, dropwise adding ammonia water until the pH value of the solution is 2.2, heating to 95 ℃, stirring and reacting for 3 hours, and adding the SiO prepared in the step S1 2 And (3) carrying out a sol carrier, stirring and reacting for 1h, centrifuging, washing with deionized water, and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
Test example 1
The catalysts for preparing hydrocyanic acid by ammoxidation of methanol prepared in examples 1 to 3 and comparative examples 1 to 10 of the present invention were subjected to performance test.
And carrying out specific surface area analysis and pore structure test on the catalyst by using a QuadraSorb SI type physical adsorption instrument.
Catalyst surface acidity determination: by N 2 The carrier gas was a saturated pyridine vapor at 0℃as an adsorbent at a flow rate of 30mL/min, and a bridge flow of 70mA, and was adsorbed at 100 ℃. The catalyst was dehydrated by air treatment at 400℃for 1 hour and then weighed. Acidity is expressed in milliequivalents of pyridine adsorbed per gram of catalyst
The results are shown in Table 1.
TABLE 1
As can be seen from the above table, the catalysts for preparing hydrocyanic acid by methanol ammoxidation prepared in examples 1-3 of the present invention have the advantages of large specific surface area, large pore volume, improved average pore diameter and strong acidity.
Because ammonia is an alkaline substance, methanol has amphiprotic property, the strong acidity of the catalyst is beneficial to improving the activity of the catalyst, and the larger specific surface area and pore volume are also beneficial to providing catalytic sites, so that the catalytic efficiency is greatly improved.
Example 4
The present embodiment provides a method for preparing hydrocyanic acid, under the action of the catalyst prepared in embodiment 1, using a fluidized bed reactor to perform a reaction, so as to perform a catalytic oxidation reaction on methanol, ammonia and oxygen, where the molar ratio of the methanol to the ammonia to the oxygen is 1:0.95:9.5, the pressure of the catalytic oxidation reaction is 0.2MPa, the weight space velocity is 0.05/h, the reaction temperature is 395 ℃, and the hydrocyanic acid is obtained.
Example 5
The present example provides a method for preparing hydrocyanic acid, under the action of the catalyst prepared in example 2, using a fixed bed reactor to perform a reaction, so as to perform a catalytic oxidation reaction on methanol, ammonia and oxygen, wherein the molar ratio of the methanol to the ammonia to the oxygen is 1:1.25:13, the pressure of the catalytic oxidation reaction is 0.4MPa, the weight space velocity is 0.45/h, the reaction temperature is 405 ℃, and the hydrocyanic acid is obtained.
Example 6
The present example provides a method for preparing hydrocyanic acid, under the action of the catalyst prepared in example 3, using a fixed bed reactor to perform a reaction, so as to perform a catalytic oxidation reaction on methanol, ammonia and oxygen, wherein the molar ratio of the methanol to the ammonia to the oxygen is 1:1:10, the pressure of the catalytic oxidation reaction is 0.3MPa, the weight space velocity is 0.25/h, the reaction temperature is 400 ℃, and the hydrocyanic acid is obtained.
Comparative examples 11 to 20
In comparison with example 6, the catalysts were prepared from comparative examples 1 to 10, respectively.
Test example 2
The preparation methods in examples 4 to 6 and comparative examples 11 to 20 of the present invention were tested and monitored, and the results are shown in Table 2.
In each group of preparation methods, long-period 200h operation was performed to test the stability of the catalyst.
TABLE 2
As can be seen from the above table, the method of examples 4 to 6 of the present invention has high methanol conversion, high HCN selectivity and high catalyst stability.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. A method for preparing a catalyst for preparing hydrocyanic acid by methanol ammoxidation, which is characterized by comprising the following steps:
s1, porous magnetic SiO 2 Preparation of nanospheres: dissolving ferric salt and ferrous salt in water, adding an emulsifying agent and a pore-forming agent, and uniformly mixing to obtain a water phase; dissolving alkyl orthosilicate in an organic solvent to obtain an oil phase; dropwise adding the water phase into the oil phase, emulsifying, dropwise adding ammonia water, heating and stirring for reaction, centrifuging, washing, drying, calcining to obtain porous magnetic SiO 2 A nanosphere;
s2, surface modification of the wrinkled graphene oxide: dissolving graphene oxide in water, and adding the porous magnetic SiO prepared in the step S1 2 Nanospheres are stirred and mixed uniformly, and spray-dried to prepare the pleated graphene oxide modified porous magnetic SiO 2 A nanosphere;
s3, fixing beta-zeolite molecular sieve nanocrystals: dissolving pseudo-boehmite in water, adding tetraethyl ammonium hydroxide, white carbon black and the pleated graphene oxide modified porous magnetic SiO prepared in the step S2 2 Nanospheres, heating and stirring to react to prepare the beta-zeolite molecular sieve nanocrystalline fixed fold porous magnetic SiO 2 A nanosphere;
s4, modifying polydopamine: the beta-zeolite molecular sieve nanocrystalline prepared in the step S3 is fixed to form the wrinkled porous magnetic SiO 2 Adding nanospheres into water, adding dopamine hydrochloride and a catalyst, heating, stirring for reaction, centrifuging, and washingDrying to obtain modified SiO 2 A nanosphere;
s5, depositing Co/V doped Fe-Mo oxide: dissolving molybdate in water to obtain solution A; dissolving ferric salt, cobalt salt and vanadium salt in water to obtain solution B; adding the liquid A into the liquid B, and adding the modified SiO prepared in the step S4 2 And (3) dropwise adding ammonia water into the nanospheres, heating and stirring for reaction, centrifuging, washing and drying to obtain the catalyst for preparing hydrocyanic acid by methanol ammoxidation.
2. The preparation method according to claim 1, wherein in the step S1, the molar ratio of the iron salt to the ferrous salt is 2:1, the iron salt is at least one of ferric chloride and ferric nitrate, the ferrous salt is at least one of ferrous chloride and ferrous nitrate, the emulsifying agent is at least one of span-20, span-40, span-60, span-80, tween-20, tween-40, tween-60 and tween-80, the pore-forming agent is at least one of cetyl trimethyl ammonium bromide, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO106, the mass ratio of the alkyl orthosilicate, the iron salt, the emulsifying agent and the pore-forming agent is at least one of methyl orthosilicate or ethyl orthosilicate is 25-35:12-15:1-2:0.5-1, the dropwise adding to the solution has a pH value of 8.5-9, the heating reaction temperature is 65-75 h.
3. The method according to claim 1, wherein the graphene oxide, porous magnetic SiO in step S2 2 The mass ratio of the nanospheres is 12-15:25-30, the spray drying condition is that the air inlet temperature is 85-100 ℃, the air outlet temperature is 40-70 ℃, and the evaporation water amount is 1700-2200mL/h.
4. The method according to claim 1, wherein the pseudo-boehmite, tetraethylammonium hydroxide, white carbon black, and pleated graphene oxide modified porous magnetic SiO in step S3 2 The mass ratio of the nanospheres is 2-3:4.5-6.5:7-10:12-15, and in the heating and stirring reaction, the temperature of a heater is 110-1The reaction time is 18-20h at 30 ℃.
5. The method of claim 1, wherein the beta zeolite molecular sieve nanocrystalline immobilized pleated porous magnetic SiO in step S4 2 The mass ratio of the nanospheres to the dopamine hydrochloride to the catalyst is 15-20:7-10:0.5-1, the catalyst is Tris-HCl solution with pH=8.5-9, the temperature of the heating and stirring reaction is 40-50 ℃, and the time is 2-4h.
6. The method according to claim 1, wherein the molybdate in step S5 is (NH 4 ） 6 Mo 7 O 24 The ferric salt is ferric nitrate, ferric sulfate or ferric chloride, the cobalt salt is cobalt chloride or cobalt nitrate, the vanadium salt is vanadium chloride, and the molybdate, ferric salt, cobalt salt, vanadium salt and modified SiO 2 The mass ratio of the nanospheres is 25-30:98-105:3-5:2-4:100-120, dropwise adding ammonia water until the pH value of the solution is 2-2.5, and heating and stirring to react for 2-4 hours at the temperature of 90-100 ℃.
7. A catalyst for preparing hydrocyanic acid by ammoxidation of methanol, which is prepared by the preparation method as claimed in any one of claims 1 to 6.
8. A process for preparing hydrocyanic acid, which comprises the step of subjecting methanol, ammonia and oxygen to catalytic oxidation under the action of the catalyst of claim 7.
9. The method of claim 8, wherein the method uses a fixed bed reactor or a fluidized bed reactor for the reaction.
10. The method of claim 8, wherein the molar ratio of methanol, ammonia and oxygen is 1: (0.95-1.25): (9.5-13), wherein the pressure of the catalytic oxidation reaction is 0.2-0.4MPa, the weight space velocity is 0.05-0.45/h, and the reaction temperature is 395-405 ℃.
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