CN107720777A - The clean preparation method of hydrogen cyanide - Google Patents

The clean preparation method of hydrogen cyanide Download PDF

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Publication number
CN107720777A
CN107720777A CN201710818806.5A CN201710818806A CN107720777A CN 107720777 A CN107720777 A CN 107720777A CN 201710818806 A CN201710818806 A CN 201710818806A CN 107720777 A CN107720777 A CN 107720777A
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catalyst
molybdenum
hydrogen cyanide
acid
ammonia
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CN201710818806.5A
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宋帅
孙振民
李建明
乔培华
王廷伟
陈苏昌
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WEIFANG BINHAI PETROLEUM CHEMICAL CO Ltd
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WEIFANG BINHAI PETROLEUM CHEMICAL CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00Cyanogen; Compounds thereof
    • C01C3/02Preparation, separation or purification of hydrogen cyanide
    • C01C3/0208Preparation in gaseous phase
    • C01C3/0212Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
    • C01C3/0216Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • B01J37/086Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention proposes a kind of clean preparation method of hydrogen cyanide, using methanol, liquefied ammonia, air as raw material, methanol ammonoxidation reaction is carried out in fixed bed reactors under the effect of molybdenum bismuth catalyst, obtain synthesis gas A, then synthesis gas is sent into ammonia and is neutralized, cooled in cooling tower, synthesis gas C is obtained, synthesis gas C obtains hydrogen cyanide through absorbing, after rectifying.Molybdenum bismuth catalyst is made up of the oxide of molybdenum, bismuth and manganese, and the empirical formula that the catalyst has is:MoaBibMncOd;A, b, c are atomic ratios, during a=1, b=1~3, c=2~6, d be the generation of catalyst component chemical combination corresponding oxide in oxygen atom sum.This method there is product yield height, ammonia to be cleaned than low, production process, without the characteristics of waste water produces, energy utilization rate is high.

Description

The clean preparation method of hydrogen cyanide
Technical field
The invention belongs to industrial chemicals intermediate preparing technical field, and in particular to a kind of clean manufacturing side of hydrogen cyanide Method.
Background technology
Hydrogen cyanide is a kind of important industrial chemicals intermediate, available for preparing nylon, insecticide, acrylonitrile and gold and silver The plating of copper etc., organic synthesis etc., there is the very big market space.
The method of production hydrogen cyanide mainly has methane ammonia oxidation, acrylonitrile by-product method, light oil cracking method etc..Methane ammonia oxygen Change reaction temperature more than 1000 DEG C, hydrogen cyanide yield can only achieve 60~70%, and reaction temperature is high, brings unsafe factor. Acrylonitrile by-product method is to carry out catalysis oxidation synthesis of acrylonitrile, while by-product part hydrogen cyanide by raw material of propylene, air and ammonia, Due to updating for acrylonitrile catalyst, accessory substance hydrogen cyanide is fewer and fewer.Light oil cracking method be using light oil, petroleum coke as Primary raw material, carry out pyroreaction with ammonia and synthesize hydrogen cyanide, the production technology needs constantly addition solid coke, and building-up process is not It is stable, it is difficult to continuously and stably to produce.
Methanol feedstock is sufficient, has competitiveness in price, and also have advantage for security standpoint.Therefore, first is passed through Ammoxidation from methanol gets more and more people's extensive concerning to prepare the route of hydrogen cyanide, but in actual applications, is primarily present product receipts Rate is low, can not realize the problem of clean manufacturing.CN101157458B is disclosed with iron/molybdenum oxide catalysis methanol ammoxidation Reach the method for explosion-proof yield increasing using datonation-inhibition gas is added in technique, ignore the reduction of reaction yield and anti-in fixed bed The problem of caused reaction heat is withdrawn from difficulty and may led to grave consequences in device is answered, the addition of nitrogen and vapor both increased Production cost, the yield of waste gas and sewage is added again, and the mixing of unstripped gas is carried out in Venturi tube, exist The problem of uneven is mixed, thus also results in and reacts not thorough enough, production efficiency reduction.
The content of the invention
The present invention proposes a kind of clean preparation method of hydrogen cyanide, this method have product yield is high, ammonia than it is low, produced Cheng Qingjie, without waste water produce, energy utilization rate is high the characteristics of.
The technical proposal of the invention is realized in this way:
A kind of clean preparation method of hydrogen cyanide, including following methods:
1) ammoxidation reaction:
Mixed after first methanol is vaporized respectively with liquefied ammonia, then entered with the gas of the molecule-containing keto after compressed, heating After row mixing, normal pressure carries out ammoxidation reaction in fixed bed reactors under the conditions of existing for molybdenum bismuth catalyst, is mixed Gas A;
2) neutralize:
Mixed gas A is sent into the bottom in ammonia with cooling tower after heat exchanger cools and carries out sour neutralization reaction, is mixed Gas B and ammonium salt solution are closed, after mixed gas B is cooled down through the top in ammonia with cooling tower, obtains mixed gas C;Wherein, Ammonium salt solution enters decyanation tower to remove hydrogen cyanide therein, then returns to the hydrogen cyanide of removing in ammonia and cooling tower;
3) absorb:
Mixed gas C is sent into absorption tower and absorbed with water, obtains hydrocyanic acid aqueous solution;
4) rectifying:
Hydrocyanic acid aqueous solution is added in rectifying column and distilled, hydrogen cyanide, tower bottom liquid are obtained in the tower top of rectifying column Absorption tower mutually is returned to after heat exchange cools down, as absorption water circulation use;
Wherein, the molybdenum bismuth catalyst is made up of the oxide of molybdenum, bismuth and manganese, the empirical formula that the catalyst has For:MoaBibMncOd;A, b, c are atomic ratios, and during a=1, b=1~3, c=2~6, d are the generation of catalyst component chemical combination The sum of oxygen atom in corresponding oxide.
Preferably, the molybdenum bismuth catalyst is prepared by the following method to obtain:
It is sufficiently mixed chelating agent in water, is added as the dissolution of raw material of catalyst component, heat treatment forms slurry, will Slurry is spray-dried, and obtains catalyst granules;By catalyst granules after 1~10h of preliminary calcining at a temperature of 350~450 DEG C, In 600~800 DEG C of 2~12h of temperature calcination.
Preferably as the raw material of catalyst molybdenum composition, from molybdenum oxide, molybdenum chloride, nitric acid molybdenum, carbonic acid molybdenum, oxalic acid molybdenum, One or more in molybdenum phosphate;As the raw material of catalyst bismuth composition, from bismuth oxide, waltherite, bismuth nitrate, bismuth oxalate One or more;As the raw material of catalyst manganese composition, from its oxide, inorganic acid salt or acylate;Described chela Mixture is one kind in sodium thiosulfate, triethanolamine, ethylenediamine, citric acid, lactic acid, tartaric acid, grape acid, and chelating agent adds Enter amount accounts for material quality 6~12%.
Preferably, the reaction temperature of the step 1) is 350 DEG C~500 DEG C, the mol ratio of ammonia and methanol for 0.85~ 1.15:1, the mol ratio of molecular oxygen and methanol is 1.0~1.5:1.
Preferably, reaction velocity is 3000~6000h-1
Preferably, the acid used in pickling is selected from sulfuric acid, hydrochloric acid or nitric acid.
Preferably, the operating pressure in step (2) in ammonia and in cooling tower is 0.11~0.2MPa.
Preferably, the temperature of step (3) reclaimed water is 0-10 DEG C.
Preferably, the reflux ratio that rectifying column operates in step (4) is 1~8.
Methanol after vaporization and liquefied ammonia are well mixed by the production technology of the present invention first, then the gas with molecule-containing keto again Body is mixed so that into fixed bed reactors mixed material gas can be sufficiently mixed uniformly, reaction also can completely with Thoroughly, it is that normal pressure progress reaction condition is gentle so as to improve production efficiency, and react, reduces production cost.
The heat transfer medium of fixed bed reactors uses the fused salt mixed by potassium nitrate and natrium nitrosum in the present invention, by It is exothermic reaction in the ammoxidation reaction that inside reactor occurs, is normally cooled down the fused salt after absorbing reaction heat during production With recovered steam, reactor is then back to, forms a circulation loop.
Beneficial effects of the present invention:
1st, the present invention was used as research to the work of each component in catalyst, and it is the key component of catalytic activity to find Bi, no Catalyst containing Bi, hydrogen cyanide yield are very low;And it was found that the proportion of composing of Bi in the catalyst for catalyst activity and Stability has important influence;Mn is added and in the range of rational addition, can effectively improve the utilization rate of ammonia, is reduced Ammonia usage, dosage sour used in the ammonia of reaction is had neither part nor lot in so as to reduce to neutralize, to reducing production cost and control ring Border is polluted, and realizes that methanol ammonoxidation prepares the clean manufacturing of hydrogen cyanide.
2nd, the reaction in the present invention is exothermic reaction, the thermal source that its heat energy discharged can separate as rectifying, while The abundant heat exchange of high/low temperature logistics can be carried out so that the energy expenditure in whole technical process substantially reduces, to outside energy Dependence it is small.
Embodiment
Embodiment 1
Molybdenum bismuth catalyst
23.5g molybdenum chlorides are dissolved in 300ml water and form solution, 85.0g bismuth nitrates and 19.6g oxygen are added portionwise thereto Change manganese, mixed solution is formed with 16.3g ethylenediamines (gross mass 10%).It is under conditions of being sufficiently stirred, 82g Ludox is (total Quality 50%) add in mixed solution, heat treatment forms slurry under the conditions of 100 DEG C while stirring.Rotating disk is used afterwards Slurry is spray-dried by formula spray dryer.The fine spherical particle of gained is calcined into 6h at 350 DEG C, forged at 750 DEG C Burn 1h.
The catalyst of preparation obtains following empirical formulas:Mo1Bi1.5Mn2.6O36.9(SiO2)1.35
Embodiment 2
Molybdenum bismuth catalyst
65.8g nitric acid molybdenums are dissolved in 300ml water and form solution, 83.1g waltherites and 53.56g are added portionwise thereto Manganese oxide, mixed solution is formed with 22g citric acids (12%).Under conditions of being sufficiently stirred, by 73.36g titanium oxide (40%) Add in mixed solution, heat treatment forms slurry under the conditions of 100 DEG C while stirring.It is spray-dried afterwards using disc type Slurry is spray-dried by device.The fine spherical particle of gained is calcined into 2h at 450 DEG C, 4h is calcined at 600 DEG C.
The catalyst of preparation obtains following empirical formulas:Mo1Bi1.75Mn3.3O15.05(TiO2)0.92
Embodiment 3
A kind of clean preparation method of hydrogen cyanide, including following methods:
1) ammoxidation reaction:
Mixed after first methanol is vaporized respectively with liquefied ammonia, then entered with the gas of the molecule-containing keto after compressed, heating Row mixing after, existing for the molybdenum bismuth catalyst in embodiment 1 under the conditions of in fixed bed reactors normal pressure in 450 DEG C carry out ammonia oxygen Change reaction, obtain mixed gas A;The mol ratio of ammonia and methanol is 0.9:1, the mol ratio of molecular oxygen and methanol is 1.2:1, enter Expect mixed gas in blender in normal conditions in volume flow hourly and fixed bed reactors catalyst volume The ratio between loadings, i.e. reaction velocity are 5000h-1
2) neutralize:
Mixed gas A is sent into the bottom in ammonia with cooling tower after heat exchanger cools and carries out sulfuric acid neutralization reaction, is obtained Mixed gas B and the ammonium sulfate that pH value is 3, after mixed gas B is cooled down through the top in ammonia with cooling tower, are mixed Close gas C;Wherein, ammonium salt solution enters decyanation tower to remove hydrogen cyanide therein, then returns to the hydrogen cyanide of removing in ammonia And cooling tower;
3) absorb:
Mixed gas C is sent into absorption tower and absorbed with 6 DEG C of water, obtains the hydrogen cyanide water that concentration is 1.1wt% Solution;
4) rectifying:
Hydrocyanic acid aqueous solution is added in rectifying column and distilled, rectifying column tower top temperature is 28 DEG C, and bottom temperature is 101 DEG C, reflux ratio 4, tower top pressure 0.102MPa, hydrogen cyanide is obtained in the tower top of rectifying column, bottom of towe liquid phase is after heat exchange Absorption tower is returned to, as absorption water circulation use.
As a result show:In terms of methanol, the yield of hydrogen cyanide is 88%, and purity is more than 99.9%.
Embodiment 4
A kind of clean preparation method of hydrogen cyanide, including following methods:
1) ammoxidation reaction:
Mixed after first methanol is vaporized respectively with liquefied ammonia, then entered with the gas of the molecule-containing keto after compressed, heating Row mixing after, existing for the molybdenum bismuth catalyst in embodiment 2 under the conditions of in fixed bed reactors normal pressure in 500 DEG C carry out ammonia oxygen Change reaction, obtain mixed gas A;The mol ratio of ammonia and methanol is 0.85:1, the mol ratio of molecular oxygen and methanol is 1.35:1, Mixed gas in entry mixers volume flow hourly and the body of catalyst in fixed bed reactors in normal conditions The ratio between product loadings, i.e., reaction velocity is 5000h-1
2) neutralize:
Mixed gas A is sent into the bottom in ammonia with cooling tower after heat exchanger cools and carries out hydrochloric acid neutralization reaction, is obtained Mixed gas B and ammonium chloride solution, after mixed gas B is cooled down through the top in ammonia with cooling tower, obtain mixed gas C; Wherein, ammonium salt solution enters decyanation tower to remove hydrogen cyanide therein, then returns to the hydrogen cyanide of removing in ammonia and cooling tower;
3) absorb:
Mixed gas C is sent into absorption tower and absorbed with 4 DEG C of water, obtains the hydrogen cyanide water that concentration is 1.2wt% Solution;
4) rectifying:
Hydrocyanic acid aqueous solution is added in rectifying column and distilled, rectifying column tower top temperature is 27 DEG C, and bottom temperature is 101 DEG C, reflux ratio 5, tower top pressure 0.102MPa, hydrogen cyanide is obtained in the tower top of rectifying column, bottom of towe liquid phase is after heat exchange Absorption tower is returned to, as absorption water circulation use.
As a result show:In terms of methanol, the yield of hydrogen cyanide is 85%, and purity is more than 99.9%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.

Claims (6)

1. a kind of clean preparation method of hydrogen cyanide, it is characterised in that including following methods:
1) ammoxidation reaction:
Mixed after first methanol is vaporized respectively with liquefied ammonia, then mixed with the gas of the molecule-containing keto after compressed, heating After conjunction, normal pressure carries out ammoxidation reaction in fixed bed reactors under the conditions of existing for molybdenum bismuth catalyst, obtains mixed gas A;
2) neutralize:
Mixed gas A is sent into the bottom in ammonia with cooling tower after heat exchanger cools and carries out sour neutralization reaction, obtains gaseous mixture Body B and ammonium salt solution, after mixed gas B is cooled down through the top in ammonia with cooling tower, obtain mixed gas C;Wherein, ammonium salt Solution enters decyanation tower to remove hydrogen cyanide therein, then returns to the hydrogen cyanide of removing in ammonia and cooling tower;
3) absorb:
Mixed gas C is sent into absorption tower and absorbed with water, obtains hydrocyanic acid aqueous solution;
4) rectifying:
Hydrocyanic acid aqueous solution is added in rectifying column and distilled, hydrogen cyanide, bottom of towe liquid phase warp are obtained in the tower top of rectifying column Absorption tower is returned to after heat exchange cooling, as absorption water circulation use;
Wherein, the molybdenum bismuth catalyst is made up of the oxide of molybdenum, bismuth and manganese, and the empirical formula that the catalyst has is: MoaBibMncOd;A, b, c are atomic ratios, and during a=1, b=1~3, c=2~6, d are the correspondence of catalyst component chemical combination generation The sum of oxygen atom in oxide.
2. the clean preparation method of hydrogen cyanide according to claim 1, it is characterised in that the molybdenum bismuth catalyst by with Lower section method is prepared:
It is sufficiently mixed chelating agent in water, is added as the dissolution of raw material of catalyst component, heat treatment forms slurry, by slurry Spray drying, obtains catalyst granules;By catalyst granules after 1~10h of preliminary calcining at a temperature of 350~450 DEG C, 600~800 DEG C of 2~12h of temperature calcination.
3. the clean preparation method of hydrogen cyanide according to claim 2, it is characterised in that the original as catalyst molybdenum composition Material, from the one or more in molybdenum oxide, molybdenum chloride, nitric acid molybdenum, carbonic acid molybdenum, oxalic acid molybdenum, molybdenum phosphate;As catalyst bismuth into The raw material divided, from the one or more in bismuth oxide, waltherite, bismuth nitrate, bismuth oxalate;Original as catalyst manganese composition Material, from its oxide, inorganic acid salt or acylate;Described chelating agent be sodium thiosulfate, triethanolamine, ethylenediamine, One kind in citric acid, lactic acid, tartaric acid, grape acid, the addition of chelating agent account for the 6~12% of material quality.
4. the clean preparation method of hydrogen cyanide according to claim 1 or 2, it is characterised in that the reaction of the step 1) Temperature is 350 DEG C~500 DEG C, and the mol ratio of ammonia and methanol is 0.85~1.15:1, the mol ratio of molecular oxygen and methanol is 1.0 ~1.5:1.
5. the clean preparation method of hydrogen cyanide according to claim 1 or 2, it is characterised in that reaction velocity be 3000~ 6000h-1
6. the clean preparation method of hydrogen cyanide according to claim 1, it is characterised in that the acid used in pickling is selected from sulphur Acid, hydrochloric acid or nitric acid.
CN201710818806.5A 2017-09-12 2017-09-12 The clean preparation method of hydrogen cyanide Pending CN107720777A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470815A (en) * 1992-12-31 1995-11-28 Korea Advanced Institute Of Science And Technology Multicomponent oxide catalyst
CN1182728A (en) * 1996-11-16 1998-05-27 德古萨股份公司 Process for preparing prussiate by ammoxidation
JPH10180107A (en) * 1996-05-30 1998-07-07 Asahi Chem Ind Co Ltd Catalyst composition for ammoxidation of alkane and production of nitrile compound using thereof
CN105502436A (en) * 2016-01-19 2016-04-20 浦为民 Clean production technology of hydrocyanic acid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470815A (en) * 1992-12-31 1995-11-28 Korea Advanced Institute Of Science And Technology Multicomponent oxide catalyst
JPH10180107A (en) * 1996-05-30 1998-07-07 Asahi Chem Ind Co Ltd Catalyst composition for ammoxidation of alkane and production of nitrile compound using thereof
CN1182728A (en) * 1996-11-16 1998-05-27 德古萨股份公司 Process for preparing prussiate by ammoxidation
CN105502436A (en) * 2016-01-19 2016-04-20 浦为民 Clean production technology of hydrocyanic acid

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Application publication date: 20180223