CN111533136A - Production system and process of hydrocyanic acid - Google Patents
Production system and process of hydrocyanic acid Download PDFInfo
- Publication number
- CN111533136A CN111533136A CN202010629911.6A CN202010629911A CN111533136A CN 111533136 A CN111533136 A CN 111533136A CN 202010629911 A CN202010629911 A CN 202010629911A CN 111533136 A CN111533136 A CN 111533136A
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- China
- Prior art keywords
- methanol
- ammonia
- hydrocyanic acid
- catalyst
- air
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000006200 vaporizer Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000013021 overheating Methods 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/0216—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
-
- 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
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/022—Apparatus therefor
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production system and a process of hydrocyanic acid, wherein the hydrocyanic acid is produced by a methanol ammonia oxidation method, raw materials of the hydrocyanic acid comprise methanol, liquid ammonia and air, and the hydrocyanic acid is generated under the action of a catalyst, and the production system comprises the following steps: (1) the methanol and the liquid nitrogen are superheated and gasified and then are introduced into a mixer for mixing; (2) introducing the mixture and air into a raw material mixer for mixing; (3) the three are mixed and then pass through a fixed bed reactor to generate hydrocyanic acid (4) under the action of a catalyst to neutralize unreacted ammonia gas. The invention improves the conversion rate, improves the production efficiency and reduces the cost by changing the proportion of the catalyst, changing the particle size of the catalyst and changing the proportion and the temperature of the raw materials.
Description
Technical Field
The invention relates to the technical field of hydrocyanic acid production, in particular to a hydrocyanic acid production system and a hydrocyanic acid production process.
Background
Hydrocyanic acid is a chemical product with wide application range, can be used for manufacturing nylon, pesticides, acrylonitrile, acrylic resin and the like, particularly the demand of hexanediol and methacrylate resin on hydrocyanic acid shows great market demand. However, hydrocyanic acid has special physical properties, is a highly toxic chemical, is very easy to diffuse at normal temperature and pressure, is miscible with water, is soluble in ethanol, ether, glycerol, benzene, chloroform and the like, is easy to self-polymerize, blocks pipelines and equipment, and influences the production of the device and even downstream devices. The traditional process for producing hydrocyanic acid is mainly an Andrussow method, and a series of ammonia oxidation methods, BMA methods, acrylonitrile by-product methods and light oil cracking methods led from the Andrussow method. In the traditional methanol ammonia oxidation method, the gas containing hydrogen cyanide is produced firstly, but in the traditional process and device, the oxidation process is not sufficient, the reaction degree is limited, the consumption of raw materials is increased, and the cost is greatly increased.
Therefore, a production system and a process capable of improving the reaction degree, reducing the reaction time, sufficiently improving the utilization rate of raw materials and reducing the production cost are needed.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problems to be solved by the invention are as follows: how to provide a hydrocyanic acid production system and a hydrocyanic acid production process which can improve the reaction degree, reduce the reaction time, fully improve the utilization rate of raw materials and reduce the production cost.
In order to solve the technical problems, the invention adopts the following technical scheme:
a production system and a process of hydrocyanic acid adopt a methanol ammonia oxidation method to prepare hydrocyanic acid, raw materials comprise methanol, liquid ammonia and air, and the production system is characterized by comprising the following steps:
(1) putting methanol and liquid ammonia into a methanol vaporizer and an ammonia vaporizer respectively for overheating and vaporizing, and simultaneously heating air in an air heater 4;
(2) introducing the gasified methanol gas and ammonia gas into a methanol-ammonia mixer for mixing;
(3) introducing the mixed methanol ammonia and air into a main mixer for mixing;
(4) introducing a mixture of methanolic ammonia and air into a reactor;
(5) adding a catalyst into a reactor;
(6) heating the reactor to 480-500 ℃;
(7) returning part of the mixture after the reaction is finished to the step (1) and the step (2) to preheat air, methanol and ammonia;
(8) and (3) introducing the mixture of the air, the methanol and the ammonia gas used for heating in the step (7) and the mixture not used for heating into a mixer for mixing, then introducing the mixture in the mixer into a neutralizing tower, and neutralizing the unreacted ammonia gas.
Therefore, through the steps, the product hydrocyanic acid can be better prepared, the forward progress of the reaction can be promoted by the excessive ammonia, the forward progress of the methanol oxidation can be promoted by the high temperature, the mixture after the reaction is completed is used for preheating the raw materials, meanwhile, the mixture is cooled, and the energy is saved.
Further, the ratio of ammonia to methanol was 1.13: 1. The excess ammonia promotes the forward direction of the methanol oxidation reaction.
Further, the catalyst is a solid phase iron molybdenum catalyst. The use of a catalyst enables a rapid forward reaction of the starting materials.
Further, by changing Fe in the catalyst2O3With MoO3The ratio of Fe/Mo in the catalyst was 1.6. The degree of oxidation reaction can be improved.
Further, the length of the solid phase iron-molybdenum catalyst particles is 4-4.5mm, the diameter is 3.8-4.2mm, and the bulk density is 1200kg/m3-1300kg/m3. The smaller the catalyst particles, the wider the area of contact with the raw material, and the forward progress of the reaction can be promoted.
In conclusion, the device can better improve the reaction degree, reduce the reaction time, fully improve the utilization rate of raw materials, improve the resource utilization rate and reduce the production cost.
Drawings
FIG. 1 is a schematic system flow diagram of a hydrocyanic acid production system and process according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
In specific implementation, as shown in fig. 1, a production system and a process for hydrocyanic acid adopt a methanol ammonia oxidation method to prepare hydrocyanic acid, wherein raw materials comprise methanol, liquid ammonia and air, and the production system and the process are characterized by comprising the following steps:
(1) putting methanol 2 and liquid ammonia 3 into a methanol vaporizer 5 and an ammonia vaporizer 6 respectively for overheating and vaporizing, and heating air in an air heater 4;
(2) introducing the gasified methanol gas and ammonia gas into a methanol-ammonia mixer 7 for mixing;
(3) introducing the mixed methanolic ammonia and air 1 into a main mixer 8 for mixing;
(4) introducing a mixture of methanolic ammonia and air into reactor 9;
(5) adding a catalyst into a reactor;
(6) heating the reactor to 480-500 ℃;
(7) returning part of the mixture after the reaction is finished to the step (1) and the step (2) to preheat air, methanol and ammonia;
(8) and (3) introducing the mixture of the air, the methanol and the ammonia gas used for heating in the step (7) and the mixture not used for heating into a mixer 10 for mixing, and then introducing the mixture in the mixer into a neutralizing tower 11 for neutralizing the unreacted ammonia gas. Therefore, through the steps, the product hydrocyanic acid can be better prepared, the forward progress of the reaction can be promoted by the excessive ammonia, the forward progress of the methanol oxidation can be promoted by the high temperature, the mixture after the reaction is completed is used for preheating the raw materials, meanwhile, the mixture is cooled, and the energy is saved.
In this example, the ratio of ammonia to methanol was 1.13: 1. The excess ammonia promotes the forward direction of the methanol oxidation reaction.
In this example, the catalyst is a solid phase iron molybdenum catalyst. The use of a catalyst enables a rapid forward reaction of the starting materials.
In this example, the catalyst was modified by changing Fe2O3With MoO3The ratio of Fe/Mo in the catalyst was 1.6. The degree of oxidation reaction can be improved.
In this example, the solid phase iron molybdenum catalyst particles had a length of 4 to 4.5mm, a diameter of 3.8 to 4.2mm and a bulk density of 1200kg/m3-1300kg/m3. The smaller the catalyst particles, the wider the area of contact with the raw material, and the forward progress of the reaction can be promoted.
The working principle and the flow of the production system and the production process are as follows:
when the production system and the process are used, firstly, liquid methanol and ammonia are gasified by overheating, air is heated, then the mixture is introduced into a methanol-ammonia mixer for mixing, the mixture is introduced into a main mixer for mixing with the heated air, the mixture is introduced into a reactor containing a catalyst after mixing, the mixture is heated to 480-500 ℃ for reaction, then the mixture after reaction is divided into two parts and sent out, one part is used for heating the air, the methanol and the ammonia, the other part is sent into the mixer, then one part of the mixture for heating is sent into the mixer, the two parts are mixed, finally the mixture is sent into a neutralization tower for neutralizing the unreacted ammonia, and the obtained product is introduced into the next unit.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art; the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; these modifications and substitutions do not cause the essence of the corresponding technical solution to depart from the scope of the technical solution of the embodiments of the present invention, and are intended to be covered by the claims and the specification of the present invention.
Claims (5)
1. A production system and a process of hydrocyanic acid adopt a methanol ammonia oxidation method to prepare hydrocyanic acid, raw materials comprise methanol, liquid ammonia and air, and the production system is characterized by comprising the following steps:
(1) putting methanol and liquid ammonia into a methanol vaporizer and an ammonia vaporizer respectively for overheating and vaporizing, and simultaneously heating air in an air heater;
(2) introducing the gasified methanol gas and ammonia gas into a methanol-ammonia mixer for mixing;
(3) introducing the mixed methanol ammonia and air into a main mixer for mixing;
(4) introducing a mixture of methanolic ammonia and air into a reactor;
(5) adding a catalyst into a reactor;
(6) heating the reactor to 480-500 ℃ to obtain hydrocyanic acid and unreacted ammonia gas;
(7) returning part of the mixture after the reaction is finished to the step (1) and the step (2) to preheat air, methanol and ammonia;
(8) and (3) introducing the mixture of the air, the methanol and the ammonia gas used for heating in the step (7) and the mixture not used for heating into a mixer for mixing, then introducing the mixture in the mixer into a neutralizing tower, and neutralizing the unreacted ammonia gas.
2. The hydrocyanic acid production system and process according to claim 1, wherein a ratio of the ammonia gas to the methanol gas is 1.13: 1.
3. The hydrocyanic acid production system and process according to claim 1, wherein the catalyst is a solid phase iron molybdenum catalyst.
4. The hydrocyanic acid production system and process according to claim 3, wherein the catalyst is modified by changing Fe2O3With MoO3The ratio of Fe/Mo in the catalyst was 1.6.
5. The hydrocyanic acid production system and process according to claim 3, wherein the solid phase iron-molybdenum catalyst particles have a length of 4 to 4.5mm, a diameter of 3.8 to 4.2mm, and a bulk density of 1200kg/m3-1300kg/m3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010629911.6A CN111533136A (en) | 2020-07-03 | 2020-07-03 | Production system and process of hydrocyanic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010629911.6A CN111533136A (en) | 2020-07-03 | 2020-07-03 | Production system and process of hydrocyanic acid |
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| Publication Number | Publication Date |
|---|---|
| CN111533136A true CN111533136A (en) | 2020-08-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010629911.6A Pending CN111533136A (en) | 2020-07-03 | 2020-07-03 | Production system and process of hydrocyanic acid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006099252A1 (en) * | 2005-03-11 | 2006-09-21 | Nevada Chemicals, Inc. | Producing calcium cyanide at a mine site using easily transportable starting materials |
| CN101353173A (en) * | 2007-07-23 | 2009-01-28 | 罗姆有限公司 | Reactor for preparing hydrogen cyanide by the andrussow process |
| US20110033362A1 (en) * | 2008-03-20 | 2011-02-10 | Arkema France | Process for Producing Hydrocyanic Acid |
| CN105502436A (en) * | 2016-01-19 | 2016-04-20 | 浦为民 | Clean production technology of hydrocyanic acid |
| CN106669705A (en) * | 2016-12-26 | 2017-05-17 | 阳泉煤业（集团）有限责任公司 | Catalyst used for methanol ammoxidation and preparation and forming method thereof |
-
2020
- 2020-07-03 CN CN202010629911.6A patent/CN111533136A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006099252A1 (en) * | 2005-03-11 | 2006-09-21 | Nevada Chemicals, Inc. | Producing calcium cyanide at a mine site using easily transportable starting materials |
| CN101353173A (en) * | 2007-07-23 | 2009-01-28 | 罗姆有限公司 | Reactor for preparing hydrogen cyanide by the andrussow process |
| US20110033362A1 (en) * | 2008-03-20 | 2011-02-10 | Arkema France | Process for Producing Hydrocyanic Acid |
| CN105502436A (en) * | 2016-01-19 | 2016-04-20 | 浦为民 | Clean production technology of hydrocyanic acid |
| CN106669705A (en) * | 2016-12-26 | 2017-05-17 | 阳泉煤业（集团）有限责任公司 | Catalyst used for methanol ammoxidation and preparation and forming method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 潘蓉等: "甲醇氨氧化法合成氢氰酸技术研究进展", 《山西化工》 * |
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Application publication date: 20200814 |
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