CN110498428A - A method of for producing hydrogen cyanide - Google Patents
A method of for producing hydrogen cyanide Download PDFInfo
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- CN110498428A CN110498428A CN201910911785.0A CN201910911785A CN110498428A CN 110498428 A CN110498428 A CN 110498428A CN 201910911785 A CN201910911785 A CN 201910911785A CN 110498428 A CN110498428 A CN 110498428A
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- hydrogen cyanide
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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
- C01C3/0262—Preparation, separation or purification of hydrogen cyanide from cyanides
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- 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
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- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of methods for producing hydrogen cyanide, include the following steps, 1) mixture of one or more of crude carbinol, thick dimethyl ether or other substances containing methoxyl group passes through an intermediate reactor；2) product by step 1) after intermediate reactor and oxygen, ammonia etc. enter a fluidized-bed reactor jointly, generate hydrogen cyanide.The present invention realizes the uplifting value of current low value-added product, can be relieved the hydrogen cyanide production capacity problem of domestic urgent need, is expected to break through the raw material production capacity bottleneck of butadiene legal system adiponitrile, has great economy meaning.The present invention is directly entered fluidized-bed reactor relative to raw materials such as methanol and reacts, and can significantly increase the service life of catalyst, increases equipment capacity.The present invention can reduce domestic hydrogen cyanide production capacity to the dependence of acrylonitrile installation by-product hydrogen cyanide, and overall flow is simple, easy to operate, high degree of automation, be convenient for industrialization promotion.
Description
Technical field
The invention belongs to technical field of chemical synthesis, more particularly, to a kind of method for producing hydrogen cyanide.
Background technique
Hydrogen cyanide (HCN), molecular weight 27.03, for colourless transparent liquid, 25.7 ゜ C of boiling point, relative density 0.6884 has
Semen armeniacae amarae taste is a kind of severe poisonous chemicals, keeps it all limited in transport and use process.In consideration of it, some main hydrogen cyanogen
Acid production country starts production and the control stringent using progress to hydrogen cyanide.Hydrogen cyanide is that a kind of chemical property is very special
Compound, many derivatives can be generated by it.These derivatives are in medicine, pesticide, dyestuff, feed addictive, sensitized
There is important use in the fields such as product, engineering material, and most products belong to fine-chemical intermediate scope.
There are about more than 50, production equipment more than 70 covers for the manufacturer of global hydrogen cyanide, and about 2,200,000 tons/year of aggregated capacity.Wherein
The production capacity of direct method production hydrogen cyanide accounts for the 70% of aggregated capacity, and the hydrogen cyanide of acrylonitrile by-product method production accounts for 30%.
Hydrogen cyanide production in the country's depends on the by-product in the production process of ammoxidation of propylene acrylonitrile production at present, realizes
The production of the hydrogen cyanide of stability and high efficiency and safety and environmental protection becomes the current field urgent problem to be solved.
Summary of the invention
In view of this, the present invention is directed to propose a kind of method for producing hydrogen cyanide, with overcome the deficiencies in the prior art.
The present invention first carries out intermediate reaction, recycles ammoxidation work using raw material abundance and cheap crude carbinol or thick dimethyl ether
The carbon-oxygen bond of ehter bond or hydroxyl is become-CN by ammonia oxidation process by skill, to obtain the hydrogen cyanide of high value, synthesis gas system
Hydrogen cyanide process flow is simple, is suitable for being widely applied.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A method of for producing hydrogen cyanide, include the following steps,
1) use raw material A for the mixing of one or more of crude carbinol, thick dimethyl ether or other substances containing methoxyl group
Object is reacted into intermediate reactor；
2) the product B for generating step 1) enters fluidized-bed reactor with the ammonia and air of preheating jointly and carries out ammonia
Oxidation reaction generates hydrogen cyanide.
In intermediate reactor, reaction can convert mix products B for thick dimethyl ether or crude carbinol, mixture B together into
Row ammoxidation reaction produces hydrogen cyanide；In addition there is a small amount of by-product such as higher alcohol in intermediate reactor, it is anti-to carry out ammoxidation
It answers, can partially generate hydrogen cyanide, there are also the by-products such as a small amount of acetonitrile, propionitrile to generate；In addition there is a small amount of by-product in intermediate reactor
Object such as higher alkane, carries out ammoxidation reaction, and product has CO, CO2And a small amount of acetonitrile, propionitrile etc..
Preferably, in raw material A used in step 1), organic matter mass content is 50%~100%；Also contain in crude carbinol
One or more of water, dimethyl ether, formaldehyde, ethanol material, also aqueous, methanol, ethyl alcohol, formaldehyde substance in thick dimethyl ether
One or more of.
Preferably, intermediate reactor reaction pressure is 0.1-30MPa, preferably 0.1-3MPa；Temperature is excellent in 220~300 ゜ C
Select 250-265 ゜ C；And it is 5000~10000h that unstripped gas, which enters the air speed of ammoxidation reaction kettle,-1·ml/gcat。
Preferably, in step 1), the catalyst used is aluminium oxide catalyst, and catalyst passes through pre-treatment；Preferably,
The reducing gas of pre-treatment is the mixed gas of hydrogen and nitrogen, and wherein the molar fraction of hydrogen is 3%~10%, and nitrogen rubs
Your score is 90~97%, and the sum of molar fraction of the two is 100%；Reduction pressure be normal pressure, reduction temperature 200-250 ゜ C,
Recovery time 10-100h.
Preferably, aluminium oxide catalyst is Al/ γ-Al2O3, the molar ratio of each component is (0.5~1): (5~20),
Preferably, Al/ γ-Al2O3, the molar ratio of each component is 1:10；
1000~4000h of volume space velocity when raw material A and above-mentioned catalyst reaction-1·ml/gcat。
Preferably, in step 2), step 1) production is in gaseous intermediate product B, is mixed with air, the ammonia after preheating
Into in fluidized-bed reactor, and step 1) production intermediate product B and air, ammonia molar ratio be 1:20~40:1.2~
2.4；The reaction temperature of ammoxidation reaction is 350-500 ゜ C, preferably 380-450 ゜ C；Pressure is 0-1MPa, preferably 0.01-
0.2MPa；It preferably, is 200~400 ゜ C into the preheating temperature of fluidized-bed reactor air, ammonia.Guarantee that charging is mixing
Hereinafter, the hydrogen cyanide generated chilling in subsequent knockout tower cools down, surplus air is discharged the lower explosion limit of material as gas phase.
Preferably, in step 2), what it is into fluidized-bed reactor further includes the mixed of one or both of nitrogen, vapor
Object is closed, and the volume ratio of the mixture of nitrogen, vapor or both and intermediate product B are 0~5.
Preferably, in step 2), the catalyst of ammoxidation reaction is catalyst with base of molybdenum, and component includes MoO3, NiO,
Al2O3, Bi2O3, molar ratio is 10:(3~5): (1.5~2): (0.8~1.2), wherein binder/support is the oxidation of silicon
Object；Preferably, molar ratio 10:4:2:1.
Preferably, in step 1), during generating intermediate product B, intermediate product B and raw material that discharge port gives off
Gas is gas, and gas-liquid separation is realized in cooling, and the gas isolated goes to downstream to continue to participate in reaction；The liquid discharge isolated；
The gas isolated passes through preheater, becomes gaseous state, excessive ammonia, air mix under lower explosion limit safety condition below
Charging enters step 2) progress ammoxidation reaction, can suitably supplement N2Or vapor changes the lower explosion limit of mixed gas.
Raw material passes through intermediate reactor, product and may the unstripped gas of remaining gas-liquid separation is realized after cooling, using changing
Product temperatur is reduced to 100 ゜ C or so by hot device, and thermal conductivity hot oil is used to preheat to air and ammonia, the gas that above-mentioned separation finishes
Body product continues to inject in fluidized-bed reactor as product B continues to participate in reaction.
Compared with the existing technology, the method for the present invention for producing hydrogen cyanide, has the advantage that
Technique provided by the invention, mixture charging reaction of less demanding to the technical difficulty of first step reaction, final
The product arrived is more single；Reaction condition is easier to realize, and convenient for control, which has obtained under other process conditions
It is verified to stable application, it is highly-safe.
Technique provided by the invention, after the first step is reacted, product B enters reaction, material in fluidized-bed reactor
More preferable to catalyst affinity, catalyst life obviously increases, and can increase equipment capacity.
Raw material is more sufficient and cheap, and the yield of hydrogen cyanide is higher, and the cost of existing hydrogen cyanide is greatly lowered；
The present invention mainly by thick dimethyl ether or crude carbinol, first passes through an intermediate reaction, and obtained product not exclusively cools down,
Separation liquid phase does not separate, and then directly enters fluidized bed ammoxidation with the ammonia after preheating, the air mixed feeding after preheating
Hydrogen cyanide is made in device, and reaction unit is by intermediate reaction device, separator, preheating device, ammonification device, separator group
At crude carbinol or thick dimethyl ether conversion are effectively hydrogen cyanide by the device, realize the conversion liter of current low value-added product
Value can be relieved the hydrogen cyanide production capacity problem of domestic urgent need, is expected to break through the raw material production capacity bottleneck of butadiene legal system adiponitrile, have
Great economy meaning.The present invention can reduce dependence of the domestic hydrogen cyanide production capacity to acrylonitrile installation by-product hydrogen cyanide, bulk flow
Journey is simple, easy to operate, high degree of automation, is convenient for industrialization promotion.
Detailed description of the invention
Fig. 1 is the schematic device that hydrogen cyanide is produced described in the embodiment of the present invention；
Wherein,
1, intermediate reactor；2, separator；3, preheater；4, preheater；5, fluidized-bed reactor；6, knockout tower.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
Reaction unit is by intermediate reactor 1 (intermediate reforming unit), separator 2 (separator), (the pre- hot charging of preheater 3
Set), fluidized-bed reactor 4 (ammonification device), knockout tower 5 (separator) composition.
Embodiment 1
Hydrogen (remaining 95% be nitrogen) reduction-oxidation Al catalysts in intermediate reactor of 5% molar ratio of normal pressure
(Al/γ-Al2O3, and the molar ratio of a few persons is 1:10), reduction temperature 230 ゜ C, recovery time 40h, volume space velocity when reduction
8000h-1·ml/gcat.It is passed through crude carbinol in intermediate reactor, aqueous 15% in crude carbinol, contains dimethyl ether 5%, boosting, instead
Answer pressure 0.1MPa, reaction temperature initial 250 ゜ C, volume space velocity 3000h-1·ml/gcat.By mixed after self-operated type counterbalance valve
It closes gas and is passed through heat-condutive oil heat exchanger, 50 ゜ C conduction oils are into being reduced to 80 ゜ C or so for product temperatur, liquid phase is discharged.Product B is in gas
Mutually and after preheating (molar ratio of product B and air, ammonia enters fluidized bed for 1:40:2.4) for the air of 200 ゜ C, ammonia mixing
Reactor, 430 ゜ C of reaction temperature, under normal pressure with catalyst with base of molybdenum (including MoO3, NiO, Al2O3, Bi2O3, mole between several persons
Hydrogen cyanide, volume space velocity 7000h are generated than reacting for 10:4:2:1)-1Ml/gcat, the hydrogen cyanide of generation is in subsequent separation
Remaining ammonia, chilling cooling are absorbed in tower, surplus air is discharged as gas phase.Hydrogen cyanide yield 92%.
Embodiment 2
Hydrogen (remaining 95% be nitrogen) reduction-oxidation Al catalysts in intermediate reactor of 5% molar ratio of normal pressure
(Al/γ-Al2O3, and the molar ratio of a few persons is 1:10), reduction temperature 230 ゜ C, recovery time 40h, volume space velocity when reduction
8000h-1·ml/gcat.It is passed through thick dimethyl ether in intermediate reactor, contains methanol 10% in thick dimethyl ether, aqueous 5%, boosting,
Reaction pressure 1MPa, reaction temperature initial 250 ゜ C, air speed 1000h-1·ml/gcat.Pass through the gaseous mixture after self-operated type counterbalance valve
It is passed through heat-condutive oil heat exchanger, 90 ゜ C conduction oils are into being reduced to 120 ゜ C or so for product temperatur.Product mix B is in gas phase and preheating
The air of 400 ゜ C, ammonia (molar ratio of product B and air, ammonia is 1:20:1.2) are mixed into fluidized-bed reactor afterwards, instead
Answer 430 ゜ C of temperature, under normal pressure with catalyst with base of molybdenum (including MoO3, NiO, Al2O3,Bi2O3, the molar ratio between several persons is 10:4:
2:1 reaction, volume space velocity 7000h-1Ml/gcat, generates hydrogen cyanide, and the hydrogen cyanide of generation absorbs surplus in subsequent knockout tower
Remaining ammonia, surplus air are discharged as gas phase.Hydrogen cyanide yield 90%.
Embodiment 3
Hydrogen (remaining 95% be nitrogen) reduction-oxidation Al catalysts in intermediate reactor of 5% molar ratio of normal pressure
(Al/γ-Al2O3, and the molar ratio of a few persons is 1:10), reduction temperature 230 ゜ C, recovery time 40h, volume space velocity when reduction
8000h-1·ml/gcat.It is passed through thick dimethyl ether in intermediate reactor, contains methanol 10% in thick dimethyl ether, aqueous 5%, boosting,
Reaction pressure 0.1MPa, reaction temperature initial 250 ゜ C, air speed 1000h-1·ml/gcat.Pass through the mixing after self-operated type counterbalance valve
Gas is passed through heat-condutive oil heat exchanger, and 90 ゜ C conduction oils are into being reduced to 80 ゜ C or so for product temperatur, isolate liquid phase.Product B is in gas
Mutually and after preheating air, the ammonia of 400 ゜ C are mixed into fluidized-bed reactor, and product B and the empty gas and water of 400 ゜ C after preheating are steamed
(molar ratio of product B and air, ammonia is 1:36:2.4 for gas, ammonia；The volume ratio of the nitrogen and product B that separately supplement is 1) to mix
Close and enter fluidized-bed reactor, under reaction temperature 430 ゜ C, gauge pressure 60kpa with catalyst with base of molybdenum (including MoO3, NiO, Al2O3,
Bi2O3, the molar ratio between several persons is 10:4:2:1) and reaction generates hydrogen cyanide, volume space velocity 7000h-1Ml/gcat is generated
Hydrogen cyanide remaining ammonia is absorbed in subsequent knockout tower, surplus air is as gas phase discharge.Hydrogen cyanide yield 94%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method for producing hydrogen cyanide, it is characterised in that: include the following steps,
1) use raw material A for the mixture of one or both of crude carbinol, thick dimethyl ether or other substances containing methoxyl group, into
Enter intermediate reactor reaction；
2) the product B for generating step 1) enters fluidized-bed reactor with the ammonia and air of preheating jointly and carries out ammoxidation
Reaction generates hydrogen cyanide.
2. the method according to claim 1 for producing hydrogen cyanide, it is characterised in that: raw material A used in step 1)
In, organic matter mass content is 50%~100%；One of also aqueous in crude carbinol, dimethyl ether, formaldehyde, ethanol material or
It is two or more, one or more of also aqueous, methanol, ethyl alcohol, formaldehyde substance in thick dimethyl ether.
3. the method according to claim 1 for producing hydrogen cyanide, it is characterised in that: in step 1), intermediate reactor
Reaction pressure be 0.1-30MPa, preferably 0.1-3MPa；Temperature is in 220~300 DEG C, preferably 250-265 DEG C；And unstripped gas into
The air speed for entering ammoxidation reaction kettle is 5000~10000h-1·ml/gcat。
4. the method according to claim 1 for producing hydrogen cyanide, it is characterised in that: in step 1), the catalysis that uses
Agent is aluminium oxide catalyst, and catalyst passes through pre-treatment；Preferably, the reducing gas of pre-treatment is the mixing of hydrogen and nitrogen
Gas, wherein the molar fraction of hydrogen is 3%~10%, and the molar fraction of nitrogen is 90~97%, the molar fraction of the two it
Be 100%；Reduction pressure be normal pressure, 200-250 DEG C of reduction temperature, recovery time 10-100h.
5. the method according to claim 4 for producing hydrogen cyanide, it is characterised in that: aluminium oxide catalyst is Al/ γ-
Al2O3, the molar ratio of each component is (0.5~1): (5~20), it is preferred that Al/ γ-Al2O3, the molar ratio of each component
For 1:10；
1000~4000h of volume space velocity when raw material A and above-mentioned catalyst reaction-1·ml/gcat。
6. the method according to claim 1 for producing hydrogen cyanide, it is characterised in that: in step 2), step 1) production
Be in gaseous intermediate product B, be mixed into fluidized-bed reactor with air, the ammonia after preheating, and step 1) production
The molar ratio of intermediate product B and air, ammonia is 1:20~40:1.2~2.4；The reaction temperature of ammoxidation reaction is 350-500
DEG C, preferably 380-450 DEG C；Pressure is 0-1MPa, preferably 0.01-0.2MPa；Preferably, into fluidized-bed reactor air, ammonia
The preheating temperature of gas is 200~400 DEG C.
7. the method according to claim 6 for producing hydrogen cyanide, it is characterised in that: in step 2), into fluidized bed
Reactor further include one or both of nitrogen, vapor mixture, and the mixture of nitrogen, vapor or both with
The volume ratio of intermediate product B is 0~5.
8. the method according to claim 1 for producing hydrogen cyanide, it is characterised in that: in step 2), ammoxidation reaction
Catalyst be catalyst with base of molybdenum, component includes MoO3, NiO, Al2O3, Bi2O3, molar ratio is 10:(3~5): (1.5~
2): (0.8~1.2), wherein binder/support is the oxide of silicon；Preferably, molar ratio 10:4:2:1.
9. the method according to claim 1 for producing hydrogen cyanide, it is characterised in that: generate intermediate product in step 1)
During B, the intermediate product B and unstripped gas that discharge port gives off, are gas, and gas-liquid separation is realized in cooling, are isolated
Gas goes to downstream to continue to participate in reaction；The liquid discharge isolated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910911785.0A CN110498428A (en) | 2019-09-25 | 2019-09-25 | A method of for producing hydrogen cyanide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910911785.0A CN110498428A (en) | 2019-09-25 | 2019-09-25 | A method of for producing hydrogen cyanide |
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| CN110498428A true CN110498428A (en) | 2019-11-26 |
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| CN201910911785.0A Pending CN110498428A (en) | 2019-09-25 | 2019-09-25 | A method of for producing hydrogen cyanide |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108883366A (en) * | 2016-01-09 | 2018-11-23 | 奥升德高性能材料公司 | The carbon monoxide-olefin polymeric directly prepared and method for the hydrogen cyanide in acrylonitrile reactor feeding logistics |
-
2019
- 2019-09-25 CN CN201910911785.0A patent/CN110498428A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108883366A (en) * | 2016-01-09 | 2018-11-23 | 奥升德高性能材料公司 | The carbon monoxide-olefin polymeric directly prepared and method for the hydrogen cyanide in acrylonitrile reactor feeding logistics |
Non-Patent Citations (1)
| Title |
|---|
| 赵炜等: "《综合性与设计性化学实验》", 31 January 2009, 中国矿业大学出版社 * |
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Application publication date: 20191126 |