CN107555450A - The process for cleanly preparing of hydrogen cyanide - Google Patents
The process for cleanly preparing of hydrogen cyanide Download PDFInfo
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- CN107555450A CN107555450A CN201710817645.8A CN201710817645A CN107555450A CN 107555450 A CN107555450 A CN 107555450A CN 201710817645 A CN201710817645 A CN 201710817645A CN 107555450 A CN107555450 A CN 107555450A
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Abstract
The present invention proposes a kind of process for cleanly preparing 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 magnesium, and the empirical formula that the catalyst has is：MoaBibMgcOd；A, b, c are atomic ratios, during a=1, b=1~3, c=1~4, 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
Technical field
The invention belongs to industrial chemicals intermediate preparing technical field, and in particular to a kind of clean manufacturing work of hydrogen cyanide
Skill.
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 process for cleanly preparing 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 process for cleanly preparing 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 magnesium, the empirical formula that the catalyst has
For：MoaBibMgcOd；A, b, c are atomic ratios, and during a=1, b=1~3, c=1~4, 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 2~8h of preliminary calcining at a temperature of 300~400 DEG C,
In 600~800 DEG C of 2~10h 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 magnesium component, 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 330 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；Mg 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 18.93g are added portionwise thereto
Magnesium carbonate, mixed solution is formed with 16.3g ethylenediamines (gross mass 10%).Under conditions of being sufficiently stirred, by 82g Ludox
(gross mass 50%) is added in mixed solution, and heat treatment forms slurry under the conditions of 100 DEG C while stirring.Afterwards using rotation
Slurry is spray-dried by pan spray drier.The fine spherical particle of gained is calcined into 8h at 300 DEG C, at 650 DEG C
Calcine 8h.
The catalyst of preparation obtains following empirical formulas：Mo1Bi1.5Mg2.6O36.9(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 51.75g are added portionwise thereto
Magnesium carbonate, 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 400 DEG C, 2h is calcined at 800 DEG C.
The catalyst of preparation obtains following empirical formulas：Mo1Bi1.75Mg3.3O15.05(TiO2)0.92。
Embodiment 3
A kind of process for cleanly preparing 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 330 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 4000h-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 87%, and purity is more than 99.9%.
Embodiment 4
A kind of process for cleanly preparing 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 6000h-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 89%, 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 process for cleanly preparing 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 magnesium, and the empirical formula that the catalyst has is：
MoaBibMgcOd；A, b, c are atomic ratios, and during a=1, b=1~3, c=1~4, d are the correspondence of catalyst component chemical combination generation
The sum of oxygen atom in oxide.
2. the process for cleanly preparing 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 2~8h of preliminary calcining at a temperature of 300~400 DEG C, 600
~800 DEG C of 2~10h of temperature calcination.
3. the process for cleanly preparing 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 magnesium component
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 process for cleanly preparing of hydrogen cyanide according to claim 1 or 2, it is characterised in that the reaction of the step 1)
Temperature is 330 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 process for cleanly preparing of hydrogen cyanide according to claim 1 or 2, it is characterised in that reaction velocity be 3000~
6000h-1。
6. the process for cleanly preparing 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.
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Citations (4)
| 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 |
-
2017
- 2017-09-12 CN CN201710817645.8A patent/CN107555450A/en active Pending
Patent Citations (4)
| 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: 20180109 |