CN104724726B - Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine - Google Patents
Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine Download PDFInfo
- Publication number
- CN104724726B CN104724726B CN201410671418.5A CN201410671418A CN104724726B CN 104724726 B CN104724726 B CN 104724726B CN 201410671418 A CN201410671418 A CN 201410671418A CN 104724726 B CN104724726 B CN 104724726B
- Authority
- CN
- China
- Prior art keywords
- hydrogen cyanide
- bis
- ketazine
- reactor
- tail gas
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/14—Cyanic or isocyanic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention provides a technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine. The technological method comprises the steps that a light oil cracking hydrogen cyanide gas mixture is used as a raw material and undergoes an ammonia removal process and a cryogenic process to obtain liquid hydrogen cyanide, wherein in the ammonia removal process, the hydrogen cyanide gas mixture is absorbed with a sulfuric acid aqueous solution; in the cryogenic process, the hydrogen cyanide gas mixture is cooled to minus 10-minus 20 DEG C, after the hydrogen cyanide gas mixture is cooled, a part of the hydrogen cyanide gas becomes liquid to obtain liquid hydrogen cyanide, and the other part of the hydrogen cyanide gas is the tail gas containing hydrogen cyanide; the tail gas containing hydrogen cyanide, which undergoes cryogenic treatment, is absorbed with a ketazine aqueous solution to obtain an aqueous solution containing bisisobutyronitrile hydrazine, and the aqueous solution containing bisisobutyronitrile hydrazine undergoes cooling, crystallization and centrifugal filtration to obtain a bisisobutyronitrile hydrazine crystalline solid. By adopting the technological method, the purification efficiency and the utilization efficiency of hydrogen cyanide can be obviously improved, meanwhile, the energy consumption in the hydrogen cyanide purification process is greatly reduced and can be reduced by 90% at most, and the utilization rate of hydrogen cyanide is more than 99.9%.
Description
Technical field
The invention belongs to chemical field, it is related to purified hydrogen cyanogen in a kind of reaction mixture gas of light oil cracking production hydrogen cyanide
Acid and the method using End gas production bis-isobutyronitrile hydrazine.
Background technology
Hydrogen cyanide is a kind of broad-spectrum industrial chemicals, can apply to medicine, agricultural chemicals, cosmetics, dyestuff, chemical fertilizer,
The various fields such as plating, macromolecular material, photograph, mining industry, metallurgy.At present, the main production process of hydrogen cyanide mainly has light oil
Cracking process, iS-One method（Andrussow method）, BMA method and acrylonitrile by-product method etc..Light oil cracking is with light oil（Or vapour
Oil）, liquefied ammonia and caustic soda be primary raw material, oil char particle and nitrogen are the working system of auxiliary material, make light oil and liquefied ammonia gas first
Change, and mix in atomizer in proportion, be preheated to 280 DEG C, immerse the boiling of petroleum coke granulosa conductive exothermal by three-phase electrode
Rise reacting furnace, under the conditions of normal pressure, 1450 DEG C, can be cleaved into hydrocyanic acid gas；IS-One method is by one by methane, ammonia and oxygen
Certainty ratio is passed through oxidator after being sufficiently mixed, with platinum-rhodium alloy or platinumiridio as catalyst, at ambient pressure, more than 1000 DEG C
Under conditions of hydrogen cyanide is synthesized；BMA method is the improvement to iS-One method it is not necessary to oxygen participates in reaction, with platinum as catalyst,
Methane and ammonia are synthesized hydrogen cyanide under conditions of normal pressure, more than 1300 DEG C；Acrylonitrile by-product method is to use propylene ammonification
The method of oxidizing process acrylonitrile production by-product hydrogen cyanide, the method is with propylene, ammonia and air in oil gas as raw material, propylene and ammonia
Mixing is sent in oxidation reactor by a certain percentage, evenly spreads in beds by distributor, air is by a certain percentage
Enter from reactor bottom, flow up through distribution grid, simultaneously by-product hydrogen cyanide.
But no matter produced using iS-One method, BMA method, light oil cracking method or the hydrogen cyanide of acrylonitrile by-product method production mix
Close gas, in gaseous mixture, major part is inert gas, only 7%～30% hydrocyanic acid gas.Hydrogen cyanide gaseous mixture greatly limit
Its range, for example, in the synthesis of acetone cyanohydrin, in order to obtain highly purified acetone cyanohydrin, generally adopt highly purified
Hydrogen cyanide liquid；Butadiene and hydrogen cyanide react production adiponitrile, and the purity requirement to hydrogen cyanide is very high, especially right
In hydrogen cyanide, the requirement of water and oxygen is strict, and for the production of these compounds, hydrogen cyanide gaseous mixture is to replace
Highly purified hydrogen cyanide liquid.In order to obtain highly purified liquid hydrogen cyanide all inevitably using the side absorbing with rectifying
Method, in traditional hydrogen cyanide purifying technique, is absorbed using water more than the method for absorption hydrogen cyanide, and this not only requires nothing more than and will absorb hydrogen cyanogen
The water of acid is refrigerated to relatively low temperature, leads to reduction temperature to need hydrogen cyanide in high energy consumption, and the hydrogen cyanide absorbing liquid of gained
Concentration relatively low（It is about 10 ~ 20g/L）, lead to hydrogen cyanide purification efficiency low, and in order to steam hydrogen cyanide soluble in water,
Need to carry out rectifying, cooling down, just can obtain highly purified liquid hydrogen cyanide, every one ton of hydrogen cyanide of rectifying, consume steam and be up to
15 tons.Additionally, traditional hydrogen cyanide purifying technique can not possibly be completely by the GAS ABSORPTION of hydrogen cyanide, therefore, tail after absorption
The hydrocyanic acid gas of meeting entrainment portions in gas, the hydrocyanic acid gas that these are carried secretly lose with the burning of tail gas, could not obtain
Make full use of, therefore, the liquefied fraction highest of hydrogen cyanide only has 95%.
Bis-isobutyronitrile hydrazine is the necessary intermediate producing azodiisobutyronitrile, and bis-isobutyronitrile hydrazine obtains idol through chlorine oxidation
Nitrogen bis-isobutyronitrile crude product, crude product, again through recrystallization, is dried, obtains azodiisobutyronitrile product.Bis-isobutyronitrile hydrazine is another kind of raw
Product method is with hydrazine hydrate, condensation reaction to occur with acetone cyanohydrin.But because the preparation of acetone cyanohydrin needs to use highly purified liquid
Body hydrogen cyanide, therefore Acetone cyanohydrin method prepare bis-isobutyronitrile hydrazine, and it is relatively costly.
It is big to there is hydrogen cyanide purifying process complexity, high cost, energy consumption in above method；Or hydrogen cyanide utilization rate is more low not
Foot, is difficult to accept in the industrial production.
Content of the invention
It is an object of the invention to overcoming the above-mentioned deficiency of prior art, providing and a kind of can significantly improve hydrogen cyanide
Purification efficiency and the utilization ratio of hydrogen cyanide, greatly reduce simultaneously in hydrogen cyanide purge process energy consumption, use light oil cracking
The reaction mixture gas producing hydrogen cyanide combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine.
With hereinafter in addition to indicating all concentration mentioned and ratio be concentration expressed in percentage by weight or weight ratio.
Technical program of the present invention lies in：With light oil cracking hydrogen cyanide gaseous mixture as raw material, through except ammonia operation, deep cooling work
Sequence obtains liquid hydrogen cyanide：Described except ammonia operation be that hydrogen cyanide gaseous mixture is absorbed with the aqueous sulfuric acid of 5～40 weight %；Institute
Stating deep cooling operation is that hydrogen cyanide gaseous mixture is cooled to -10 DEG C～-20 DEG C, hydrogen cyanide gaseous mixture after supercooling, a part of hydrogen
Cyanic acid gas is changed into liquid, obtains liquid hydrogen cyanide, and another part hydrocyanic acid gas are the tail gas containing hydrogen cyanide；Through deep cooling
The tail gas containing hydrogen cyanide absorbed with the ketazine aqueous solution, the temperature of absorption is 30 DEG C～50 DEG C, obtains containing bis-isobutyronitrile
The aqueous solution of hydrazine, obtains bis-isobutyronitrile hydrazine crystalline solid through supercooling, crystallization, centrifugal filtration.Filtrate cycle is used for preparation third
The ketazine aqueous solution absorbs the tail gas containing hydrogen cyanide.The tail gas absorbing main hydrogen after operation through ketazine enters and burns
Burn stove to be burned.
Aqueous sulfuric acid used by the operation except ammonia of the present invention is 30～40 weight % aqueous sulfuric acids, the temperature of absorption
It is less than 50 DEG C.The selection of the concentration of sulfuric acid ensures, when it absorbs ammonia, to separate out ammonia sulfate crystal, temperature control exists
During low temperature, be conducive to controlling the vapor in gaseous mixture.Described light oil cracking hydrogen cyanide gaseous mixture after sulfuric acid absorption ammonia,
Hydrogen cyanide 20%～30% in gaseous mixture, hydrogen 58%～90%, vapor 0.1%～3%.
Of the present invention except also including eliminating water operation between ammonia operation and described deep cooling operation.
Eliminating water operation of the present invention is hydrogen cyanide gaseous mixture to be passed through in the aqueous sulfuric acid of 50～80 weight %, preferably
The aqueous sulfuric acid of 65～70 weight %.
Eliminating water operation of the present invention is the aqueous sulfuric acid of 65～70 weight % of the hydrogen cyanide gaseous mixture after except ammonia
Carry out eliminating water, during eliminating water, temperature is 10 DEG C～45 DEG C.
In described raw material light oil cracking hydrogen cyanide gaseous mixture, hydrogen cyanide 20%～30%, hydrogen 58%～90%, ammonia 0.1%～
2%.
Of the present invention except also including refrigerating work procedure between ammonia operation and described eliminating water operation, described refrigerating work procedure is right
Hydrogen cyanide gaseous mixture after except ammonia is cooled down, and removes part water, and chilling temperature is 10 DEG C～20 DEG C.Cooling water circulation
To except the sulfuric acid thinned water of ammonia, in the described hydrogen cyanide gaseous mixture obtaining after part eliminating water, the content of moisture is less than
0.5%.
Eliminating water operation of the present invention is that hydrogen cyanide gaseous mixture is passed through in 50～80% aqueous sulfuric acid, preferably 65～
70% aqueous sulfuric acid.Can the concentration of sulfuric acid be directly connected to and absorb moisture, and the concentration of theoretically sulfuric acid is higher, then inhale
Water effect is more obvious, but excessive concentration, necessarily lead to increase its oxidisability, in order to prevent hydrogen cyanide oxidized, select sulphur
The concentration of acid is 65～70%；Or the described hydrogen cyanide gaseous mixture after except ammonia is directly removed with 65～70% sulfuric acid
Water, during eliminating water, temperature is 10 DEG C～40 DEG C.In hydrogen cyanide gaseous mixture after the described eliminating water through persulfuric acid, the content of water is less than
1000ppm.
Eliminating water operation of the present invention is that the hydrogen cyanide gaseous mixture after except ammonia is removed with the sulfuric acid of 65～70 weight %
Water, during eliminating water, temperature is 10 DEG C～45 DEG C.
The operation that the present invention absorbs through the tail gas ketazine aqueous solution containing hydrogen cyanide for the deep cooling is：
Add the ketazine aqueous solution in two reactors of series connection, then by above-mentioned tail gas containing hydrogen cyanide from reactor
Bottom be passed through in the ketazine aqueous solution, control tail gas flow velocity be 250 cubes ms/h, reaction temperature be 35 DEG C～40
DEG C, when the ketazine in first reactor 70% is converted into bis-isobutyronitrile hydrazine, it is incorporated in acetone in first reactor even
The water of 3 times of quality of nitrogen, continues to be passed through tail gas, when the ketazine 40% about in the second reactor is converted into bis-isobutyronitrile hydrazine, will
Feed liquid in first reactor is transferred in cooling reactor and is cooled to 0 DEG C～5 DEG C, crystallization, and suction filtration obtains bis-isobutyronitrile hydrazine crystallization
Property solid product.Feed liquid in second reactor is transferred in the first reactor, and adds above-mentioned in the first reactor
The mother liquor that suction filtration obtains, the second reactor adds new ketazine solution, continues to be passed through the tail gas containing hydrogen cyanide.Whole process
Repeat.
Absorb, through ketazine, the tail gas entrance incinerator not absorbed by ketazine after operation to be burned.
In the ketazine aqueous solution of the present invention, the concentration of ketazine is 10--70 weight %.
The described tail gas absorbing through ketazine, the content of its hydrogen cyanide is less than 5ppm, and tail gas is substantial amounts of hydrogen,
Can directly be burned, byproduct steam.
In the present invention, the described sulfuric acid after absorbing ammonia, the residual of its free Cyanide, available nitrogen or air blow
Sweep.
In the present invention, the described sulfate moieties extraction after eliminating water or whole extraction, are used for absorbing through dilution
Ammonia in hydrogen cyanide gaseous mixture；Described hydrogen cyanide gaseous mixture after eliminating water obtains liquid hydrogen cyanide, purity through deep cooling
More than 99.5%.
The comprehensive utilization operation of the described purifying of hydrogen cyanide gaseous mixture and hydrogen cyanide tail gas is all in micro-vacuum state
Under carry out.
The beneficial effects of the present invention is：The present invention adopts the side that direct deep cooling and tail gas are combined with ketazine absorption phase
Method, more traditional utilization water absorbs, the method for rectifying again, and utilization rate height, the hydrogen cyanide purifying energy consumption with hydrogen cyanide are low, relatively pass
The advantage that system process energy consumption reduces by 90%；Whole process atmospheric pressure state, it is to avoid the decomposition of hydrogen cyanide and polymerization, greatly reduces
The security risk when investment of equipment and operation；Tail gas is absorbed with ketazine, not only produces high-quality bis-isobutyronitrile hydrazine,
And decrease the loss of hydrogen cyanide, reduce the production cost of bis-isobutyronitrile hydrazine, improve the comprehensive utilization of hydrogen cyanide, hydrogen cyanogen
The utilization rate of acid is more than 99.9%, it is to avoid hydrogen cyanide, to the pollution of air and its harm to human body, has veritably accomplished ring
The production technology protected, clean.
Specific embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, below will be to the preferred embodiments of the present invention
It is described in detail.
Embodiment 1
（1）Except ammonia：To in dilute sulfuric acid measuring tank, the aqueous sulfuric acid of addition 35%, as except ammonia agent, light oil cracking is obtained
Hydrogen cyanide gaseous mixture ammonia removal column is passed through by bottom, spray into dilute sulfuric acid from ammonia removal column top, hydrogen cyanide gaseous mixture is through removing simultaneously
After ammoniacal liquor counter-current absorption removes the ammonia wherein containing, from the top of ammonia removal column out；After absorbing ammonia except ammoniacal liquor is after supercooling
Can recycle, regularly replace new dilute sulfuric acid.
（2）Eliminating water：From the top of ammonia removal column, hydrogen cyanide gaseous mixture out is passed through cooling tower, the cooling of cooling tower by bottom
Temperature is 10 DEG C～20 DEG C, and after supercooling, part vapor is changed into condensed water pipeline and is back to tower hydrogen cyanide gaseous mixture
Bottom, the hydrogen cyanide gaseous mixture after part eliminating water comes from cooling tower ejection, and the condensed water containing hydrogen cyanide of bottom of towe also may be used
To be recycled to the thinned water of dilute sulfuric acid；To in sulfuric acid measuring tank add 70% aqueous sulfuric acid as dehydrating agent, from cooling tower
Tower top gaseous mixture out be passed through in dehydrating tower by bottom again, spray into dehydrating agent from dehydration top of tower, after eliminating water simultaneously
Hydrogen cyanide gaseous mixture from dehydration column overhead out；Absorb the dehydrating agent after water can recycle, regularly replace new dehydration
Agent, or the dehydrating agent part extraction after being diluted, add the dehydrating agent after 98% sulfuric acid is diluted and are adjusted to 70%
Concentration.After absorbing water, the dehydrating agent of extraction is recycled to ammonia removal column and uses.
（3）Deep cooling：Will out hydrogen cyanide gaseous mixture be passed through deep-cooling heat exchanger, deep-cooling heat exchanger by bottom from eliminating water column overhead
Chilling temperature be -10 DEG C～-20 DEG C, after supercooling, most of hydrocyanic acid gas are changed into the hydrogen cyanide gaseous mixture after dehydration
Liquid stays the bottom of hydrogen cyanide receiver, introduces from the top blast pipe of hydrogen cyanide receiver containing a small amount of hydrogen cyanide tail gas
Absorb operation；The hydrogen cyanide purity liquid obtaining through deep cooling is more than 99.5%, and liquefied fraction is 80.5%.
（4）Tail gas absorption：Add the ketazine aqueous solution in two reactors carrying stirring of series connection, then will be upper
After stating deep cooling operation, tail gas containing hydrogen cyanide is passed through the ketazine aqueous solution from the bottom of reactor, and the flow velocity of control tail gas is
250 cubes ms/h, reaction temperature is 35 DEG C～40 DEG C, and the ketazine when in first reactor 70% is converted into two isobutyls
Nitrile hydrazine, is incorporated in the water of 3 times of quality of ketazine in first reactor, continues to be passed through tail gas, when 40% in the second reactor
Ketazine about when being converted into bis-isobutyronitrile hydrazine, the feed liquid in first reactor is transferred in cooling reactor and is cooled to 0
DEG C～5 DEG C, crystallization, suction filtration obtains bis-isobutyronitrile hydrazine wet product.Feed liquid in second reactor is transferred in the first reactor, with
And add the mother liquor that above-mentioned suction filtration obtains in the first reactor, the second reactor adds new ketazine solution, continues logical
Enter the tail gas containing hydrogen cyanide.Whole process repeats.
Embodiment 2
The present embodiment is with the difference of embodiment 1：
Cancelled cooling de-watering before sulfuric acid eliminating water.
（1）Except ammonia：35% dilute sulfuric acid aqueous solution, the hydrogen cyanide that light oil cracking is obtained is added in dilute sulfuric acid measuring tank
Gaseous mixture is passed through ammonia removal column by bottom, sprays into dilute sulfuric acid from ammonia removal column top simultaneously, and reaction mixture gas are through inhaling except ammoniacal liquor adverse current
Receive after removing the ammonia wherein containing, from the top of ammonia removal column out；Using through supercooling Posterior circle except ammoniacal liquor after absorbing ammonia, fixed
The dilute sulfuric acid that phase more renews.
（2）Eliminating water：Add 70% sulfuric acid as dehydrating agent in sulfuric acid measuring tank, from the tower top of cooling tower out mixed
Close gas to be passed through in dehydrating tower by bottom again, spray into dehydrating agent from dehydration top of tower, the hydrogen cyanide gaseous mixture after eliminating water simultaneously
From dehydration column overhead out；Absorb the dehydrating agent after water can recycle, regularly replace new dehydrating agent, or will be diluted
Dehydrating agent part extraction afterwards, adds the concentration that the dehydrating agent after 98% sulfuric acid is diluted is adjusted to 70%.Adopt after absorbing water
The dehydrating agent going out is recycled to ammonia removal column and uses.
（3）Deep cooling：Will out hydrogen cyanide gaseous mixture be passed through deep cooling tower, the cooling temperature of deep cooling tower by bottom from eliminating water column overhead
Spend for -10 DEG C～-20 DEG C, after supercooling, most of part hydrocyanic acid gas are changed into liquid and stay tower hydrogen cyanide gaseous mixture
Bottom, containing a small amount of hydrogen cyanide tail gas from the tower top of deep cooling tower out；The hydrogen cyanide purity liquid obtaining through deep cooling is more than
99.5%, liquefied fraction is 80.5%.
（4）Tail gas absorption：Add the ketazine aqueous solution in two reactors of series connection, then by above-mentioned containing hydrogen cyanide
Tail gas is passed through the ketazine aqueous solution from the bottom of reactor, controls the flow velocity of tail gas to be 250 cubic meters/hour, reaction temperature
For 35 DEG C～40 DEG C, the ketazine when in first reactor 70% is converted into bis-isobutyronitrile hydrazine, adds in first reactor
Enter the water of 3 times of quality of ketazine, continue to be passed through tail gas, when being converted into two about 40% ketazine in the second reactor
Isobutyronitrile hydrazine, the feed liquid in first reactor is transferred in cooling reactor and is cooled to 0 DEG C～5 DEG C, crystallization, and it is different that suction filtration obtains two
Butyronitrile hydrazine wet product.Feed liquid in second reactor is transferred in the first reactor, and adds above-mentioned in the first reactor
The mother liquor that suction filtration obtains, the second reactor adds new ketazine solution, continues to be passed through the tail gas containing hydrogen cyanide.Whole process
Repeat.
Finally illustrate, above example only in order to technical scheme to be described and unrestricted, although with reference to relatively
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent, the objective without deviating from technical solution of the present invention and scope, and it all should be covered at this
In the middle of the right of invention.
Claims (10)
1. a kind of combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine it is characterised in that：Including being split with light oil
Solution hydrogen cyanide gaseous mixture is raw material, through obtaining liquid hydrogen cyanide except ammonia operation, deep cooling operation：Described except ammonia operation be by hydrogen cyanogen
Sour gaseous mixture is absorbed with the aqueous sulfuric acid of 5～40 weight %；Described deep cooling operation is that hydrogen cyanide gaseous mixture is cooled to -10 DEG C
～-20 DEG C, after supercooling, a part of hydrocyanic acid gas are changed into liquid to hydrogen cyanide gaseous mixture, obtain liquid hydrogen cyanide, another portion
Hydrocyanic acid gas are divided to be the tail gas containing hydrogen cyanide；Inhaled with the ketazine aqueous solution through the tail gas containing hydrogen cyanide for the deep cooling
Receive, the temperature of absorption is 30 DEG C～50 DEG C, obtains the aqueous solution containing bis-isobutyronitrile hydrazine, obtains through supercooling, crystallization, centrifugal filtration
Bis-isobutyronitrile hydrazine crystalline solid.
2. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 1 it is characterised in that：Institute
State except aqueous sulfuric acid used by ammonia operation be 30～40 weight % aqueous sulfuric acids, the temperature of absorption is less than 50 DEG C.
3. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 1 it is characterised in that：Institute
State except also including eliminating water operation between ammonia operation and described deep cooling operation.
4. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 3 it is characterised in that：Institute
Stating eliminating water operation is that hydrogen cyanide gaseous mixture is passed through in the aqueous sulfuric acid of 50～80 weight %.
5. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 3 it is characterised in that：Institute
Stating eliminating water operation is that hydrogen cyanide gaseous mixture is passed through the aqueous sulfuric acid of 65～70 weight %.
6. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 3 it is characterised in that：Institute
State the hydrogen cyanide gaseous mixture that eliminating water operation is after except ammonia and carry out eliminating water with the aqueous sulfuric acid of 65～70 weight %, during eliminating water
Temperature is 10 DEG C～45 DEG C.
7. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 3 it is characterised in that：Institute
State except also including refrigerating work procedure between ammonia operation and described eliminating water operation, described refrigerating work procedure is to the hydrogen cyanogen after except ammonia
Sour gaseous mixture is cooled down, and chilling temperature is 10 DEG C～20 DEG C.
8. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 1 it is characterised in that warp
Crossing the operation that the tail gas ketazine aqueous solution containing hydrogen cyanide of deep cooling absorbs is：
Series connection two reactors in add the ketazine aqueous solution, then by through the tail gas containing hydrogen cyanide for the deep cooling from
The bottom of reactor is passed through in the ketazine aqueous solution, controls the flow velocity of tail gas to be 250 cubes ms/h, reaction temperature is 35
DEG C～40 DEG C, when the ketazine in first reactor 70% is converted into bis-isobutyronitrile hydrazine, add third in first reactor
The water of 3 times of quality of ketazine, continues to be passed through the tail gas containing hydrogen cyanide through deep cooling, the ketazine in the second reactor
40% about is converted into bis-isobutyronitrile hydrazine, the feed liquid in first reactor is transferred in cooling reactor and is cooled to 0 DEG C～5 DEG C, knot
Crystalline substance, suction filtration obtains bis-isobutyronitrile hydrazine crystalline solid product；Feed liquid in second reactor is transferred in the first reactor, with
And add the mother liquor that above-mentioned suction filtration obtains in the first reactor, the second reactor adds new ketazine solution, continues logical
Enter the tail gas containing hydrogen cyanide through deep cooling, whole process repeats.
9. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 1 or 8, its feature exists
In：In the described ketazine aqueous solution, the concentration of ketazine is 10～70 weight %.
10. combine the process preparing liquid hydrogen cyanide and bis-isobutyronitrile hydrazine according to claim 1 or 8, its feature exists
In：Absorb, through ketazine, the tail gas entrance incinerator not absorbed by ketazine after operation to be burned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410671418.5A CN104724726B (en) | 2014-11-21 | 2014-11-21 | Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410671418.5A CN104724726B (en) | 2014-11-21 | 2014-11-21 | Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104724726A CN104724726A (en) | 2015-06-24 |
| CN104724726B true CN104724726B (en) | 2017-02-22 |
Family
ID=53449231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410671418.5A Active CN104724726B (en) | 2014-11-21 | 2014-11-21 | Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104724726B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020831A (en) * | 2017-06-09 | 2018-12-18 | 辽宁双旗精细化工有限公司 | A kind of preparation method of azodiisobutyronitrile |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10034193A1 (en) * | 2000-07-13 | 2002-03-28 | Roehm Gmbh | Process for the production of hydrogen cyanide |
| CN101033412B (en) * | 2007-03-29 | 2010-09-29 | 河北志诚化工集团有限公司 | Circulation utilization method for light oil cracking tail gas |
| FR2928910B1 (en) * | 2008-03-20 | 2010-03-12 | Arkema France | IMPROVED PROCESS FOR THE PRODUCTION OF CYANHYDRIC ACID |
| CN101445471B (en) * | 2008-12-18 | 2011-11-23 | 上海试四赫维化工有限公司 | Method for synthesizing bis-isobutyronitrile hydrazine |
| CN102502707B (en) * | 2011-10-26 | 2014-04-23 | 重庆紫光化工股份有限公司 | Method for purifying hydrocyanic acid from mixed gas containing hydrocyanic acid |
| CN102633283A (en) * | 2012-04-01 | 2012-08-15 | 重庆紫光化工股份有限公司 | Purification method of hydrocyanic acid |
-
2014
- 2014-11-21 CN CN201410671418.5A patent/CN104724726B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104724726A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102502708B (en) | Preparation method for preparing alkali metal or alkali earth metal cyanide with high purity and high yield | |
| US20200172475A1 (en) | Urea Manufacturing Method And Urea Manufacturing Apparatus | |
| CN102303874B (en) | Method for preparing ammonium sulfate by conversion of phosphogyspum with polycrystalline method | |
| US8585870B2 (en) | Process to C-manufacture acrylonitrile and hydrogen cyanide | |
| CN102730720B (en) | Method and system for recovering ammonia from gas containing hydrocyanic acid | |
| CN104724724B (en) | A kind of combine the process preparing liquid hydrocyanic acid and Cyanogran. | |
| CN104725269B (en) | A kind of combine the process preparing liquid hydrocyanic acid and hydroxyacetonitrile | |
| CN104724726B (en) | Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine | |
| RU2454403C1 (en) | Method of producing carbamide | |
| CN109231168B (en) | Method and device for reducing sulfuric acid content in hydrochloric acid and acetic acid by-products in chloroacetic acid production | |
| CN103274921B (en) | Device and method for preparing calcium formate by utilizing yellow phosphorus tail gas | |
| CN112919439A (en) | Method and device for continuously preparing high-purity phosphorus pentachloride | |
| AU2006244735B2 (en) | Method for concentrating an aqueous ammonium carbamate stream | |
| KR20030095999A (en) | Improved Process for Producing Acetone Cyanohydrin | |
| CN203159238U (en) | Equipment for jointly producing ammonium sulfate, hydrogen chloride and methane chloride | |
| CN113044857B (en) | Production process for preparing high-purity sodium cyanide or potassium cyanide with high yield | |
| CN106745066A (en) | Produce, purify the safe technology and system of hydrogen cyanide | |
| CN217398465U (en) | Production device for preparing high-purity sodium cyanide or potassium cyanide with high yield | |
| CN210065171U (en) | Chlorosulfonic acid production system | |
| US2675298A (en) | Hydrazine manufacture | |
| US1332581A (en) | Sulfuric and haloid acids | |
| MXPA02007551A (en) | Process for preparing melamine from urea. | |
| CN109292808A (en) | A kind of caprolactam production process with low ammonia consumption | |
| RU2529462C1 (en) | Method of producing carbamide | |
| CN109179352B (en) | Utilization method of chlorination by-product generated in preparation of phosphorus pentachloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |