CN102502707A - Method for purifying hydrocyanic acid from mixed gas containing hydrocyanic acid - Google Patents
Method for purifying hydrocyanic acid from mixed gas containing hydrocyanic acid Download PDFInfo
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- CN102502707A CN102502707A CN2011103290271A CN201110329027A CN102502707A CN 102502707 A CN102502707 A CN 102502707A CN 2011103290271 A CN2011103290271 A CN 2011103290271A CN 201110329027 A CN201110329027 A CN 201110329027A CN 102502707 A CN102502707 A CN 102502707A
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Abstract
The invention discloses a method for purifying hydrocyanic acid from mixed gas containing the hydrocyanic acid, which comprises an absorption step and a rectification step, wherein in the absorption step, pressurizing the mixed gas containing the hydrocyanic acid to 0.11-1.5 MPa, then cooling to 10-80 DEG C, introducing into a pressure absorption tower, and pressurizing and absorbing the hydrocyanic acid in the mixed gas with absorption liquid, i.e. acidic aqueous solution with a pH value of 1-6 under the conditions that the pressure in the tower is 0.11-1.0 MPa, and the temperature is 0-60 DEG C to obtain hydrocyanic acid absorption liquid. The method has the beneficial effects that the existing atmospheric absorption method is replaced by a pressure absorption method to absorb the hydrocyanic acid in the mixed gas containing the hydrocyanic acid; the absorption temperature can be improved to 60 DEG C; the concentration of the hydrocyanic acid in the hydrocyanic acid absorption liquid can be improved by 3-10 times, so that the purifying efficiency of the hydrocyanic acid can be remarkably improved; and meanwhile, the energy consumption is greatly reduced and can be reduced by 80 percent to a maximum extent.
Description
Technical field
The invention belongs to chemical field, relate to a kind of from the reaction mixture gas of producing prussic acid the method for purified hydrogen cyanic acid.
Background technology
Prussic acid is a kind of broad-spectrum industrial chemicals, can be applicable to various fields such as medicine, agricultural chemicals, makeup, dyestuff, chemical fertilizer, plating, polymer, photograph, mining industry, metallurgy.The working method of prussic acid mainly contains iS-One method (Andrussow method), BMA method, light oil cracking method, vinyl cyanide by-product method etc.IS-One method is that methane, ammonia and oxygen are fed oxidation reactor behind the thorough mixing by a certain percentage, is catalyzer with platinum rhodium or platinum iridium alloy, the synthetic prussic acid of reaction under normal pressure, condition more than 1000 ℃.The BMA method is the improvement to iS-One method, does not need oxygen to participate in reaction, is to be catalyzer with platinum, and prussic acid is synthesized in the reaction under normal pressure, condition more than 1300 ℃ of methane and ammonia.Light oil cracking method is to be main raw material with light oil (or gasoline), liquefied ammonia and caustic soda; Refinery coke grain and nitrogen are the working system of auxiliary material; At first make the gasification of light oil and liquefied ammonia, and in spraying gun, mix in proportion, be preheated to 280 ℃; Boiling reaction stove through three-phase electrode immersion refinery coke granulosa conductive exothermal promptly can be cleaved into the splitting gas that contains 20 ~ 25% prussic acid under normal pressure, 1450 ℃ of conditions.Vinyl cyanide by-product method is the method with propylene ammmoxidation process acrylonitrile production coproduct hydrogen cyanic acid, and this method is a raw material with propylene, ammonia and air in the petroleum gas, and propylene and ammonia mix by a certain percentage sends into oxidation reactor, is evenly spread in the beds by sparger; Air gets into from reactor bottom by a certain percentage, upwards flows through grid distributor, mixes with propylene, ammonia and makes the catalyst bed laminarization; Reactant generates down vinyl cyanide at 440 ~ 450 ℃ with catalyst action, while coproduct hydrogen cyanic acid.The reaction mixture gas that adopts iS-One method, BMA method or light oil cracking method production prussic acid to obtain need pass through except that ammonia, absorption, rectifying three step process, could obtain highly purified liquid hydrogen cyanic acid.Wherein, removing the ammonia step is to remove the unreacted that contains in reaction mixture gas raw material ammonia completely; Absorption step is under condition of normal pressure, to absorb the hydrocyanic acid gas that contains except that in the gas mixture behind the ammonia with acid absorption liquid, obtains the prussic acid absorption liquid; Rectification step is that the prussic acid absorption liquid is carried out atmospheric distillation, collects the prussic acid cut, promptly obtains liquid hydrogen cyanic acid after the condensation.That adopts that vinyl cyanide by-product method makes contains the prussic acid gas mixture and need not remove ammonia, through absorption, rectifying two step process, just can obtain highly purified liquid hydrogen cyanic acid.But in the above-mentioned prussic acid purifying technique; Absorption step not only requires lower absorption temperature (10 ~ 15 ℃); The energy consumption of needs of causing lowering the temperature is high, and the prussic acid concentration in the gained prussic acid absorption liquid lower (being about 10g/L), causes the prussic acid purification efficiency low.
Summary of the invention
In view of this; The object of the present invention is to provide a kind of from contain the prussic acid gas mixture method of purified hydrogen cyanic acid, do not need lower absorption temperature, and the concentration of prussic acid is higher in the gained prussic acid absorption liquid; Thereby can significantly improve the purification efficiency of prussic acid, cut down the consumption of energy greatly simultaneously.
For achieving the above object, the present invention provides following technical scheme:
The method of purified hydrogen cyanic acid from contain the prussic acid gas mixture; Comprise absorption step and rectification step, said absorption step is to be forced into 0.11 ~ 1.5MPa with containing the prussic acid gas mixture, is cooled to 10 ~ 80 ℃ again; Feed the pressurizing absorption tower; In the tower internal pressure is that 0.11 ~ 1.0MPa, temperature are under 0 ~ 60 ℃ the condition, and using absorption liquid is that pH is the hydrocyanic acid gas in 1 ~ 6 the acidic aqueous solution pressurizing absorption gas mixture, obtains the prussic acid absorption liquid.Said acidic aqueous solution both can be inorganic aqueous acids such as sulfuric acid, hydrochloric acid, phosphoric acid, also can be the organic acid aqueous solution such as acetic acid, oxalic acid, the preferably sulfuric acid aqueous solution.
(gas compression is bigger than more because of the gas compression meeting causes gas temperature to rise; Gas temperature raises more), hypertonia will increase the energy consumption of compression and cooling, and prussic acid belongs to severe toxicity type material; High pressure will increase facility investment and security risk greatly; And therefore the easy polymerization of prussic acid under the hot conditions and influence product yield, selects suitable absorption pressure and absorption temperature extremely important in absorption step.Preferably; Said absorption step is to be forced into 0.2 ~ 0.7MPa with containing the prussic acid gas mixture; Being cooled to 30 ~ 50 ℃ again, feeding the pressurizing absorption tower, is that 0.15 ~ 0.6Mpa, temperature are under 20 ~ 40 ℃ the condition in the tower internal pressure; Using pH is the hydrocyanic acid gas in 2 ~ 5 the acidic aqueous solution pressurizing absorption gas mixture, obtains the prussic acid absorption liquid.Preferred; Said absorption step is to be forced into 0.7MPa with containing the prussic acid gas mixture; Being cooled to 45 ℃ again, feeding the pressurizing absorption tower, is that 0.3 ~ 0.5Mpa, temperature are under 25 ~ 30 ℃ the condition in the tower internal pressure; Using pH is the hydrocyanic acid gas in 2 the aqueous sulfuric acid pressurizing absorption gas mixture, obtains the prussic acid absorption liquid.
For the better utilised system thermal and improve the recovery of prussic acid; Preferably; The distillation residual liquid of said prussic acid absorption liquid and rectification step gained carries out sending into rectifying tower after the heat exchange and carries out rectifying, and distillation residual liquid returns absorption step as the absorption liquid recycled through heat exchange and after being cooled to absorption temperature.
Rectification step of the present invention both can be an atmospheric distillation, also can be rectification under vacuum, and concrete processing condition can be confirmed according to the boiling point of water and prussic acid.Wherein, atmospheric distillation is that 90 ~ 120 ℃, tower top temperature are to carry out under 15 ~ 40 ℃ the condition in tower still temperature preferably, is that 100 ~ 110 ℃, tower top temperature are to carry out under 20 ~ 30 ℃ the condition in tower still temperature more preferably; Rectification under vacuum is that 60 ~ 80 ℃, tower top temperature are to carry out under 0 ~ 15 ℃ the condition in tower still temperature preferably.Rectification under vacuum can reduce the service temperature of rectifying tower, makes the service temperature that absorbs with rectifying more approaching, further reduces production energy consumption.
Above-mentioned prussic acid method of purification is applicable to all prussic acid working methods of in industry, using at present; For example iS-One method, BMA method, light oil cracking method, vinyl cyanide by-product method etc. are specially adapted to purified hydrogen cyanic acid from the reaction mixture gas of the synthetic prussic acid of iS-One method.
From the reaction mixture gas of the synthetic prussic acid of iS-One method, BMA method or light oil cracking method during purified hydrogen cyanic acid; Before absorption step, also comprise and remove the ammonia step; The said ammonia step of removing is to remove the unreacted that contains in reaction mixture gas raw material ammonia completely, in subsequent processes, causes polymerization, the decomposition of prussic acid to prevent this part ammonia.Ammonia-removal method both can adopt sulfuric acid process, promptly utilized sulfuric acid absorption ammonia to generate the sulphur ammonium; Also can adopt phosphorus ammonium method, its principle is to absorb the ammonia in the gas mixture at low temperatures with phosphorus ammonium barren liquor (the NH3/H3PO4 mol ratio is 1.1 ~ 1.4), generates diammonium phosphate and emits heat; The phosphorus ammonium barren liquor that has absorbed ammonia becomes phosphorus ammonium pregnant liquor (mol ratio of NH3/H3PO4 is 1.7 ~ 1.9); Desorb is decomposed under hot conditions again, emits ammonia and absorbs heat, changes phosphorus ammonium barren liquor into and after cooling, recycles; The ammonia that desorb is emitted obtains ammoniacal liquor through condensation, and ammoniacal liquor obtains liquefied ammonia through rectifying.
Beneficial effect of the present invention is: the present invention adopts the pressurizing absorption method to substitute existing normal pressure absorption process in absorption step; 1. the concentration of prussic acid can improve 3 ~ 10 times in the prussic acid absorption liquid; When the prussic acid absorption liquid of follow-up rectifying equal volume, can once obtain the more liquid hydrogen cyanic acid of volume, thereby improve the prussic acid purification efficiency greatly; 2. absorption temperature can be increased to 60 ℃, does not need again reaction mixture gas to be cooled to lesser temps (10 ~ 15 ℃), thereby reduces the cooling energy consumption greatly; 3. the prussic acid absorption liquid that makes of pressurizing absorption has certain pressure; Variation owing to pressure when it gets into normal pressure or rectification under vacuum tower can flash distillation steam the part hydrocyanic acid gas; And; Because the concentration of prussic acid improves in the gained prussic acid absorption liquid, the rectifying time that obtaining equivalent liquid hydrogen cyanic acid needs shortens, thereby reduces the rectifying energy consumption greatly; 4. distillation residual liquid can return absorption step as the absorption liquid recycled through heat exchange and after further being cooled to absorption temperature, because absorption temperature obviously improves, then distillation residual liquid is cooled to the needed energy consumption of absorption temperature and also significantly reduces; Comprehensive above-mentioned several aspects through engineering calculation and experimental verification, adopt the inventive method, and production energy consumption is the highest to descend 80%.
Description of drawings
Fig. 1 is the device synoptic diagram of purified hydrogen cyanic acid from contain the prussic acid gas mixture, and wherein 1 for removing the ammoniacal liquor test tank, and 2 for removing the ammonia tower, and 3 for removing the ammoniacal liquor water cooler; 4 for removing ammonia gas mixture water cooler, and 5 is compressor, and 6 are pressurization gas mixture water cooler, and 7 are pressurization gas mixture surge tank; 8 is the pressurizing absorption tower, and 9 is interchanger, and 10 is the atmospheric distillation tower, and 11 are the rectifying reboiler; 12 is the prussic acid condensing surface, and 13 is the prussic acid receiving tank, and 14 is the distillation residual liquid water cooler.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer, will combine accompanying drawing that the preferred embodiments of the present invention are carried out detailed description below.
Embodiment 1, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
The device synoptic diagram is as shown in Figure 1.
A. remove ammonia: in removing ammoniacal liquor test tank 1, add and remove ammoniacal liquor (pH is 4 aqueous sulfuric acid); The reaction mixture gas of the synthetic prussic acid of iS-One method is fed except that ammonia tower 2 by the bottom; Spray into except that ammoniacal liquor from removing ammonia tower 2 tops simultaneously; Reaction mixture gas comes out from removing ammonia tower 2 tops after removing the ammonia that wherein contains except that the ammoniacal liquor counter-current absorption, is cooled to 40 ℃ through removing ammonia gas mixture water cooler 4; The ammoniacal liquor that removes behind the absorption ammonia recycles after removing 3 coolings of ammoniacal liquor water cooler, regularly replaces the new ammoniacal liquor that removes;
B. absorb: will be forced into 0.7MPa with compressor 5 except that the reaction mixture gas behind the ammonia, and be cooled to 45 ℃ through pressurization gas mixture water cooler 6 again, and feed pressurization gas mixture surge tank 7; Pressurization gas mixture in the pressurization gas mixture surge tank 7 is fed pressurizing absorption tower 8 with constant pressure 0.7MPa by the bottom; Top from pressurizing absorption tower 8 sprays into absorption liquid (pH is 2 aqueous sulfuric acid) simultaneously; The control tower internal pressure is that 0.4MPa, temperature are 30 ℃; Hydrocyanic acid gas in the absorption liquid counter-current absorption pressurization gas mixture, obtaining concentration is the prussic acid absorption liquid of 68g/L;
C. rectifying: after will carrying out heat exchange through interchanger 9 from the effusive prussic acid absorption liquid in pressurizing absorption tower 8 bottoms and from the effusive distillation residual liquid in atmospheric distillation tower 10 bottoms; Feed atmospheric distillation tower 10 by the middle part; Flash distillation steams the part hydrocyanic acid gas, and remaining liq carries out atmospheric distillation after 11 heating of the rectifying reboiler at the bottom of the tower, and control tower still temperature is 110 ℃; The dephlegmator of top of the tower temperature is 28 ℃; The gas that comes out from atmospheric distillation tower 10 tops is sent into prussic acid receiving tank 13 after 12 coolings of prussic acid condensing surface, promptly obtain the liquid hydrogen cyanic acid of high purity (quality percentage composition >=99%); From the effusive distillation residual liquids in atmospheric distillation tower 10 bottoms (prussic acid that contains quality percentage composition＜0.01%) with carry out heat exchange from the effusive prussic acid absorption liquid in pressurizing absorption tower 8 bottoms through interchanger 9 after; Be cooled to 25 ℃ through distillation residual liquid water cooler 14, return pressurizing absorption tower 8 as the absorption liquid recycled.
Embodiment 2, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
The difference of present embodiment and embodiment 1 is:
In the absorption step, the pressure of control pressurizing absorption tower 8 is that 0.3MPa, temperature are 25 ℃, and finally obtaining concentration is the prussic acid absorption liquid of 52g/L.
Embodiment 3, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
The difference of present embodiment and embodiment 1 is:
In the absorption step, the pressure of control pressurizing absorption tower 8 is that 0.5MPa, temperature are 28 ℃, and finally obtaining concentration is the prussic acid absorption liquid of 72g/L.
Embodiment 4, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
The difference of present embodiment and embodiment 1 is:
Absorption step is with being forced into 0.11MPa except that the reaction mixture gas behind the ammonia with compressor 5, being cooled to 10 ℃ through pressurization gas mixture water cooler 6 again, feeding pressurization gas mixture surge tank 7; Pressurization gas mixture in the pressurization gas mixture surge tank 7 is fed pressurizing absorption tower 8 with constant pressure 0.11MPa by the bottom; Spray into absorption liquid (pH is 1 aqueous hydrochloric acid) simultaneously from pressurizing absorption tower 8 tops; The control tower internal pressure is that 0.11MPa, temperature are 0 ℃; Hydrocyanic acid gas in the absorption liquid counter-current absorption pressurization gas mixture, obtaining concentration is the prussic acid absorption liquid of 25g/L;
Rectification step is to be 90 ℃ in tower still temperature, and the dephlegmator of top of the tower temperature is to carry out atmospheric distillation under 15 ℃ the condition; Distillation residual liquid returns pressurizing absorption tower 8 as the absorption liquid recycled through heat exchange and after further being cooled to 0 ℃.
Embodiment 5, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
The difference of present embodiment and embodiment 1 is:
Absorption step is with being forced into 0.2MPa except that the reaction mixture gas behind the ammonia with compressor 5, being cooled to 30 ℃ through pressurization gas mixture water cooler 6 again, feeding pressurization gas mixture surge tank 7; Pressurization gas mixture in the pressurization gas mixture surge tank 7 is fed pressurizing absorption tower 8 with constant pressure 0.2MPa by the bottom; Spray into absorption liquid (pH is 3 phosphate aqueous solution) simultaneously from pressurizing absorption tower 8 tops; The control tower internal pressure is that 0.15MPa, temperature are 20 ℃; Hydrocyanic acid gas in the absorption liquid counter-current absorption pressurization gas mixture, obtaining concentration is the prussic acid absorption liquid of 43g/L;
Rectification step is to be 100 ℃ in tower still temperature, and the dephlegmator of top of the tower temperature is to carry out atmospheric distillation under 20 ℃ the condition; Distillation residual liquid returns pressurizing absorption tower 8 as the absorption liquid recycled through heat exchange and after further being cooled to 20 ℃.
Embodiment 6, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
The difference of present embodiment and embodiment 1 is:
Absorption step is with being forced into 0.6MPa except that the reaction mixture gas behind the ammonia with compressor 5, being cooled to 50 ℃ through pressurization gas mixture water cooler 6 again, feeding pressurization gas mixture surge tank 7; Pressurization gas mixture in the pressurization gas mixture surge tank 7 is fed pressurizing absorption tower 8 with constant pressure 0.6MPa by the bottom; Spray into absorption liquid (pH is 5 acetic acid aqueous solution) simultaneously from pressurizing absorption tower 8 tops; The control tower internal pressure is that 0.6MPa, temperature are 40 ℃; Hydrocyanic acid gas in the absorption liquid counter-current absorption pressurization gas mixture, obtaining concentration is the prussic acid absorption liquid of 45g/L;
Rectification step is to be 105 ℃ in tower still temperature, and the dephlegmator of top of the tower temperature is to carry out atmospheric distillation under 30 ℃ the condition; Distillation residual liquid returns pressurizing absorption tower 8 as the absorption liquid recycled through heat exchange and after further being cooled to 30 ℃.
Embodiment 7, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
The difference of present embodiment and embodiment 1 is:
Absorption step is with being forced into 1.5MPa except that the reaction mixture gas behind the ammonia with compressor 5, being cooled to 60 ℃ through pressurization gas mixture water cooler 6 again, feeding pressurization gas mixture surge tank 7; Pressurization gas mixture in the pressurization gas mixture surge tank 7 is fed pressurizing absorption tower 8 with constant pressure 1.5MPa by the bottom; Spray into absorption liquid (pH is 6 oxalic acid aqueous solution) simultaneously from pressurizing absorption tower 8 tops; The control tower internal pressure is that 1.0MPa, temperature are 60 ℃; Hydrocyanic acid gas in the absorption liquid counter-current absorption pressurization gas mixture, obtaining concentration is the prussic acid absorption liquid of 38g/L;
Rectification step is to be 120 ℃ in tower still temperature, and the dephlegmator of top of the tower temperature is to carry out atmospheric distillation under 40 ℃ the condition; Distillation residual liquid returns pressurizing absorption tower 8 as the absorption liquid recycled through heat exchange and after further being cooled to 60 ℃.
Embodiment 8, from the reaction mixture gas of the synthetic prussic acid of iS-One method purified hydrogen cyanic acid
A. remove ammonia: identical with embodiment 1;
B. absorb: will be forced into 0.5MPa with compressor 5 except that the reaction mixture gas behind the ammonia, and be cooled to 40 ℃ through pressurization gas mixture water cooler 6 again, and feed pressurization gas mixture surge tank 7; Pressurization gas mixture in the pressurization gas mixture surge tank 7 is fed pressurizing absorption tower 8 with constant pressure 0.5MPa by the bottom; Spray into absorption liquid (pH is 5 acetic acid aqueous solution) simultaneously from pressurizing absorption tower 8 tops; The control tower internal pressure is that 0.4MPa, temperature are 30 ℃; Hydrocyanic acid gas in the absorption liquid counter-current absorption pressurization gas mixture, obtaining concentration is the prussic acid absorption liquid of 45g/L;
C. rectifying: after will carrying out heat exchange through interchanger from the effusive prussic acid absorption liquid of pressurizing absorption tower bottom and from the effusive distillation residual liquid of rectification under vacuum tower bottom; Feed the rectification under vacuum tower by the middle part; Flash distillation steams the part hydrocyanic acid gas; Remaining liq carries out rectification under vacuum after the heating of the rectifying reboiler at the bottom of the tower, control tower still temperature is 75 ℃, and the dephlegmator of top of the tower temperature is 10 ℃; After the cooling of prussic acid condensing surface, send into the prussic acid receiving tank from the gas that the rectification under vacuum top of tower comes out, promptly obtain the liquid hydrogen cyanic acid of high purity (quality percentage composition >=99%); From the effusive distillation residual liquid of rectification under vacuum tower bottom (prussic acid that contains quality percentage composition＜0.01%) with carry out heat exchange from the effusive prussic acid absorption liquid of pressurizing absorption tower bottom through interchanger after; Be cooled to 30 ℃ through the distillation residual liquid water cooler, return the pressurizing absorption tower as the absorption liquid recycled.
Embodiment 9, from the reaction mixture gas of the synthetic prussic acid of light oil cracking method purified hydrogen cyanic acid
The difference of present embodiment and embodiment 1 is:
Remove in the ammonia step; The reaction mixture gas of the synthetic prussic acid of light oil cracking method is fed except that ammonia tower 2 by the bottom; Spray into except that ammoniacal liquor from removing ammonia tower 2 tops simultaneously; Reaction mixture gas comes out from removing ammonia tower 2 tops after removing the ammonia that wherein contains except that the ammoniacal liquor counter-current absorption, is cooled to 40 ℃ through removing ammonia gas mixture water cooler 4.
Embodiment 10, be equipped with purified hydrogen cyanic acid the prussic acid gas mixture from the light oil cracking legal system
The difference of present embodiment and embodiment 9 is:
Rectification step is with after carrying out heat exchange from the effusive prussic acid absorption liquid of pressurizing absorption tower bottom and from the effusive distillation residual liquid of rectification under vacuum tower bottom through interchanger; Feed the rectification under vacuum tower by the middle part; Flash distillation steams the part hydrocyanic acid gas; Remaining liq carries out rectification under vacuum after the heating of the rectifying reboiler at the bottom of the tower, control tower still temperature is 73 ℃, and the dephlegmator of top of the tower temperature is 15 ℃; After the cooling of prussic acid condensing surface, send into the prussic acid receiving tank from the gas that the rectification under vacuum top of tower comes out, promptly obtain the liquid hydrogen cyanic acid of high purity (quality percentage composition >=99%); From the effusive distillation residual liquid of rectification under vacuum tower bottom (prussic acid that contains quality percentage composition＜0.01%) with carry out heat exchange from the effusive prussic acid absorption liquid of pressurizing absorption tower bottom through interchanger after; Be cooled to 25 ℃ through the distillation residual liquid water cooler, return the pressurizing absorption tower as the absorption liquid recycled.
Embodiment 11, contain purified hydrogen cyanic acid the prussic acid gas mixture from vinyl cyanide by-product method gained
A. absorb: will be forced into 1.5MPa with compressor 5 except that the prussic acid gas mixture behind the ammonia, and be cooled to 80 ℃ through pressurization gas mixture water cooler 6 again, and feed pressurization gas mixture surge tank 7; Pressurization gas mixture in the pressurization gas mixture surge tank 7 is fed pressurizing absorption tower 8 with constant pressure 1.5MPa by the bottom; Spray into absorption liquid (pH is 6 oxalic acid aqueous solution) simultaneously from pressurizing absorption tower 8 tops; The control tower internal pressure is that 1.0MPa, temperature are 60 ℃; Hydrocyanic acid gas in the absorption liquid counter-current absorption pressurization gas mixture, obtaining concentration is the prussic acid absorption liquid of 48g/L;
B. rectifying: after will carrying out heat exchange through interchanger 9 from the effusive prussic acid absorption liquid in pressurizing absorption tower 8 bottoms and from the effusive distillation residual liquid in atmospheric distillation tower 10 bottoms; Feed atmospheric distillation tower 10 by the middle part; Flash distillation steams the part hydrocyanic acid gas, and remaining liq carries out atmospheric distillation after 11 heating of the rectifying reboiler at the bottom of the tower, and control tower still temperature is 120 ℃; The dephlegmator of top of the tower temperature is 40 ℃; The gas that comes out from atmospheric distillation tower 10 tops is sent into prussic acid receiving tank 13 after 12 coolings of prussic acid condensing surface, promptly obtain the liquid hydrogen cyanic acid of high purity (quality percentage composition >=99%); From the effusive distillation residual liquids in atmospheric distillation tower 10 bottoms (prussic acid that contains quality percentage composition＜0.01%) with carry out heat exchange from the effusive prussic acid absorption liquid in pressurizing absorption tower 8 bottoms through interchanger 9 after; Be cooled to 60 ℃ through distillation residual liquid water cooler 14, return pressurizing absorption tower 8 as the absorption liquid recycled.
Embodiment 12, contain purified hydrogen cyanic acid the prussic acid gas mixture from vinyl cyanide by-product method gained
The difference of present embodiment and embodiment 11 is:
Rectification step is with after carrying out heat exchange from the effusive prussic acid absorption liquid of pressurizing absorption tower bottom and from the effusive distillation residual liquid of rectification under vacuum tower bottom through interchanger; Feed the rectification under vacuum tower by the middle part; Flash distillation steams the part hydrocyanic acid gas; Remaining liq carries out rectification under vacuum after the heating of the rectifying reboiler at the bottom of the tower, control tower still temperature is 60 ℃, and the dephlegmator of top of the tower temperature is 0 ℃; After the cooling of prussic acid condensing surface, send into the prussic acid receiving tank from the gas that the rectification under vacuum top of tower comes out, promptly obtain the liquid hydrogen cyanic acid of high purity (quality percentage composition >=99%); From the effusive distillation residual liquid of rectification under vacuum tower bottom (prussic acid that contains quality percentage composition＜0.01%) with carry out heat exchange from the effusive prussic acid absorption liquid of pressurizing absorption tower bottom through interchanger after; Be cooled to 60 ℃ through the distillation residual liquid water cooler, return the pressurizing absorption tower as the absorption liquid recycled.
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although through invention has been described with reference to the preferred embodiments of the present invention; But those of ordinary skill in the art should be appreciated that and can make various changes to it in form with on the details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (6)
1. the method for purified hydrogen cyanic acid from contain the prussic acid gas mixture; Comprise absorption step and rectification step, it is characterized in that: said absorption step is to be forced into 0.11 ~ 1.5MPa with containing the prussic acid gas mixture, is cooled to 10 ~ 80 ℃ again; Feed the pressurizing absorption tower; In the tower internal pressure is that 0.11 ~ 1.0MPa, temperature are under 0 ~ 60 ℃ the condition, and using absorption liquid is that pH is the hydrocyanic acid gas in 1 ~ 6 the acidic aqueous solution pressurizing absorption gas mixture, obtains the prussic acid absorption liquid.
2. according to claim 1 from contain the prussic acid gas mixture method of purified hydrogen cyanic acid; It is characterized in that: said absorption step is to be forced into 0.2 ~ 0.7MPa with containing the prussic acid gas mixture; Being cooled to 30 ~ 50 ℃ again, feeding the pressurizing absorption tower, is that 0.15 ~ 0.6Mpa, temperature are under 20 ~ 40 ℃ the condition in the tower internal pressure; Using pH is the hydrocyanic acid gas in 2 ~ 5 the acidic aqueous solution pressurizing absorption gas mixture, obtains the prussic acid absorption liquid.
3. according to claim 2 from contain the prussic acid gas mixture method of purified hydrogen cyanic acid; It is characterized in that: said absorption step is to be forced into 0.7MPa with containing the prussic acid gas mixture; Being cooled to 45 ℃ again, feeding the pressurizing absorption tower, is that 0.3 ~ 0.5Mpa, temperature are under 25 ~ 30 ℃ the condition in the tower internal pressure; Using pH is the hydrocyanic acid gas in 2 the aqueous sulfuric acid pressurizing absorption gas mixture, obtains the prussic acid absorption liquid.
4. according to claim 1 from contain the prussic acid gas mixture method of purified hydrogen cyanic acid; It is characterized in that: the distillation residual liquid of said prussic acid absorption liquid and rectification step gained carries out sending into rectifying tower after the heat exchange and carries out rectifying, and distillation residual liquid returns absorption step as the absorption liquid recycled through heat exchange and after being cooled to absorption temperature.
According to the arbitrary claim of claim 1 to 4 described from contain the prussic acid gas mixture method of purified hydrogen cyanic acid; It is characterized in that: the said prussic acid gas mixture that contains is produced the reaction mixture gas that prussic acid obtains for adopting iS-One method, BMA method or light oil cracking method, and before absorption step, has removed the ammonia that contains in the reaction mixture gas through removing the ammonia step.
According to the arbitrary claim of claim 1 to 4 described from contain the prussic acid gas mixture method of purified hydrogen cyanic acid, it is characterized in that: the said reaction mixture gas that contain prussic acid of prussic acid gas mixture that contain for adopting vinyl cyanide by-product method to make.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725269A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Technological method for jointly preparing liquid hydrogen cyanide and hydroxynitrile |
| CN104724724A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Process method for co-preparing liquid hydrocyanic acid and sodium cyanide |
| CN104724725A (en) * | 2014-11-21 | 2015-06-24 | 重庆紫光化工股份有限公司 | Hydrocyanic acid gas separation and purification system and method |
| CN104724726A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine |
| CN105315175A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Iminodiacetonitrile cleaner production method |
| CN105366692A (en) * | 2015-12-04 | 2016-03-02 | 中国天辰工程有限公司 | Process and system for preparing high-purity liquid hydrogen cyanide |
| CN105502436A (en) * | 2016-01-19 | 2016-04-20 | 浦为民 | Clean production technology of hydrocyanic acid |
| CN113680087A (en) * | 2021-08-27 | 2021-11-23 | 重庆山巨化工机械股份有限公司 | Double-tower efficient energy-saving rectification process |
| CN114044525A (en) * | 2021-10-28 | 2022-02-15 | 山东宏旭化学股份有限公司 | Efficient hydrocyanic acid recycling method and system |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725269A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Technological method for jointly preparing liquid hydrogen cyanide and hydroxynitrile |
| CN104724724A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Process method for co-preparing liquid hydrocyanic acid and sodium cyanide |
| CN104724725A (en) * | 2014-11-21 | 2015-06-24 | 重庆紫光化工股份有限公司 | Hydrocyanic acid gas separation and purification system and method |
| CN104724726A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Technological method for jointly preparing liquid hydrogen cyanide and bisisobutyronitrile hydrazine |
| CN104725269B (en) * | 2014-11-21 | 2017-01-04 | 枣阳市金鹿化工有限公司 | A kind of combine the process preparing liquid hydrocyanic acid and hydroxyacetonitrile |
| CN104724724B (en) * | 2014-11-21 | 2017-01-04 | 枣阳市金鹿化工有限公司 | A kind of combine the process preparing liquid hydrocyanic acid and Cyanogran. |
| CN105315175A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Iminodiacetonitrile cleaner production method |
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| CN105502436A (en) * | 2016-01-19 | 2016-04-20 | 浦为民 | Clean production technology of hydrocyanic acid |
| CN113680087A (en) * | 2021-08-27 | 2021-11-23 | 重庆山巨化工机械股份有限公司 | Double-tower efficient energy-saving rectification process |
| CN114044525A (en) * | 2021-10-28 | 2022-02-15 | 山东宏旭化学股份有限公司 | Efficient hydrocyanic acid recycling method and system |
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