CN106365178A - Method for purification of hydrocyanic acid - Google Patents
Method for purification of hydrocyanic acid Download PDFInfo
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- CN106365178A CN106365178A CN201610750631.4A CN201610750631A CN106365178A CN 106365178 A CN106365178 A CN 106365178A CN 201610750631 A CN201610750631 A CN 201610750631A CN 106365178 A CN106365178 A CN 106365178A
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- tower
- hydrocyanic acid
- liquid
- stripping
- rectifying column
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 294
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000000746 purification Methods 0.000 title claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 108
- 238000010521 absorption reaction Methods 0.000 claims abstract description 45
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims description 39
- 239000012071 phase Substances 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims description 3
- -1 absorption step Chemical compound 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 23
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000010992 reflux Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for the purification of hydrocyanic acid. The method for the purification of hydrocyanic acid comprises an absorption step, a stripping step and a distillation step, and is characterized in that hydrocyanic acid-containing absorption liquid obtained in the absorption step enters the top of a stripping tower from a tower kettle of an absorption tower through pipelines; distillation tower kettle liquid in the distillation step is withdrawn through a circulating pump, part of the distillation tower kettle liquid is returned to the lower segment of a distillation tower, and the other part of the distillation tower kettle liquid is sent to the top of the stripping tower. The method for the purification of hydrocyanic acid can achieve the control of the liquid level in the distillation tower and ensure that polymerization phenomena does not occur in the distillation process of the hydrocyanic acid.
Description
Technical field
The present invention relates to the separating-purifying of chemical intermediate, more particularly, to a kind of method of purification of hydrocyanic acid.
Background technology
Hydrocyanic acid, as a kind of important chemical intermediate, can be used for manufacturing glyphosate, Methionine, acrylic resin and Buddhist nun
The production of the important chemical products, especially acrylic resin and nylon66 fiber such as dragon 66 needs substantial amounts of high purity liquid state hydrocyanic acid.
The physical property of hydrocyanic acid is more special, is a kind of colourless, transparent, volatile liquid, has Semen Armeniacae Amarum taste, is a kind of acute
Malicious chemicals.Miscible with water, dissolve in ethanol, ether, glycerol, benzene etc., hydrocyanic acid has autohemagglutination characteristic, especially produce liquified hydrogen
Often aggregation problem occurs in the distillation process of cyanic acid, in turn result in rectification tower packing caking or blocking column plate, impact produces dress
The normal operation put, and thereby resulted in safety in production hidden danger.
The method mainly having following several preparation hydrocyanic acid in commercial production: iS-One method, methanol ammonoxidation method, acrylonitrile pair
Product method, light oil cracking method.Using these methods synthesize hydrocyanic acid obtain be Multicomponent hydrocyanic acid synthesis gas, and by its
It is prepared into high purity liquid state hydrocyanic acid, also need through the purifying technique process such as absorption, rectification.
Existing hydrocyanic acid rectification and purification technique is operated in normal pressure or condition of negative pressure, due to tower reactor operation temperature
Higher, and in distillation process, hydrocyanic acid federation is in the easy concentration ranges that polymerization occurs, and hydrogen cyanogen easily occurs in rectifying column
Acid polymerization, in turn results in blocking or the filler caking of column plate, have impact on normal production operation, and cause potential safety hazard.
Patent cn1771197 discloses a kind of method of purifying hydrocyanic acid.It is carried out to hydrocyanic acid by bubble-cap plate column
Distillation, contains the hydrocyanic acid solution of the mass percent more than 50% of hydrocyanic acid in the method, be 1～2.5bar in operating pressure,
Column bottom temperature is 100～130 DEG C, and tower top temperature carries out distilation under conditions of being 25～54 DEG C.The certain journey of this method of purification
The polymerization of hydrocyanic acid can be reduced on degree, but be only suitable for purifying the hydrocyanic acid solution that concentration is more than 50%, for low concentration (1-
10%) hydrocyanic acid solution is in addition it is also necessary to concentrate before carrying out rectification, thus increased cost of investment and running cost, and the method
In purification process, operating pressure, temperature are higher, can lead to reboiler and tower body heavy corrosion, additionally, its pressurized operation, equipment system
Make and have strict requirements.
Patent cn101511734 discloses by condensate circulation, by high for hydrocyanic acid acid compound etc. boiling product high temperature punching
Wash off, this method can only extend the operating time of hydrocyanic acid rectifier unit, what also presence was stopped work because of hydrocyanic acid polymerization can
Energy.
In patent cn102502707, high-purity hydrogen cyanic acid is obtained using the method for pressurizing absorption and atmospheric distillation, it will
Hydrocyanic acid gaseous mixture sends into the absorption tower that tower pressure interior force is 1.5～6bar after being forced into 2～7bar, absorbing liquid sends into rectifying column,
Rectifying column then adopts conventional rectificating method in hydrocyanic acid documents and materials.This invents for the purpose of reducing energy consumption, in pressurized conditions
When sending into rectifying column after the lower mixed gas absorption by hydrocyanic acid, because absorbing liquid is with pressure, can be with flash distillation thus shortening a part of rectification
Time, reduce energy consumption of rectification, reduce the polymerization probability of hydrocyanic acid.But the polymerization of hydrocyanic acid still can occur under these conditions,
And pressurizing absorption reduces the safety of operation.
Patent cn102633283 discloses a kind of method of purification of hydrocyanic acid, and the method to be reduced using micro-negative pressure operation
Raw material preheating is entered rectifying column to after 40～60 DEG C by operation temperature first, adds polymerization inhibitor, in the tower of negative pressure 10～90kpa
Pressure on top surface, tower top temperature is 0～25 DEG C, the tower reactor pressure of negative pressure 20～95kpa, and bottom temperature is 60～100 DEG C, and reflux ratio is
Carry out rectification and purification, although this method of purification reduces distillation operation temperature by negative pressure, thus reducing under conditions of 3～15
The possibility of hydrocyanic acid polymerization, but condition of negative pressure increased the control difficulty of rectifying column operating condition, and the fluctuation of vacuum can be directly
Have influence on the separating-purifying effect of rectifying column, increased energy consumption simultaneously.
It is to obtain pure hydrocyanic acid from hydrocyanic acid aqueous solution in patent us25710099, hydrocyanic acid aqueous solution rectification is taken off
Water.In the process, obtain anhydrous hydrocyanic acid using dehydrant, but in commercial production using dehydrant such as molecular sieve etc. be
Expensive and laborious, dehydrant has to contact with aqueous hydrocyanic acid, regenerates after then removing from the hydrocyanic acid of dehydration again.
Patent cn104724727 discloses a kind of hydrocyanic acid double-column in series rectification process for separating and purifying, and aqueous hydrocyanic acid is entered
Enter first rectifying column, partial condensation flows back, add polymerization inhibitor, Second distillation column rectification, partial condensation backflow separates again.Patent
The method that cn105366692 discloses the hydrocyanic acid gas purification production high purity liquid state hydrocyanic acid that a kind of ammonia oxidation obtains, hydrogen
Cyanic acid purification completes in three-stage rectifying column, and distillation process stage casing carries out partial condensation backflow to hydrocyanic acid gas phase, and
Rectifying tower top is provided with gas-liquid separator, to obtain highly purified liquid hydrocyanic acid.Above-mentioned two patents are all by rectification
Process stage casing gas phase portion condensing reflux, solves the aggregation problem of hydrocyanic acid.But, contain on its rectifying column in above-mentioned two patents
There is one section of rectifying column between the feed entrance point of hydrocyanic acid aqueous solution and reflux condenser.Obviously, the hydrocyanic acid in this section of rectifying column
Concentration is in easy polymerization interval, and temperature is higher, therefore, hydrocyanic acid polymerization easily occurs in this section of rectifying column.
Additionally, also having some manufacturers in hydrocyanic acid preparation process, cause rectifying column to tackle hydrocyanic acid polymerization
Block the trouble brought to production operation process, select sectioning filler, install in the concentration area of hydrocyanic acid easily polymerization in bulk
Dumped packing is removed cleaning to facilitate when rectifying column blocks by filler.It will be apparent that this simply reduces the reply of operational readiness
Measure, without fundamentally solving because polymerization in hydrocyanic acid distillation process, and then causes blocking or fills out to rectifying column
The harm such as material caking, the problems such as have impact on normal production operation, and cause potential safety hazard.
Content of the invention
It is an object of the invention to provide a kind of method of purification of hydrocyanic acid, this method of purification can achieve in rectifying tower reactor
The control of liquid level, and guarantee that hydrocyanic acid distillation process no polymerism occurs.
The purpose of the present invention is achieved through the following technical solutions:
A kind of method of purification of hydrocyanic acid, including absorption step, stripping step and rectification step it is characterised in that: described
The absorbing liquid containing hydrocyanic acid of gained in absorption step, is entered the tower top of described stripping tower by the tower reactor on absorption tower through pipeline；Institute
, after circulating pump extraction, part returns rectifying column hypomere, partly delivers to stripping top of tower to state rectifying column kettle liquid in rectification step.
As optimizing further, above-mentioned rectifying column kettle liquid after circulating pump extraction, part return rectifying column hypomere 20～
Between 10 blocks of column plates, between preferably 17～12 blocks column plates, between more preferably 15～13 blocks column plates.
As optimizing further, the outer circulation amount that above-mentioned rectifying column kettle liquid produces through circulating pump, with part return rectifying column
Ratio between the capacity of returns of hypomere is 0.1～1.0, preferably 0.3～0.8, more preferably 0.5～0.6.
As optimizing further, in above-mentioned rectification step, rectifying column kettle liquid, after circulating pump extraction, first cools down through outer circulation
Device cools down, and part returns rectifying column hypomere afterwards, partly delivers to stripping top of tower.
As optimizing further, the method for purification of above-mentioned hydrocyanic acid, comprise the steps:
(1) absorption step
Hydrocyanic acid synthesis gas is sent into absorption tower, and is passed through spray liquid in absorption tower tower top, spray-absorption obtains hydrogeneous cyanogen
The absorbing liquid of acid；Wherein, spray liquid is selected containing organic aqueous acid such as the mineral acids such as sulphuric acid, phosphoric acid or acetic acid, glycolic,
The ph value of its spray liquid is controlled to 1～3, and temperature control is 5～10 DEG C；
(2) stripping step
Absorbing liquid is produced, heated rear feeding stripping top of tower, part is evaporated by the absorbing liquid containing hydrocyanic acid, is formed equal
Gas phase containing hydrocyanic acid and liquid phase, gas phase enters rectifying tower reactor by the vapor delivery line of stripping column overhead, and liquid phase is by stripping tower tower
Top flows back into tower reactor, and through reboiler heating evaporation, the hydrocyanic acid in aqueous solution is separated in stripping tower, obtains containing Microamounts of Hydrogen
The stripping residual liquid of cyanic acid；After stripping residual liquid is cooled to 5～10 DEG C, sends into absorption tower tower top, hydrocyanic acid synthesis gas absorbed,
Obtain the absorbing liquid containing hydrocyanic acid in absorption tower tower reactor；
(3) rectification step
Add polymerization inhibitor in rectifying column tower top, rectifying tower is entered by the gas phase containing hydrocyanic acid that stripping column overhead is come
Kettle, and further separating-purifying, the extremely low hydrocyanic acid gas of the water content obtaining in rectifying column, are refluxed condenser all cold
Coagulate for hydrocyanic acid liquid, partial condensation liquid flows back, partial condensation liquid produces as finished product liquid hydrogen cyanide product；Rectifying column kettle liquid
Produced by circulating pump, after again through outer circulation cooler cool down, afterwards part return rectifying column hypomere, partly deliver to stripping tower top
Portion, in order to control liquid level equilibrium in rectifying tower reactor.
As optimizing further, above-mentioned stripping tower and above-mentioned rectifying column may each be plate column, also may each be packed tower.
As optimizing further, the method for purification of above-mentioned hydrocyanic acid, comprise the steps:
(1) absorption step
Hydrocyanic acid synthesis gas is sent into absorbing tower bottom, and is passed through spray liquid in absorption tower tower top, spray-absorption is contained
The absorbing liquid of hydrocyanic acid；Wherein, spray liquid selects the water containing the organic acid such as the mineral acids such as sulphuric acid, phosphoric acid or acetic acid, glycolic
Solution, the ph value of its spray liquid is controlled to 1～3, and temperature control is 5～10 DEG C；
(2) stripping step
Absorbing liquid is produced by pump, after hot and cold heat exchanger heating, sends into stripping top of tower, the absorbing liquid containing hydrocyanic acid will
Part is evaporated, and forms all gas phase containing hydrocyanic acid and liquid phase, and gas phase enters rectifying tower reactor by the vapor delivery line of stripping column overhead,
Liquid phase flows back into tower reactor by stripping column overhead, and through reboiler heating evaporation, the hydrocyanic acid in aqueous solution is divided in stripping tower
From obtaining the stripping residual liquid containing micro hydrocyanic acid；Stripping residual liquid is cooled to 5～10 DEG C through hot and cold heat exchanger, freezing water- to-water heat exchanger
Afterwards, send into absorption tower tower top, hydrocyanic acid synthesis gas is absorbed, obtains the absorbing liquid containing hydrocyanic acid in absorption tower tower reactor；
(3) rectification step
Add polymerization inhibitor dilute sulfuric acid in rectifying column tower top, rectification is entered by the gas phase containing hydrocyanic acid that stripping column overhead is come
Tower tower reactor, and further separating-purifying, the extremely low hydrocyanic acid gas of the water content obtaining in rectifying column, are refluxed condenser complete
Portion is condensed into hydrocyanic acid liquid, and partial condensation liquid flows back, and partial condensation liquid produces as finished product liquid hydrogen cyanide product；Rectifying column
Kettle liquid is produced by circulating pump, after again through outer circulation cooler cooling cause 5～8 DEG C of its temperature drop, afterwards part return rectification
Between 15～13 blocks of column plates of tower hypomere, partly deliver to stripping top of tower, and the outer circulation that rectifying column kettle liquid produces through circulating pump
Ratio between amount, and the capacity of returns of part return rectifying column is 0.5～0.6.
The method have the advantages that
The invention provides a kind of method of purification of hydrocyanic acid, it by being adopted the tower bottoms in rectifying column by circulating pump
Go out, partly deliver to stripping top of tower it is achieved that control to liquid level in rectifying tower reactor, change rectifying column hypomere hydrocyanic acid easily poly-
Close the concentration in area, the concentration shielding of hydrocyanic acid in rectifying column is outer in easy interval of being polymerized, also part tower bottoms is returned essence simultaneously
Evaporate tower hypomere circulating reflux so that the polymerization inhibitor in tower bottom of rectifying tower is evenly distributed, improve the resist effect of rectifying column hypomere,
Avoid regional area in kettle and be easily caused the generation of polymerism because lacking polymerization inhibitor it is ensured that hydrocyanic acid distillation process is no poly-
Close phenomenon to occur；And after the tower bottoms in rectifying column is produced by circulating pump, then carry out suitable cooling through outer circulation cooler,
Reduce the temperature of rectifying column hypomere, further ensure that hydrocyanic acid distillation process is not polymerized.Inhale in stripping step
Receive liquid to be fed by stripping column overhead position, stripping column overhead does not set rectifying section, and the whole tower of stripping tower is in the easy polymerization concentration of hydrocyanic acid
Outside region, and due to there being polymerization inhibitor in absorbing liquid, ph value controls 1～3, thus hydrocyanic acid polymerization will not occur in stripping tower
Problem.Additionally, through engineering calculation, the cooling that only circulation fluid need to be carried out somewhat by outer circulation cooler, increasing that will not be excessive
Plus the energy consumption of distillation process；Absorbing liquid and distillation residual liquid carry out heat exchange by same hot and cold heat exchanger, considerably reduce energy
Consumption.
Brief description
Fig. 1 is the structural representation of the process units employed in the method for purification of hydrocyanic acid described in the embodiment of the present invention 1
Figure.
Specific embodiment
Below by specific embodiment, the present invention is specifically described, it is pointed out here that following examples are served only for this
Bright be further described it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art of this area can root
According to foregoing invention content, the present invention is made with some nonessential improvement and adjust.
Embodiment 1
A kind of method of purification of hydrocyanic acid, wherein, the structure such as description of the process units that this method of purification is adopted is attached
Shown in Fig. 1, absorption tower 1 is provided with spray liquid feed liquor pipeline, hydrocyanic acid synthesis gas admission line and exhaust pipe；Stripping tower 2
In the connecting pipeline of setting between the tower top on tower reactor and absorption tower 1, it is sequentially provided with along from stripping tower 2 to the direction on absorption tower 1
Hot and cold heat exchanger 4 and freezing water- to-water heat exchanger 5；In the connecting pipeline of setting between the tower reactor on the tower top of stripping tower 2 and absorption tower 1,
It is connected with hot and cold heat exchanger 4；Reboiler 6 is connected by pipeloop with stripping tower 2；The tower top of stripping tower 2 and the tower of rectifying column 3
Kettle connects；The tower reactor of rectifying column 3 is also connected with circulating pump 7；Circulating pump 7 is also connected with outer circulation cooler 8；Outer circulation cooler
8 are also connected with the tower top of stripping tower 2, rectifying column 3 hypomere respectively, and the connection position of outer circulation cooler 8 and rectifying column 3 hypomere
Put, at 13 blocks of column plates of rectifying column 3；Polymerization inhibitor feeding line and complete condenser 9 are connected with the tower top of rectifying column 3, and entirely coagulate
It is additionally provided with reflux pipeline between the tower top of device 9 and rectifying column 3；Complete condenser 9 is also connected with product discharge pipeline；Pass through between each equipment
Pipeline communication, and take cold insulation Insulation；
This method of purification specifically follows the steps below:
Synthesize hydrocyanic acid in a set of industrialization iS-One method reaction unit, obtaining hydrocyanic acid percentage by weight is 9.4%, temperature
The hydrocyanic acid synthesis gas of 40 DEG C of degree；By this hydrocyanic acid synthesis gas by absorbing tower bottom feeding absorption tower, absorbing tower pressure on top surface
0.05mpa, and it is passed through 10 DEG C of the ph value low-concentration sulfuric acid aqueous solution spray-absorption for 1～3 in absorption tower tower top, after absorbing
The absorbing liquid that hydrocyanic acid percentage by weight is 1.65% is obtained, the tail gas after absorption goes burning disposal in tower reactor；By absorbing liquid by
Pump produces, and carries out heat exchange through hot and cold heat exchanger 4 and the stripping residual liquid from stripping tower and realizes heating, sends into stripping tower 2 afterwards
Top, the hydrocyanic acid in absorbing liquid is evaporated, and forms all gas phase containing hydrocyanic acid and liquid phase, gas phase is by the gas of stripping column overhead
Phase pipeline enters rectifying tower reactor, and liquid phase flows back into tower reactor by stripping column overhead, through reboiler heating evaporation, the hydrogen in aqueous solution
Cyanic acid is separated in stripping tower, obtains the stripping residual liquid containing micro hydrocyanic acid, hydrocyanic acid content in sampling detection stripping residual liquid
For 20ppm；Stripping residual liquid is cooled to after 10 DEG C through hot and cold heat exchanger 4, freezing water- to-water heat exchanger 5 successively, sends into absorption tower tower top, right
Hydrocyanic acid synthesis gas is absorbed, and is so circulated absorption；Add polymerization inhibitor dilute sulfuric acid in rectifying column tower top, by stripping tower tower
The gas phase containing water, hydrocyanic acid that top is come enters tower bottom of rectifying tower, and further separating-purifying in rectifying column, and obtain is aqueous
Measure extremely low hydrocyanic acid gas, enter complete condenser and be condensed as liquid hydrocyanic acid, partial condensation liquid flows back, and reflux ratio is 5,
Partial condensation liquid produces as finished product liquid hydrocyanic acid target product, and in finished product, the percentage by weight of hydrocyanic acid is 99.79%；Essence
Evaporate tower bottoms to be produced by circulating pump, decline 5 DEG C through outer circulation cooler chilling temperature, part returns to the 13 of rectifying column hypomere afterwards
At block column plate, partly deliver to stripping top of tower, and the outer circulation flow quantity that rectifying column kettle liquid produces through circulating pump, return with part
Ratio between the capacity of returns of rectifying column is 0.50.
Learn through the detection of many sub-samplings, the no polymerism of the whole hydrocyanic acid distillation process in rectifying column occurs, therefore, this
Invention is by circulating pump extraction rectifying tower kettle liquid, and its part is delivered to stripping top of tower it is achieved that to liquid in rectifying tower reactor
The control of position, changes the concentration of the easy polymeric area of rectifying column hypomere hydrocyanic acid, and the concentration of hydrocyanic acid in rectifying column is shielded easy
Polymerization is interval outer, and part tower bottoms is returned rectifying column hypomere circulating reflux so that the polymerization inhibitor in kettle is evenly distributed, and changes
It has been apt to the resist effect of rectifying column hypomere, it is to avoid in kettle, regional area is easily caused sending out of polymerism because lacking polymerization inhibitor
Raw.
Embodiment 2-6
In embodiment 2-6, the structure of process units adopting and each equipment are all same as Example 1, and its preparation process
Also same as Example 1, differ only in and in embodiment 2-6, set different technological parameters, to carry out the rectification of hydrocyanic acid
Purification process；In embodiment 2-6, the operational factor setting and each detection data see table shown in 1:
The operational factor setting in table 1 embodiment 2-6 and each detection data
Additionally, the present invention also carried out following operation as a comparison case, the structure of its process units being adopted and each
Equipment is all same as Example 1, and each the technological parameter setting in its preparation process is also same as Example 1, and difference is only
Be that in this comparative example, circulating pump 7 and outer circulation cooler 8 all stop (i.e. rectifying column kettle liquid all resides in rectifying column, and
Have no the steps such as outer circulation, cooling)；Final detection through many sub-samplings learns there is hydrocyanic acid polymerism in rectifying tower reactor, its
Distillation process causes the harm such as blocking or filler caking to rectifying column, have impact on normal production operation, and it is hidden to cause safety
The problems such as suffer from.
Claims (10)
1. a kind of method of purification of hydrocyanic acid, including absorption step, stripping step and rectification step it is characterised in that: described suction
Receive the absorbing liquid containing hydrocyanic acid of gained in step, entered the tower top of described stripping tower by the tower reactor on absorption tower through pipeline；Described
In rectification step, after circulating pump extraction, part returns rectifying column hypomere to rectifying column kettle liquid, partly delivers to stripping top of tower.
2. as claimed in claim 1 hydrocyanic acid method of purification it is characterised in that: described rectifying column kettle liquid produces through circulating pump
Afterwards, part returns between 20～10 blocks of column plates of rectifying column hypomere.
3. hydrocyanic acid as claimed in claim 1 method of purification it is characterised in that: described rectifying column kettle liquid through circulating pump produce
Afterwards, part returns between 17～12 blocks of column plates of rectifying column hypomere.
4. hydrocyanic acid as claimed in claim 1 method of purification it is characterised in that: described rectifying column kettle liquid through circulating pump produce
Afterwards, part returns between 15～13 blocks of column plates of rectifying column hypomere.
5. described hydrocyanic acid as arbitrary in claim 1-4 method of purification it is characterised in that: described rectifying column kettle liquid is through circulating pump
Ratio between the outer circulation amount of extraction, and the capacity of returns of part return rectifying column hypomere is 0.1～1.0.
6. described hydrocyanic acid as arbitrary in claim 1-4 method of purification it is characterised in that: described rectifying column kettle liquid is through circulating pump
Ratio between the outer circulation amount of extraction, and the capacity of returns of part return rectifying column hypomere is 0.3～0.8.
7. described hydrocyanic acid as arbitrary in claim 1-4 method of purification it is characterised in that: described rectifying column kettle liquid is through circulating pump
Ratio between the outer circulation amount of extraction, and the capacity of returns of part return rectifying column hypomere is 0.5～0.6.
8. described hydrocyanic acid as arbitrary in claim 1-7 method of purification it is characterised in that: rectifying tower reactor in described rectification step
After circulating pump extraction, first through the cooling of outer circulation cooler, part returns rectifying column hypomere to liquid afterwards, partly delivers to stripping tower top
Portion.
9. the method for purification of described hydrocyanic acid as arbitrary in claim 1-7 is it is characterised in that comprise the steps:
(1) absorption step
Hydrocyanic acid synthesis gas is sent into absorption tower, and is passed through spray liquid in absorption tower tower top, spray-absorption obtains containing hydrocyanic acid
Absorbing liquid；Wherein, from containing sulphuric acid, phosphoric acid, acetic acid or ethanol aqueous acid, the ph value of its spray liquid is controlled to spray liquid
1～3, temperature control is 5～10 DEG C；
(2) stripping step
Absorbing liquid is produced, heated rear feeding stripping top of tower, part is evaporated by the absorbing liquid containing hydrocyanic acid, is formed and all contains
The gas phase of hydrocyanic acid and liquid phase, gas phase enters rectifying tower reactor by the vapor delivery line of stripping column overhead, and liquid phase is returned by stripping column overhead
Stream enters tower reactor, and through reboiler heating evaporation, the hydrocyanic acid in aqueous solution is separated in stripping tower, obtains containing micro hydrocyanic acid
Stripping residual liquid；After stripping residual liquid is cooled to 5～10 DEG C, sends into absorption tower tower top, hydrocyanic acid synthesis gas is absorbed, inhaling
Receive tower tower reactor and obtain the absorbing liquid containing hydrocyanic acid；
(3) rectification step
Add polymerization inhibitor in rectifying column tower top, tower bottom of rectifying tower is entered by the gas phase containing hydrocyanic acid that stripping column overhead is come, and
In rectifying column, further separating-purifying, the extremely low hydrocyanic acid gas of the water content obtaining, are refluxed condenser and are all condensed into
Hydrocyanic acid liquid, partial condensation liquid flows back, and partial condensation liquid produces as finished product liquid hydrogen cyanide product；Rectifying column kettle liquid is by following
Ring pump produce, after again through outer circulation cooler cool down, afterwards part return rectifying column hypomere, partly deliver to stripping top of tower.
10. the method for purification of hydrocyanic acid as claimed in claim 1 is it is characterised in that comprise the steps:
(1) absorption step
Hydrocyanic acid synthesis gas is sent into absorbing tower bottom, and is passed through spray liquid in absorption tower tower top, spray-absorption obtains hydrogeneous cyanogen
The absorbing liquid of acid；Wherein, spray liquid is from containing sulphuric acid, phosphoric acid, acetic acid or ethanol aqueous acid, the ph value control of its spray liquid
It is made as 1～3, temperature control is 5～10 DEG C；
(2) stripping step
Absorbing liquid is produced by pump, sends into stripping top of tower after hot and cold heat exchanger heating, the absorbing liquid containing hydrocyanic acid is by part
Evaporation, forms all gas phase containing hydrocyanic acid and liquid phase, and gas phase enters rectifying tower reactor, liquid phase by the vapor delivery line of stripping column overhead
Tower reactor is flowed back into by stripping column overhead, through reboiler heating evaporation, the hydrocyanic acid in aqueous solution is separated in stripping tower, obtains
To the stripping residual liquid containing micro hydrocyanic acid；Stripping residual liquid is cooled to after 5～10 DEG C through hot and cold heat exchanger, freezing water- to-water heat exchanger, send
Enter absorption tower tower top, hydrocyanic acid synthesis gas is absorbed, obtain the absorbing liquid containing hydrocyanic acid in absorption tower tower reactor；
(3) rectification step
Add polymerization inhibitor in rectifying column tower top, tower bottom of rectifying tower is entered by the gas phase containing hydrocyanic acid that stripping column overhead is come, and
In rectifying column, further separating-purifying, the extremely low hydrocyanic acid gas of the water content obtaining, are refluxed condenser and are all condensed into
Hydrocyanic acid liquid, partial condensation liquid flows back, and partial condensation liquid produces as finished product liquid hydrogen cyanide product；Rectifying column kettle liquid is by following
Ring pump produces, after cause 5～8 DEG C of its temperature drop through the cooling of outer circulation cooler again, part returns rectifying column hypomere afterwards
Between 15～13 blocks of column plates, partly deliver to stripping top of tower, and the outer circulation amount that rectifying column kettle liquid produces through circulating pump, with part
Returning the ratio between the capacity of returns of rectifying column is 0.5～0.6.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20210034658A (en) * | 2018-07-30 | 2021-03-30 | 에보니크 오퍼레이션즈 게엠베하 | Method for purifying hydrogen cyanide |
| 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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| 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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|---|---|
| CN106365178B (en) | 2018-07-27 |
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