CN102633283A - Purification method of hydrocyanic acid - Google Patents
Purification method of hydrocyanic acid Download PDFInfo
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- CN102633283A CN102633283A CN2012100947040A CN201210094704A CN102633283A CN 102633283 A CN102633283 A CN 102633283A CN 2012100947040 A CN2012100947040 A CN 2012100947040A CN 201210094704 A CN201210094704 A CN 201210094704A CN 102633283 A CN102633283 A CN 102633283A
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- purification
- acid
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- prussic acid
- stopper
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 238000000746 purification Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 238000007670 refining Methods 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims description 26
- 241000282326 Felis catus Species 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- ZFHSIBJQGYOTQN-UHFFFAOYSA-N oxygen(2-) phosphane titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].P ZFHSIBJQGYOTQN-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000004821 distillation Methods 0.000 abstract description 5
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 reactive dyestuffs Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000000605 extraction Methods 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
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a purification method of hydrocyanic acid. In the method, a purification raw material adopts 1-10% by weight of hydrocyanic acid water solution. The purification method comprises the following steps of: preheating the purification raw material to 40-60 DEG C, then introducing into a rectifying tower, adding a polymerization inhibitor, and performing distillation under the conditions that the tower top pressure is 10-90KPa negative pressure, the tower top temperature is 0-25 DEG C, the tower kettle pressure is 20-95KPa negative pressure, the tower kettle temperature is 60-100 DEG C and the reflux ratio is 3-15 so as to realize refining and purification of the hydrocyanic acid. The whole device comprises a vacuum pump which is connected with a reflux tank for operating and used for maintaining the negative pressure in the tower, and the trace hydrocyanic acid contained in exhaust gas of the vacuum pump is sent to an incinerator for incineration treatment. According to the purification method disclosed by the invention, the pressure difference between the tower top and the tower kettle is reduced, the operation temperature is reduced, the corrosion of all the devices can be avoided or reduced, and the polymerization of the hydrocyanic acid is further eliminated, thus the quality of a hydrocyanic acid product and the yield thereof are further improved; and the purification method has the characteristics that the purification method is more economic, energy-saving, environment-friendly and safer.
Description
Technical field
The present invention relates to the refining purification of prussic acid, relate in particular to a kind of method of purification of prussic acid.
Background technology
Prussic acid is the colourless liquid of a kind of slightly acidic, severe toxicity, highly volatile; But also be a kind of important Essential Chemistry material simultaneously; Be mainly used in and produce TEB 3K, adiponitrile, sodium cyanide, amino acid (like methionine(Met)); Intercalating agent (EDTA, DTPA etc.), yellow prussiate of soda/potassium, weedicide (like Glyphosate 62 IPA Salt), dyestuff (as indigo etc.), medicine (like microbiotic), white dyes, reactive dyestuffs, agrochemical.
The method of producing prussic acid on the technical scale mainly contains three kinds: 1) Andrussow method (iS-One method); Namely for methane, ammonia and air/oxygen are under catalyst action; Rapid reaction synthesis of hydrogen cyanida gaseous mixture under 1000～1200 ℃ of high temperature is through absorbing, make with extra care acquisition prussic acid; 2), vinyl cyanide by-product; With a certain proportion of propylene, ammonia, air; Under catalyst action, at about 410 ℃ of following rapid reaction synthesis of acrylonitrile, acetonitrile, prussic acid gaseous mixture, through the prussic acid that absorbs, separates, refining acquisition accounts for vinyl cyanide 2.5%～11%; 3), light oil cracking method, LIGHT DIESEL OIL mixes with ammonia, in electric arc furnace, carries out scission reaction, does carrier with refinery coke, seals with nitrogen, anti-oxidation, synthesis of hydrogen cyanida, again through absorb, the refining prussic acid that obtains.
In the aforesaid method, the synthetic prussic acid method of the most frequently used industry is iS-One method.Usually; This method production process is following: (1) Sweet natural gas, ammonia, air get into synthesis reactor after mixing, preheating; In the presence of catalyzer, rapid reaction synthesis of hydrogen cyanida gaseous mixture under 1000 ℃～1200 ℃ high temperature, hydrogen cyanide content 7～11% in its mixture; (2) use water as prussic acid in the absorption agent absorption extraction gaseous mixture, obtain the dilute prussic acid aqueous solution; (3) dilute prussic acid solution often in the prussic acid rectifying tower, carry out, low-pressure distillation, cat head obtains prussic acid, is absorption agent water at the bottom of the tower, returns absorption system.
IS-One method is produced in the prussic acid process; The purification process of its dilute prussic acid aqueous solution roughly is described below: the prussic acid dilute solution from absorption system is used steam heating through feed heater, gets in the rectifying tower from the 7th block of column plate of counting down (be HETP, the back together); And in rectifying tower, flow downward along the filler top layer; Carry out material and transfer of heat exchange with from bottom to top steam, make that from the tower still to cat head, volatile prussic acid obtains purification; From cat head to tower still, difficult evaporable absorption agent water obtains proposing dense separation; In the prussic acid gas that cat head gas phase outlet line steams, add the gas phase stopper; To prevent gas phase pipeline prussic acid polymerization obstruction, the prussic acid gas that steams gets into overhead condensation water cooler condensation cooling, and the prussic acid condensation flows to backflash after being cooled to liquid; Its part is as phegma; And adding the liquid phase stopper in case after the polymerization of solution stopping phase prussic acid, return rectifying tower top together, part is used for product prussic acid supplies follow-up workshop section; Rectifying bottom product part use steam heating in reboiler, after get back in the tower to keep tower still temperature, part cooling in the input and output material interchanger is then got back to absorption system as absorption agent and is recycled; Whole Distallation systm is kept the tower internal pressure by the pump that connects operation, and the micro-prussic acid that the discharging gas of pump includes is sent into the incinerator burning disposal.During this was produced, the rectification and purification technology of prussic acid was operated under normal pressure or low pressure, and its tower still service temperature is higher; Reboiler and tower still seriously corroded; The polymerization obstruction can often take place in prussic acid in the tower, and influences the ordinary production operation, causes and stops the cleaning maintenance frequently; Have a strong impact on stability, continuity, product yield and the product quality of production operation, also increased the security risk of production management and operation.
Patent CN1771197A discloses and a kind ofly in the bubble-cap tray column, prussic acid has been carried out the distillatory method; Contain the prussic acid solution of prussic acid mass percent more than 50% in this method rectifying tower feeding liquid; Working pressure is 1～2.5bar; Column bottom temperature is 100～130 ℃, and tower top temperature is to distill purification under 25～54 ℃ the condition.Though this method of purification has solved the frequent polymeric problem of prussic acid; But only being fit to purification concentration is the prussic acid solution more than 50%, for lower concentration prussic acid solution, and for example 1～10%; Also need carry out concentrating before the rectifying, thereby increase cost of investment and running cost; And working pressure, temperature in this method rectification and purification process are higher, can cause reboiler and tower body heavy corrosion.In addition, its pressurization operation, device fabrication and Distallation systm have strict demand, if leakage is arranged, prussic acid will flow in the environment, and security risk is very big.
Summary of the invention
The object of the present invention is to provide a kind of method of purification of prussic acid, this method adopts micro-negative pressure operation, can reduce service temperature, alleviates equipment corrosion, and in operation, adds stopper, and can alleviate or eliminate the prussic acid polymerization greatly, reduces security risk.
The objective of the invention is to realize like this:
A kind of method of purification of prussic acid is characterized in that: its purification raw material employing quality percentage composition is 1～10% hydrocyanic acid aqueous solution; Feed rectifying tower with behind the said purification raw material preheating to 40～60 ℃; Add stopper; In negative pressure is the tower top pressure of 10～90 KPa, and tower top temperature is 0～25 ℃, and negative pressure is the tower still pressure of 20～95 KPa; Tower still temperature is 60～100 ℃, thereby reflux ratio is to distill the refining purification that realizes prussic acid under 3～15 the condition; Its whole device is kept negative pressure in the tower by the vacuum pump that is connected operation with backflash, and the micro-prussic acid that the discharging gas of vacuum pump includes is sent into the incinerator burning disposal.
Above-mentioned rectifying tower, employing be packing tower, its stage number is 22; Wherein, 15 of rectifying sections, 7 of stripping sections, reflux ratio is preferably 5～11.When reflux ratio is excessive, not only can reduces the throughput of device, and the distillation operation cost can be increased sharply; But when reflux ratio was too small, the hydrogen cyanide product quality that cat head comes out then can not satisfy processing requirement, and promptly prussic acid can not get enough purifications.
Above-mentioned tower top pressure is preferably the negative pressure of 20～80KPa.Adopt negative-pressure operation, the tower resistance is little, and it is low to take temperature, and liquid holdup is few in the tower, and prussic acid is short at dwell time in the tower, thereby can reduce the prussic acid polymerization and reduce equipment corrosion.
Above-mentioned stopper comprises the gentle phase stopper of liquid phase stopper; Wherein, the liquid phase stopper is organic carboxyl acids such as formic acid, acetate or propionic acid, mineral acids such as sulfuric acid or phosphoric acid, preferably sulfuric acid or phosphoric acid; The gas phase stopper is acidic oxides such as sulfurous gas or titanium dioxide phosphorus, preferred sulfurous gas.Because of the polymerization of prussic acid not only responsive to service temperature; And it is particularly responsive to acid-basicity; So add an amount of stopper respectively to phegma with in the purification materials such as prussic acid gas that cat head gas phase outlet line steams; The pH value that is the may command distillation system keeps being not more than 4.5, thereby greatly reduces the autocatalysis polymerization of prussic acid.
The add-on of above-mentioned liquid phase stopper be institute's purification feed back liquid gross weight 0.01～1.0%, preferred 0.03～0.5%; The add-on of above-mentioned gas phase stopper is 0.001～0.01% of the prussic acid gas gross weight that steams at cat head gas phase outlet line.
Above-mentioned purification raw material is to adopt to make absorption agent with water and in the absorption tower, absorbs by the prussic acid in the prussic acid synthetic gas of iS-One method production and make.
The present invention has following beneficial effect:
The inventive method has reduced cat head tower still pressure reduction through the prussic acid solution of negative pressure rectification and purification lower concentration, has reduced service temperature; Shortened the residence time of prussic acid in tower, thereby avoided or reduced reboiler, tower still, tower body suffering the acid and the high temperature corrosion of lower concentration, simultaneously through adding an amount of stopper; Further eliminated the polymerization of prussic acid; Thereby improved hydrogen cyanide product quality and yield thereof, had more economically, energy-conserving and environment-protective, safer characteristics.Use the inventive method in the actual production, obtained the quality percentage composition and reached the hydrogen cyanide product more than 99%, and its platinum-cobalt colourimetric number≤10 (the big I of product colourimetric number is judged the polymerization situation of prussic acid).In addition, adopt the inventive method, iron concentration is no more than 50ppm (but in the distillation residual liquid corrosion situation of iron ion content judgment device) in the still raffinate.In addition, through Aspen Plus process simulation system to method of purification row of the present invention the steady-state simulation and the optimization design of system, verify and guaranteed the safety of the inventive method.
Embodiment
Through embodiment the present invention is specifically described below; Be necessary to be pointed out that at this; Following examples only are used for the present invention is further explained; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the foregoing invention content.
Embodiment 1
A kind of method of purification of prussic acid; Its purification raw material adopts to be made absorption agent with water and in the absorption tower, absorbs the prussic acid in the prussic acid synthetic gas of being produced by iS-One method and make, and it specifically consists of quality percentage composition (w/w, back with) prussic acid solution described as follows: HCN 2.10%; Water 97.75%, H
2SO
40.15%; Its rectifying tower adopt diameter be 1200 mm in be filled with the rectifying tower of acid-proof ceramics filler, this rectifying tower amounts to 22 blocks of column plates, wherein rectifying section is 15,7 of stripping sections; With the flow of this purification raw material with 12050kg/ hour; Flowing through is heated to 55 ℃ in the feed heater, get into the rectifying tower from the 7th block of several down column plates afterwards, and be 19.6 ℃ in tower top temperature; Tower top pressure is the negative pressure of 80 KPa; Tower still temperature is 94.2 ℃, and tower still pressure is the negative pressure of 82.5 KPa, and reflux ratio is to carry out rectifying under 11 the condition; Amount by 2.5 liters/hour in the prussic acid gas that cat head gas phase outlet line steams adds stopper SO
2(gaseous state); The prussic acid gas that steams afterwards gets into the condensation of overhead condensation water cooler; Condensate stream is to backflash, and its part is as phegma, and it is dense for after degree 98% sulfuric acid makes stopper to add quality by 1.1kg/ hour amount; Return rectifying tower top together, part is used for the finished product prussic acid supplies follow-up workshop section; Rectifying bottom product part use steam heating in reboiler, after get back in the tower keeping tower still temperature, part cools in water cooler and then gets back to absorption system as absorption agent and recycle; Whole device is kept negative pressure in the tower by the vacuum pump that is connected operation with backflash, and the micro-prussic acid that the discharging gas of vacuum pump includes is sent into the incinerator burning disposal; Finally obtain the concrete composition of product such as following: HCN 99.55%, H
2SO
40.02%, water 0.43%; The platinum of this product-cobalt look number≤10; And the still raffinate consists of quality percentage composition (w/w) component described as follows: HCN 0.05%, H at the bottom of the tower
2SO
40.82%, water 99.13%.
Embodiment 2
A kind of method of purification of prussic acid, the concrete composition of its purification raw material prussic acid solution described as follows: HCN 10.0%, water 89.65%, H
2SO
40.35%; In feed heater, be heated to 40 ℃; Its tower top pressure is the negative pressure of 90 KPa, and tower top temperature is 25 ℃, and tower still temperature is 60 ℃, and tower still pressure is the negative pressure of 95 KPa, and reflux ratio is 15; The flow that the purification raw material was pressed 12050kg/ hour adds, and the amount by 2.5 liters/hour in the prussic acid gas that cat head gas phase outlet line steams adds stopper SO
2(gaseous state), adding mass concentration by 1.1kg/ hour amount in the phegma is that 80% phosphate aqueous solution is made stopper, and miscellaneous equipment requirement, operational requirement etc. are all with embodiment 1, and finally obtain the concrete composition of product such as following: HCN 99.22%, H
3PO
40.02%, water 0.76%; The platinum of this product-cobalt look number≤10.
Embodiment 3
A kind of method of purification of prussic acid, the concrete composition of its purification raw material prussic acid solution described as follows: HCN 8.50%, water 91.15%, H
2SO
40.35%; In feed heater, be heated to 50 ℃; Its tower top pressure is the negative pressure of 10 KPa, and tower top temperature is 23.5 ℃, and tower still temperature is 90 ℃, and tower still pressure is the negative pressure of 90 KPa, and reflux ratio is 3; The purification raw material adds with 12050kg/ hour flow, and the amount by 2.5 liters/hour in the prussic acid gas that cat head gas phase outlet line steams adds stopper SO
2(gaseous state), the amount adding mass concentration by 1.0kg/ hour in the phegma is that 85% aqueous formic acid is made stopper; Miscellaneous equipment requirement, operational requirement etc. are all with embodiment 1, and finally obtain the concrete composition of product such as following: HCN 99.56%, formic acid 0.03%, water 0.41%; The platinum of this product-cobalt look number≤10.
Embodiment 4
A kind of method of purification of prussic acid, the concrete composition of its purification raw material prussic acid solution described as follows: HCN 1.10%, water 98.55%, H
2SO
40.35%; In feed heater, be heated to 60 ℃; Its tower top pressure is the negative pressure of 20 KPa, and tower top temperature is 0 ℃, and tower still temperature is 100 ℃, and tower still pressure is the negative pressure of 20 KPa, and reflux ratio is 5; The purification raw material adds with 12050kg kg/ hour flow; In the prussic acid gas that cat head gas phase outlet line steams, add stopper sulfurous gas (gaseous state) by 2.5 liters/hour amount, adding mass concentration by 1.1kg/ hour amount in the phegma is that 80% acetic acid aqueous solution is made stopper; Miscellaneous equipment requirement, operational requirement etc. are all with embodiment 1, and finally obtain the concrete composition of product such as following: HCN 99.60%, acetate 0.02%, water 0.38%; The platinum of this product-cobalt look number≤10.
Embodiment 5
A kind of method of purification of prussic acid, the concrete composition of its purification raw material prussic acid solution described as follows: HCN 5.50%, water 94.35%, H
2SO
40.15%; In feed heater, be heated to 58 ℃; Its tower top pressure is the negative pressure of 55 KPa, and tower top temperature is 12 ℃, and tower still temperature is 75 ℃, and tower still pressure is the negative pressure of 36 KPa, and reflux ratio is 5; The purification raw material adds with 12050kg/ hour flow, and the amount by 2.5 liters/hour in the prussic acid gas that cat head gas phase outlet line steams adds stopper SO
2(gaseous state) is that to add mass concentration be that the 90% propionic acid aqueous solution is made stopper for 1.0% amount by accounting for the phegma mass ratio in the phegma; Miscellaneous equipment requirement, operational requirement etc. are all with embodiment 1, and finally obtain the concrete composition of product such as following: HCN 99.47%, propionic acid 0.02%, water 0.51%; The platinum of this product-cobalt look number≤10.
Comparative Examples 1
A kind of method of purification of prussic acid, stopper interpolation situation changes that according to the form below is said to carry out in the application example of its each sequence number, and its raw material is selected for use, and equipment requirements, operational requirement etc. are all with embodiment 1, and gained rectifying product is formed as shown in the table:
Table 1 group of products is shone in pairs
Conclusion: the present invention has eliminated the polymerization of prussic acid in the purification process, thereby has improved hydrogen cyanide product quality and yield thereof through the gentle phase stopper of while annex solution phase stopper, and its beneficial effect is remarkable.
Comparative Examples 2
A kind of method of purification of prussic acid, the working pressure situation changes that according to the form below is said to carry out in the application example of its each sequence number, and its raw material is selected for use, and equipment requirements, operational requirement etc. are measured Fe in the rectifying still raffinate all with embodiment 1 in continuous operation after 5 days
2+Content, its result is as shown in the table:
The residual middle Fe of still under the table 2 different operating pressure
2+Content
| Sequence number | Fe 2+Content (PPM) | Explanation |
| 1 | 17 | Tower still pressure 45KPa, 77 ℃ of tower still temperature |
| 2 | 377 | Tower still pressure 110KPa, 103 ℃ of tower still temperature |
Conclusion: the inventive method has reduced cat head tower still pressure reduction through the prussic acid solution of negative pressure rectification and purification lower concentration, has reduced service temperature; Thereby avoid or reduced reboiler, tower still, tower body suffering the acid and the high temperature corrosion of lower concentration; Through adding suitable stopper, further eliminated the polymerization of prussic acid, thereby improved hydrogen cyanide product quality and yield thereof simultaneously; Have more economically, energy-conserving and environment-protective, safer characteristics.
Claims (10)
1. the method for purification of a prussic acid is characterized in that: it is 1～10% hydrocyanic acid aqueous solution that its purification raw material adopts quality percentage composition; Feed rectifying tower with behind the said purification raw material preheating to 40～60 ℃; Add stopper; In negative pressure is the tower top pressure of 10～90 KPa, and tower top temperature is 0～25 ℃, and negative pressure is the tower still pressure of 20～95 KPa; Tower still temperature is 60～100 ℃, thereby reflux ratio is to distill the refining purification that realizes prussic acid under 3～15 the condition; Its whole device is kept negative pressure in the tower by the vacuum pump that is connected operation with backflash, and the micro-prussic acid that the discharging gas of vacuum pump includes is sent into the incinerator burning disposal.
2. the method for purification of prussic acid according to claim 1 is characterized in that: said rectifying tower, specifically adopt packing tower, and its stage number is 22; Wherein, 15 of rectifying sections, 7 of stripping sections, reflux ratio is 5～11.
3. the method for purification of prussic acid according to claim 1 or claim 2, it is characterized in that: said tower top pressure is the negative pressure of 20～80KPa.
4. the method for purification of prussic acid according to claim 1 or claim 2, it is characterized in that: said stopper comprises the gentle phase stopper of liquid phase stopper; Wherein, the liquid phase stopper is formic acid, acetate or propionic acid, perhaps sulfuric acid or phosphoric acid; The gas phase stopper is sulfurous gas or titanium dioxide phosphorus.
5. like the method for purification of the said prussic acid of claim 3, it is characterized in that: said stopper comprises the gentle phase stopper of liquid phase stopper; Wherein, the liquid phase stopper is formic acid, acetate or propionic acid, perhaps sulfuric acid or phosphoric acid; The gas phase stopper is sulfurous gas or titanium dioxide phosphorus.
6. like the method for purification of the said prussic acid of claim 4, it is characterized in that: said liquid phase stopper is sulfuric acid or phosphoric acid; Said gas phase stopper is a sulfurous gas.
7. like the method for purification of the said prussic acid of claim 5, it is characterized in that: said liquid phase stopper is sulfuric acid or phosphoric acid; Said gas phase stopper is a sulfurous gas.
8. like the method for purification of the arbitrary said prussic acid of claim 4-7, it is characterized in that: the add-on of said liquid phase stopper be institute's purification feed back liquid gross weight 0.01～1.0%; The add-on of said gas phase stopper is 0.001～0.01% of the prussic acid gas gross weight that steams at cat head gas phase outlet line.
9. like the method for purification of the arbitrary said prussic acid of claim 4-7, it is characterized in that: the add-on of said liquid phase stopper be institute's purification feed back liquid gross weight 0.03～0.5%; The add-on of said gas phase stopper is 0.001～0.01% of the prussic acid gas gross weight that steams at cat head gas phase outlet line.
10. like the method for purification of the arbitrary said prussic acid of claim 1-9, it is characterized in that: said purification raw material is to adopt to make absorption agent with water and in the absorption tower, absorbs by the prussic acid in the prussic acid synthetic gas of iS-One method production and make.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104724727A (en) * | 2015-03-24 | 2015-06-24 | 山东新和成氨基酸有限公司 | Dual-tower serially connected rectifying, separating and purifying process of hydrocyanic acid |
| CN110627091A (en) * | 2019-10-24 | 2019-12-31 | 重庆工商大学 | A kind of method adopting chemical method to purify the hydrocyanic acid that is used to prepare adiponitrile |
| CN114291795A (en) * | 2022-01-18 | 2022-04-08 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for preparing high-purity sulfur dioxide |
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| CN1217324A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Process for recovering and refining olefinic nitrile |
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| EP0890572A1 (en) * | 1997-07-08 | 1999-01-13 | The Standard Oil Company | Purification of acetonitrile by a distillative recovery/ion exchange resin treatment process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104724727A (en) * | 2015-03-24 | 2015-06-24 | 山东新和成氨基酸有限公司 | Dual-tower serially connected rectifying, separating and purifying process of hydrocyanic acid |
| CN110627091A (en) * | 2019-10-24 | 2019-12-31 | 重庆工商大学 | A kind of method adopting chemical method to purify the hydrocyanic acid that is used to prepare adiponitrile |
| CN114291795A (en) * | 2022-01-18 | 2022-04-08 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for preparing high-purity sulfur dioxide |
| CN114291795B (en) * | 2022-01-18 | 2023-04-18 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for preparing high-purity sulfur dioxide |
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Application publication date: 20120815 |