CN103864099B - The method of comprehensive utilization of a kind of cyanuric acid industrial gaseous waste and waste water - Google Patents
The method of comprehensive utilization of a kind of cyanuric acid industrial gaseous waste and waste water Download PDFInfo
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- CN103864099B CN103864099B CN201410036219.7A CN201410036219A CN103864099B CN 103864099 B CN103864099 B CN 103864099B CN 201410036219 A CN201410036219 A CN 201410036219A CN 103864099 B CN103864099 B CN 103864099B
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Abstract
The present invention relates to Chemical Manufacture and recycle field, the particularly method of comprehensive utilization of a kind of cyanuric acid industrial gaseous waste and waste water.The method of comprehensive utilization of this cyanuric acid industrial gaseous waste and waste water, the ammonia produced in producing with cyanuric acid, the waste water of carbonic acid gas and chloride containing calcium or sodium-chlor are for raw material, it is characterized in that: ammonia is passed in the waste water of chloride containing calcium or sodium-chlor, generate the mixed solution containing ammonium hydroxide and sodium-chlor or calcium chloride, again exhaust carbon dioxide is passed in mixed solution, produce ammonium chloride, sodium bicarbonate or calcium carbonate, isolate sodium bicarbonate or calcium carbonate according to different solubility, then obtain ammonium chloride product through condensing crystal, filtering drying.Present invention achieves the comprehensive utilization of calcium chloride or sodium-chlor in the amino carbonic acid gas of waste gas in cyanuric acid, DICHLOROISOCYANURIC ACID, Surchlor GR 60, trichloroisocyanuric acid production, waste water, feedstock circulation is utilized, both reduce production cost, additionally reduce pollution.
Description
(1) technical field
The present invention relates to Chemical Manufacture and recycle field, the particularly method of comprehensive utilization of a kind of cyanuric acid industrial gaseous waste and waste water.
(2) background technology
In prior art, in the production process of cyanuric acid (CA), can discharge a large amount of ammonias, these ammonias are byproduct of ammonium sulfate by sulfuric acid absorption; And the exhaust carbon dioxide that DICHLOROISOCYANURIC ACID (DCCA), Surchlor GR 60 (SDC), trichloroisocyanuric acid (TCCA) produce in producing enters in air, the chloride containing calcium simultaneously produced, the waste water of sodium-chlor then directly discharge; The processing mode of above-mentioned waste gas and waste water not only causes pollution to environment, also creates the waste of material.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides a kind of protection of the environment, reduces the cyanuric acid industrial gaseous waste of production cost and the method for comprehensive utilization of waste water.
The present invention is achieved through the following technical solutions:
The method of comprehensive utilization of a kind of cyanuric acid industrial gaseous waste and waste water, the ammonia produced in producing with cyanuric acid and DICHLOROISOCYANURIC ACID, Surchlor GR 60, the waste water of the exhaust carbon dioxide that trichloroisocyanuric acid produces in producing and chloride containing calcium or sodium-chlor is raw material, it is characterized in that: ammonia is passed in the waste water of chloride containing calcium or sodium-chlor, generate the mixed solution containing ammonium hydroxide and sodium-chlor or calcium chloride, again exhaust carbon dioxide is passed in mixed solution, produce ammonium chloride, sodium bicarbonate or calcium carbonate, sodium bicarbonate or calcium carbonate is isolated according to different solubility, then through condensing crystal, filtering drying obtains ammonium chloride product.
It is that raw material is through pyrolysis that the present invention passes through with urea, the sodium chloride-containing that the ammonia of releasing when condensation obtains cyanuric acid and production DICHLOROISOCYANURIC ACID, Surchlor GR 60, trichloroisocyanuric acid produce in producing or the waste liquid of calcium chloride and reacting to each other of waste gas, above-mentioned waste gas and waste liquid are effectively utilized, finally obtain the ammonium chloride product that can be used for producing, achieve the comprehensive utilization of waste gas, waste water, part material is recycled, and reduces production cost, solves environmental pollution.
More excellent scheme of the present invention is:
When described ammonia passes in the waste water of chloride containing calcium or sodium-chlor, waste water is heated, final Heating temperature to 260 DEG C, and maintain wastewater temperature at least 10 minutes, to realize the abundant absorption of ammonia.
The mixed solution of described connection CO 2 waste gas pipe after pH is reduced to adularescent Precipitation gradually, by heat concentrated, filter obtain white sodium bicarbonate or calcium carbonate, reconcentration evaporation obtain ammonium chloride product.
Present invention achieves the comprehensive utilization of calcium chloride or sodium-chlor in the amino carbonic acid gas of waste gas in cyanuric acid, DICHLOROISOCYANURIC ACID, Surchlor GR 60, trichloroisocyanuric acid production, waste water, feedstock circulation is utilized, both reduce production cost, additionally reduce pollution.
(4) embodiment
Embodiment 1:
Calcium chloride in DICHLOROISOCYANURIC ACID (DCCA) waste water, the comprehensive utilization of the useless ammonia in the carbonic acid gas in waste gas and cyanuric acid (CA).
(1) preparation of mixed solution
(1) the little basin of enamel filling 300 grams of urea and 15 grams of ammonium chlorides is put into being equipped with in safety valve, escape pipe, thermometer, the Steel Vessel A of airtight resistance to low pressure that can heat;
(2) get 300 milliliters of DICHLOROISOCYANURIC ACID mother liquid comings (mother liquid coming through the pH6-7 of chemical examination containing 10% calcium chloride through preliminary treatment), put into the reaction flask B of 500 milliliters that reflux exchanger, thermometer, acidometer, gas input conduit are housed;
(3) then the gas input conduit on reaction flask B in the escape pipe on the Steel Vessel A in step (1) and step (2) is linked up;
(4) when Steel Vessel A slowly being heated 150 DEG C, the mother liquid coming pH value in step (2) reaction flask B starts gradually to raise, and when after 25 minutes, the temperature in Steel Vessel A reaches 260 DEG C, keep 260 DEG C ten minutes; When the pH of mother liquor rises to 11-12 in step (2) reaction flask B, open the blow-off valve on Steel Vessel A, turn off the air outlet valve on Steel Vessel A;
(5) remove the adapting pipe of Steel Vessel A and reaction flask B, the solution in reaction flask B is the mother liquid coming after inhaling ammonia, and pH is 11-12, is mixed solution.
(2) mixed solution and carbon dioxide reaction
(1) 42 grams of cyanuric acids and 33 grams of calcium carbonate and 350 ml waters are put into the reaction flask C of 500 milliliters that are equipped with magnetic stirring apparatus, thermometer, acidometer, ventpipe and escape pipe, then put into cooling bath;
(2) the air outlet of reaction flask C with fill the inlet mouth that step () carries out the reaction flask B of mixed solution and couple together;
(3) magnetic agitation of reaction flask C is started, slowly open chlorine valve, logical chlorine is started with the logical chlorine speed of 0.5ml/ minute, carry out at temperature is less than 30 DEG C, pH is down to 1.5 by 6.8, the liquid pH value filled in the reaction flask B of mixed solution is reduced gradually by 11-12, the adularescent Precipitation when pH value drops to 9-10;
(4) heating filling the reaction flask B absorbing carbonic acid gas, filtering when treatment solution is concentrated to and also has 150 milliliters, obtaining the white products calcium carbonate that content is 98.3%;
(5) filtrate is continued the ammonium chloride product that concentration and evaporation obtains nitrogen content 25.8%.
Embodiment 2:
Be that raw material and its wife react with DICHLOROISOCYANURIC ACID (DCCA) and calcium carbonate, production trichloroisocyanuric acid (TCCA), the waste water of chloride containing calcium produced in production, the comprehensive utilization of exhaust carbon dioxide.
(1) preparation of mixed solution
(1) in 1000 milliliters of reaction flask A that magnetic stirring apparatus, thermometer, acidometer, Chlorination tube, blow-down pipe are housed, add DICHLOROISOCYANURIC ACID 52 grams, 15 grams, calcium carbonate and 500 milliliters, water, add dispersion agent Sodium dodecylbenzene sulfonate 1.5 grams simultaneously, sequestering agent citric acid 1 gram, then puts into cooling bath reaction flask A, starts magnetic stirring apparatus, slowly open chlorine valve, pass into chlorine with the speed of 0.3ml/min, open water coolant, make temperature of reaction lower than 30 DEG C; It is reaction emphasis when pH drops to 2-4 by 7, solids (trichloroisocyanuric acid) will be reacted leach, its filtrate is neutralized to pH6-7 with calcium hydroxide, then the waste liquid handled well is placed in the 1000ml reaction flask B that reflux exchanger, thermometer, acidometer, gas input conduit are housed;
(2) be equipped with safety valve, gas-holder, blow-down pipe, thermometer, can heat airtight be low pressure Steel Vessel C in, put into the little basin of enamel filling 300 grams of urea, 15 grams of ammonium chlorides;
(3) gas introduction tube of giving vent to anger on tubule and reaction flask B on Steel Vessel C is linked up;
(4) Steel Vessel C is slowly heated, when 150 DEG C, the mother liquid coming pH value in reaction flask B start raise, when heating is after 25 minutes, the temperature in Steel Vessel C reaches 260 DEG C, and keep 260 DEG C ten minutes; In reaction flask B, the pH value of mother liquor rises to 12, opens the blow-off valve on Steel Vessel C, turns off the air outlet valve on Steel Vessel C;
(5) remove the adapting pipe of Steel Vessel C and reaction flask B, the mother liquid coming in reaction flask B is the mother liquid coming after inhaling ammonia, and pH is 12, is ready-made mixed solution.
(2) mixed solution and carbon dioxide reaction
(1) in 1000 milliliters of reaction flask D that magnetic stirring apparatus, thermometer, acidometer, Chlorination tube, blow-down pipe and gas output tube are housed, add DICHLOROISOCYANURIC ACID 52 grams, 15 grams, calcium carbonate and 500 milliliters, water, add dispersion agent Sodium dodecylbenzene sulfonate 1.5 grams, sequestering agent citric acid 1 gram simultaneously;
(2) tubule of giving vent to anger of reaction flask D is connected with the reaction flask B that the mixed solution after inhaling ammonia is housed;
(3) start magnetic agitation, open chlorine valve, start logical chlorine with the logical chlorine speed of 0.3ml/ minute;
(4) the mixed solution pH value in reaction flask B starts to decline, and when pH drops to 9-10, adularescent material is separated out, and when pH drops to 6-7, stops absorbing carbon dioxide;
(4) will the liquid concentration of carbonic acid gas have been inhaled, filter when being concentrated to volume and being 300ml, dry content is the calcium carbonate of 98.3%, the crystallization of filtrated stock reconcentration, dry nitrogen content is the ammonium chloride product of 25.8%.
Embodiment 3:
Be that raw material and chlorine carry out react the comprehensive utilization generating exhaust carbon dioxide in sodium-chlor in waste water that trichloroisocyanuric acid (TCCA) produces and production with DICHLOROISOCYANURIC ACID (DCCA) and sodium carbonate.
(1) preparation of mixed solution
(1) the little basin of enamel filling 300 grams of urea and 15 grams of ammonium chlorides is put into being equipped with in safety valve, escape pipe, blow-down pipe, thermometer, the Steel Vessel A of airtight resistance to low pressure that can heat;
(2) get with DICHLOROISOCYANURIC ACID and volatile salt as raw material and chlorine reaction make trichloroisocyanuric acid, this waterproof, through the waste water of the pH6-7 of preliminary treatment, is put into the reaction flask B of 500 milliliters that reflux exchanger, thermometer, acidometer, gas input conduit are housed by the sodium chloride-containing in production;
(3) then the gas input conduit on reaction flask B in the escape pipe on the Steel Vessel A in step (1) and step (2) is linked up;
(4) slowly heated by Steel Vessel A, the pH value of liquid when 150 DEG C in reaction flask B starts to raise, when the temperature in Steel Vessel A reaches 260 DEG C in 25 minutes, remain on 260 DEG C ten minutes; Liquid pH value in reaction flask B rises to 11-12, then opens the blow-off valve on Steel Vessel A, turns off the air outlet valve on Steel Vessel A;
(5) remove the adapting pipe of Steel Vessel A and reaction flask B, the pH in reaction flask B is the mother liquor after the suction ammonia of 11-12, is mixed solution.
(2) mixed solution and carbon dioxide reaction
(1) 5.2 grams of DICHLOROISOCYANURIC ACID and 15 grams of sodium carbonate are put into the reaction flask C of 1000 milliliters being equipped with magnetic stirring apparatus, thermometer, acidometer and escape pipe, blow-down pipe;
(2) gas inlet pipe on the escape pipe on reaction flask C and reaction flask B is coupled together;
(3) 500 ml waters are added in reaction flask C, open magnetic agitation;
(4) liquid pH value in reaction flask B declines gradually, occurs white precipitate when pH is 9-10, reduces with pH, and precipitation increases gradually, when pH value drops to 7-8, opens the vent valve on reaction flask C;
(5) the liquid concentration after above-mentioned same carbonic acid gas, when volume about 300 milliliters, let cool rear filtration, filter rear and dry content is the sodium bicarbonate of 98.5%; Mother liquor continues condensing crystal, and filtering drying obtains the ammonium chloride finished product of nitrogen content 25.3%.
Claims (1)
1. the calcium chloride in DICHLOROISOCYANURIC ACID waste water, the method for comprehensive utilization of the useless ammonia in the carbonic acid gas in waste gas and cyanuric acid, is characterized in that:
(1) preparation of mixed solution
(1) the little basin of enamel filling 300 grams of urea and 15 grams of ammonium chlorides is put into being equipped with in safety valve, escape pipe, thermometer, the Steel Vessel A of airtight resistance to low pressure that can heat;
(2) get the DICHLOROISOCYANURIC ACID mother liquid coming of 300 milliliters of pH6-7 containing 10% calcium chloride, put into the reaction flask B of 500 milliliters that reflux exchanger, thermometer, acidometer, gas input conduit are housed;
(3) then the gas input conduit on reaction flask B in the escape pipe on the Steel Vessel A in step (1) and step (2) is linked up;
(4) when Steel Vessel A slowly being heated 150 DEG C, the mother liquid coming pH value in step (2) reaction flask B starts gradually to raise, and when after 25 minutes, the temperature in Steel Vessel A reaches 260 DEG C, keep 260 DEG C ten minutes; When the pH of mother liquor rises to 11-12 in step (2) reaction flask B, open the blow-off valve on Steel Vessel A, turn off the air outlet valve on Steel Vessel A;
(5) remove the adapting pipe of Steel Vessel A and reaction flask B, the solution in reaction flask B is the mother liquid coming after inhaling ammonia, and pH is 11-12, is mixed solution;
(2) mixed solution and carbon dioxide reaction
(1) 42 grams of cyanuric acids and 33 grams of calcium carbonate and 350 ml waters are put into the reaction flask C of 500 milliliters that are equipped with magnetic stirring apparatus, thermometer, acidometer, ventpipe and escape pipe, then put into cooling bath;
(2) the air outlet of reaction flask C with fill the inlet mouth that step () carries out the reaction flask B of mixed solution and couple together;
(3) magnetic agitation of reaction flask C is started, slowly open chlorine valve, logical chlorine is started with the logical chlorine speed of 0.5ml/ minute, carry out at temperature is less than 30 DEG C, pH is down to 1.5 by 6.8, the liquid pH value filled in the reaction flask B of mixed solution is reduced gradually by 11-12, the adularescent Precipitation when pH value drops to 9-10;
(4) heating filling the reaction flask B absorbing carbonic acid gas, filtering when treatment solution is concentrated to and also has 150 milliliters, obtaining the white products calcium carbonate that content is 98.3%;
(5) filtrate is continued the ammonium chloride product that concentration and evaporation obtains nitrogen content 25.8%.
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| CN104477962A (en) * | 2014-12-19 | 2015-04-01 | 华东理工大学 | Co-production method of calcium carbonate and hydrogen chloride gas by distilled ammonia waste liquid of sodium carbonate industry |
| CN104803531B (en) * | 2015-04-14 | 2016-08-17 | 济宁璟华环保科技有限公司 | Sym-closene mother liquor waste water processing method |
| CN106145163B (en) * | 2016-06-21 | 2018-05-22 | 中国科学院过程工程研究所 | A kind of post-processing approach of vanadium extracting waste water |
| CN111498910B (en) * | 2020-05-26 | 2022-09-16 | 宜宾海丰和锐有限公司 | Resource utilization method of chlorination waste residue |
| CN113200643A (en) * | 2021-04-13 | 2021-08-03 | 子赫科技湖北有限公司 | Process for realizing near-zero discharge of trichloroisocyanuric acid production wastewater |
| CN113501613B (en) * | 2021-08-14 | 2022-12-20 | 河南大化环保材料有限公司 | Cyanuric acid production sewage treatment device and method |
| CN114436982A (en) * | 2022-01-24 | 2022-05-06 | 河北六合化工有限公司 | Method for recovering waste water from sodium dichloroisocyanurate production |
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| CN1824667A (en) * | 2005-02-25 | 2006-08-30 | 浙江新安化工集团股份有限公司 | New method for treating glyphosate mother liquor |
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Denomination of invention: A comprehensive utilization method of cyanuric acid industrial waste gas and wastewater Effective date of registration: 20210630 Granted publication date: 20150819 Pledgee: Shandong juancheng Rural Commercial Bank Co.,Ltd. Pledgor: HEZE HUAYI CHEMICAL Co.,Ltd. Registration number: Y2021980005625 |
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Date of cancellation: 20230823 Granted publication date: 20150819 Pledgee: Shandong juancheng Rural Commercial Bank Co.,Ltd. Pledgor: HEZE HUAYI CHEMICAL CO.,LTD. Registration number: Y2021980005625 |