CN101607910A - The removing process of the oxynitride that produces in the chlorobenzene thermal insulation nitration process - Google Patents
The removing process of the oxynitride that produces in the chlorobenzene thermal insulation nitration process Download PDFInfo
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Abstract
The present invention relates to the removing process of the oxynitride that produces in a kind of chlorobenzene thermal insulation nitration process, described method steps is as follows: (1) adiabatic nitration; (2) vacuum flashing; (3) solution-air is separated: liquid phase is that the thick product of nitro-chlorobenzene goes further processing, and gaseous phase materials enters next step; (4) cooling condensation: condensed material enters next step; (5) solution-air is separated: liquid phase is that nitro-chlorobenzene and water go further to handle and utilize, and gaseous phase materials enters next step; (6) blended absorbent: nitric acid aqueous solution and hydrogen peroxide solution absorb nitrogen oxides from exhaust gas; (7) solution-air is separated: amount of nitrogen oxides back up to standard discharging in the gaseous phase materials, liquid phase is as nitration mixture batching and absorption liquid recycle.Technology of the present invention has the advantage that utilization of materials height, three wastes discharge amount are few, be easy to industrial implementation.
Description
Technical field
The present invention relates to a kind of removing process of nitrogen oxides of exhaust gas, the removing process of the oxynitride that produces in particularly a kind of chlorobenzene thermal insulation nitration process belongs to fine chemical technology and technical field of waste gas treatment.
Background technology
Oxynitride (NO
x) be meant a series of compounds of forming by nitrogen element and oxygen element, comprise N
2O, NO, N
2O
3, NO
2, N
2O
4, N
2O
5, use molecular formula NO usually
xRepresent.Except that nitrogen protoxide and nitrogen peroxide, other oxynitride are all extremely unstable, meet light, wet or thermal change becomes nitrogen peroxide and nitrogen protoxide, and nitrogen protoxide becomes nitrogen peroxide again.
Oxynitride is very big to the harm of human body, can directly cause the respiratory tract injury of human body.Oxynitride can make plant damaged even death, and under the katalysis of light, complicated photochmeical reaction takes place easy and hydrocarbons, produces photo-chemical smog, causes serious topsoil.Oxynitride also can cause the destruction of ozonosphere, and also easy and steam is combined into the acid rain that contains the nitric acid composition.Therefore, country has formulated strict NO
xEmission standard (GB13223-2003), 60m chimney in a organized way in the exhaust gas discharged oxynitride be equivalent to mass concentration in nitrogen peroxide≤2.05mg/m
3Air standard.
In the chlorobenzene thermal insulation nitration process, sulfuric acid is catalyzer, chlorobenzene and nitric acid generation nitration reaction generate the nitration product nitro-chlorobenzene, in service temperature is 60 ℃-140 ℃, working pressure is 0.4MPa-1.0MPa, chlorobenzene and the reaction of nitric acid generation continuous nitrification, chlorobenzene reacts the mixture that makes nitro-chlorobenzene through continuous thermal insulating nitration.The mixture of nitro-chlorobenzene, cools off reacting rear material rapidly by the vacuum flashing technology through the reacted material of continuous thermal insulating nitration, and makes the water byproduct and the unreacted raw material chlorobenzene that generate in the nitration reaction process enter gas phase; In vacuum flashing spent acid is concentrated, the material of nitration reaction is through liquid-liquid separation, and water is mainly sulphuric acid soln, separates through removal of impurities, recycles for nitration reaction; Oil phase is the nitro-chlorobenzene mixture, the nitro-chlorobenzene mixture obtains p-Nitrophenyl chloride, o-Nitrochlorobenzene and m-nitrochlorobenzene product further separation the after washing, alkali cleaning, washing, and the gaseous phase materials product is mainly through cooled non-condensable gases and contains NO in the flash vaporization process
xWaste gas.
Prepare in the nitro-chlorobenzene process at chlorobenzene thermal insulation nitration, the main source of nitrous oxides exhaust gas has: (1) is in the chlorobenzene thermal insulation nitration process, in order to improve the security of process, reduce the decomposition of nitric acid, adopt chlorobenzene excessive, nitric acid is as the control material of reaction process, the nitration mixture concentration of using in the also common nitrifying process of nitration mixture concentration is low, but because thermal insulation nitration temperature height, decomposition reaction at high temperature easily takes place and produces NO in nitric acid
x, therefore, have still in the chlorobenzene thermal insulation nitration process that remnants have unreacted nitric acid in the decomposition reaction of nitric acid and the reacting rear material; (2) in the nitration reaction process oxidation side reaction can take place, cause the generation of oxynitride; (3) in the chlorobenzene thermal insulation nitration process, produce nitrosyl-sulfuric acid (NOHSO
4), in the material vacuum flashing process after nitration reaction is finished, nitrosyl-sulfuric acid generation decomposition reaction also can produce oxynitride; (4) nitric acid also takes place to decompose to emit nitrogen oxide in transporting procedures.Adopt in the vacuum flashing process at reacting rear material, oxynitride enters the gaseous phase materials system, will produce the waste gas of oxynitride like this, and main component is H
2O, NO
x, air and a small amount of organism, wherein NO
xVolume fraction be between the 0.04%-0.1%.
Contain NO in the generation of chlorobenzene thermal insulation nitration process
xWaste gas, lacked volatilizable organism in addition, therefore, the emission control technology in the research and development chlorobenzene thermal insulation nitration process seems particularly important.
Obviously, traditional NO
xThe waste gas pollution control and treatment technology all is at containing NO
xGas absorb, and work as NO
xWhen containing organism in the waste gas, can cause the pollution problem of liquid product because of having organic pollutants, be converted into the liquid phase pollution thereby gaseous phase materials is polluted, the liquid phase after the absorption is handled and is just faced new problem.
Summary of the invention
Administer NO in order fundamentally to reach
xThe purpose of waste gas, and can recycle organism and the NO that produces in the gaseous phase materials system
x, realize cleaner production, the present invention is directed in the chlorobenzene thermal insulation nitration process NO
xThe characteristics that contain organism chlorobenzene, nitrated chlorobenzene in the waste gas are with NO
xAbsorption and NO
xThe comprehensive utilization that absorbs the absorption liquid of back generation is merged mutually, simultaneously in conjunction with the characteristics of chlorobenzene thermal insulation nitration technology, adopts Static Gas-liquid mixer to handle NO as absorption unit
xWaste gas.The aqueous nitric acid of process using massfraction 10%-25% of the present invention absorbs, and the acquisition and the waste gas pollution control and treatment combination of system vacuum system are carried out simultaneously.Simultaneously, with the aqueous solution (25% nitric acid, the H of 0.1%-0.5% of rare nitric acid and hydrogen peroxide
2O
2) handle the NO of the nitrated generation of chlorobenzene as absorption agent
x, the organism in the waste gas is also absorbed in the lump, and absorption liquid is used as nitration mixture preparation water and nitric acid material.
The removing process method of the oxynitride that the purpose of this invention is to provide that a kind of sepn process is simple, separation costs is low, produces in the consuming little energy, safe a kind of chlorobenzene thermal insulation nitration process.
The technical scheme that realizes above-mentioned purpose is:
(1) adiabatic nitration: in the thermal insulation nitration device, chlorobenzene is mixed the generation nitration reaction with nitration mixture, the nitration mixture in the reaction process is to be mixed by nitric acid, sulfuric acid and water, and chlorobenzene mixes the generation nitration reaction with nitration mixture, and reacted material enters next step;
(2) vacuum flashing: in vacuum flashing equipment, the material behind the previous step chlorobenzene thermal insulation nitration is carried out vacuum flashing, the material after the vacuum flashing enters next step;
(3) solution-air is separated: in the solution-air separating device, the material that previous step is obtained carries out the solution-air separation, and liquid phase nitro-chlorobenzene crude product and aqueous sulfuric acid remove further separation and purification, and gaseous phase materials enters next step;
(4) cooling condensation: in the cooling condensing equipment, the gaseous phase materials that previous step is obtained carries out indirect heat exchange cooling condensation, and condensed material enters next step;
(5) solution-air is separated: in the solution-air separating device, the material that previous step is obtained carries out the solution-air separation, and liquid phase is that chlorobenzene and water go further to handle and recycle, and gaseous phase materials enters next step;
(6) blended absorbent: in the blended absorbent device, gas, aqueous nitric acid and hydrogen peroxide are mixed, absorb the NO in the waste gas
x, the material after the blended absorbent enters next step;
(7) solution-air is separated: in the solution-air separating device, the material that previous step is obtained carries out solution-air separation, NO in the gaseous phase materials
xAdopt method discharging in a organized way after content is up to standard, liquid phase material is as NO in nitration mixture batching use in the first step chlorobenzene thermal insulation nitration process and the 6th step blended absorbent process
xAbsorption liquid recycle.
Further: the device that uses in the blended absorbent of the 6th step is in hydraulic ejector or squirt pump or the static mixer any one.
Further: the massfraction of nitric acid is 15%-25% in the absorption liquid that uses in the 6th step blended absorbent, and the massfraction of hydrogen peroxide is 0.1%-0.5%, and absorption temperature is 10 ℃-40 ℃.
The NO that produces in a kind of chlorobenzene thermal insulation nitration process of the present invention
xThe principle of work of removing process method be: adopt to contain H
2O
2Aqueous nitric acid absorb waste gas, i.e. water absorption of N O in the salpeter solution
2Gas adds H simultaneously
2O
2Make NO change NO into
2, reaction formula is:
3NO
2+H
2O＝2HNO
3+NO
NO+H
2O
2＝NO
2+H
2O
(1) makes full use of NO and NO
2Solubleness in nitric acid adopts rare nitric acid to containing NO than big this principle in water
xWaste gas absorbs; (2) contain NO from what the vacuum flashing device came out
xThe gaseous phase materials of waste gas contains NO through indirect heat exchange, solution-air after separating
xThe entering static mixer and contain H of waste gas
2O
2The nitric acid absorption liquid in static mixer, absorb operation, absorbed NO
xAfter absorption liquid recycle for nitrification as the batching of the nitrated raw material of chlorobenzene, the waste gas after further separating through solution-air carries out emptying in a organized way; (3) adopt static mixer as NO
xThe absorption unit of waste gas and the deriving means of vacuum system, Static Gas-liquid mixer is as solution-air blended absorbent device, the acquisition of vacuum system and waste gas pollution control and treatment are organically combined, when carrying out the solution-air blended absorbent, obtain to satisfy the vacuum flashing requirement of material after the chlorobenzene nitration reaction.
Realize that the main technique equipment that the present invention needs is: static mixer, absorption unit, solution-air separating device and vacuum flashing equipment etc.
Adopt the advantage of technique scheme to be: (1) is with containing H
2O
2Rare HNO
3The aqueous solution is as NO
xAbsorption liquid, can fully reclaim NO
xOrganic volatile with in the system has made full use of NO
xBe dissolved in rare HNO
3, and H
2O
2More stable in acidic medium, can oxidation NO be NO
2, simultaneously, remaining H
2O
2At high temperature decompose the characteristics of pollution-free generation; (2) use the solution-air static mixer as NO
xAbsorption unit, this absorption unit has not only that the solution-air mixed characteristic is good, absorption technique is simple, absorb characteristics completely, and obtains device as the vacuum of flash system simultaneously, and absorption equipment and pumping equipment are shared, both save facility investment, and reduced process cost; (3) with the certain density HNO of containing that obtains after the solution-air absorption
3With the additional HNO of organic absorption liquid as absorption liquid circulation fluid and nitrifying process
3And H
2The raw material of O has the utilization of materials height, and the outstanding advantage that discharge amount of exhaust gas is few helps industrializing implementation.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment one
Main technique equipment is: static mixer, absorption unit, solution-air separating device and flashing tower etc.
As shown in Figure 1, the method for the removing process of the oxynitride that produces in a kind of chlorobenzene thermal insulation nitration process, described processing step is as follows:
(1) adiabatic nitration: in SV type adiabatic nitration static mixing reactor, the nitration mixture of nitration reaction is that 98% sulfuric acid, 65% nitric acid and spent acid mix by a certain percentage by the massfraction of technical grade, the dehydration value of nitration mixture is 2.0, the mol ratio of chlorobenzene and nitric acid is 1.1: 1.0, chlorobenzene is mixed the generation nitration reaction with nitration mixture, temperature of charge after the nitration reaction is about 160 ℃, and reacted material enters next step;
(2) vacuum flashing: in flash tank, absolute working pressure is 0.08MPa, and the material behind the previous step chlorobenzene thermal insulation nitration is carried out vacuum flashing, and cooling is below 80 ℃ fast to make reacted material, and the material after the vacuum flashing enters next step;
(3) solution-air is separated: in the Sofitel air water separator, the material that previous step is obtained carries out the solution-air separation, and liquid phase nitro-chlorobenzene crude product and aqueous sulfuric acid remove further separation and purification, and gaseous phase materials enters next step;
(4) cooling condensation: in plate-type condenser, the material gaseous phase materials that previous step the is obtained condensation of lowering the temperature, the temperature out of phlegma is about 60 ℃, condensed material enters next step;
(5) solution-air is separated: in the Sofitel air water separator, the material that previous step is obtained carries out the solution-air separation, gaseous phase materials goes further off gas treatment, adopts method discharging in a organized way after amount of nitrogen oxides in the gaseous phase materials is up to standard, and liquid phase is that nitro-chlorobenzene and water enter next step;
(6) blended absorbent: in hydraulic ejector, the massfraction of nitric acid is 15% in the absorption liquid, and the massfraction of hydrogen peroxide is 0.1%, absorption temperature is 10 ℃, gas, aqueous nitric acid and hydrogen peroxide are mixed, absorb nitrogen oxides from exhaust gas, the material after the blended absorbent enters next step;
(7) solution-air is separated: in liquid-gas separator, the material that previous step is obtained carries out the solution-air separation, the volume fraction of oxynitride≤0.024% in the gaseous phase materials, adopt the 60m chimney to discharge in a organized way, liquid phase material uses as nitration mixture batching in the first step chlorobenzene thermal insulation nitration process and the 6th absorption liquid that goes on foot oxynitride in the blended absorbent process recycles.
Embodiment two
Main technique equipment is: static mixer, absorption unit, solution-air separating device and vacuum flashing equipment etc.
As shown in Figure 1, the method for the removing process of the oxynitride that produces in a kind of chlorobenzene thermal insulation nitration process, described processing step is as follows:
(1) adiabatic nitration: in SV type adiabatic nitration static mixing reactor, the nitration mixture of nitration reaction is that 98% sulfuric acid, 65% nitric acid and spent acid mix by a certain percentage by the massfraction of technical grade, the dehydration value of nitration mixture is 3.0, the mol ratio of chlorobenzene and nitric acid is 1.1: 1.0, chlorobenzene is mixed the generation nitration reaction with nitration mixture, temperature of charge after the nitration reaction is about 140 ℃, and reacted material enters next step;
(2) vacuum flashing: in flash cooler, be 0.04MPa at absolute working pressure, the material behind the previous step chlorobenzene thermal insulation nitration is carried out vacuum flashing, make reacted material cool off about 70 ℃ fast, the material after the vacuum flashing enters next step;
(3) solution-air is separated: in liquid-gas separator, the material that previous step is obtained carries out the solution-air separation, and liquid phase nitro-chlorobenzene crude product and aqueous sulfuric acid remove further separation and purification, and gaseous phase materials enters next step;
(4) cooling condensation: in shell-and tube condenser, the material gaseous phase materials that previous step the is obtained condensation of lowering the temperature, the temperature out of phlegma is about 40 ℃, the condensed material of cooling condensing equipment enters next step;
(5) solution-air is separated: in liquid-gas separator, the material that previous step is obtained carries out the solution-air separation, gaseous phase materials goes further off gas treatment, adopts method discharging in a organized way after amount of nitrogen oxides in the gaseous phase materials is up to standard, and liquid phase is that nitro-chlorobenzene and water enter next step;
(6) blended absorbent: in water jet pump, the massfraction of nitric acid is 20% in the absorption liquid, and the massfraction of hydrogen peroxide is 0.3%, absorption temperature is 20 ℃, gas, aqueous nitric acid and hydrogen peroxide are mixed, absorb nitrogen oxides from exhaust gas, the material after the blended absorbent enters next step;
(7) solution-air is separated: in the air-water separator, the material that previous step is obtained carries out the solution-air separation, the volume fraction of oxynitride≤0.024% in the gaseous phase materials, adopt the 60m chimney to discharge in a organized way, liquid phase material uses as nitration mixture batching in the first step chlorobenzene thermal insulation nitration process and the 6th absorption liquid that goes on foot oxynitride in the blended absorbent process recycles.
Embodiment three
Main technique equipment is: static mixer, absorption unit, solution-air separating device and vacuum flashing equipment etc.
As shown in Figure 1, the method for the removing process of the oxynitride that produces in a kind of chlorobenzene thermal insulation nitration process, described processing step is as follows:
(1) adiabatic nitration: in SV type adiabatic nitration static mixing reactor, the nitration mixture of nitration reaction is that 98% sulfuric acid, 65% nitric acid and water mix by a certain percentage by the massfraction of technical grade, the dehydration value of nitration mixture is 4.0, the mol ratio of chlorobenzene and nitric acid is 1.05: 1.0, chlorobenzene is mixed the generation nitration reaction with nitration mixture, temperature of charge after the nitration reaction is about 120 ℃, and reacted material enters next step;
(2) vacuum flashing: the absolute working pressure in flash tank is 0.02MPa, and the material behind the previous step chlorobenzene thermal insulation nitration is carried out vacuum flashing, makes reacted material cool off about 60 ℃ fast, and the material after the vacuum flashing enters next step;
(3) solution-air is separated: in air water separator, the material that previous step is obtained carries out the solution-air separation, and liquid phase nitro-chlorobenzene crude product and aqueous sulfuric acid remove further separation and purification, and gaseous phase materials enters next step;
(4) cooling condensation: in threaded pipe type condenser, the material gaseous phase materials that previous step the is obtained condensation of lowering the temperature, the temperature out of phlegma is about 20 ℃, condensed material enters next step;
(5) solution-air is separated: in the air-water separator, the material that previous step is obtained carries out the solution-air separation, gaseous phase materials goes further off gas treatment, adopts method discharging in a organized way after amount of nitrogen oxides in the gaseous phase materials is up to standard, and liquid phase is that nitro-chlorobenzene and water enter next step;
(6) blended absorbent: in static mixer, the massfraction of nitric acid is 25% in the absorption liquid that uses, the massfraction of hydrogen peroxide is 0.5%, absorption temperature is 40 ℃, gas, aqueous nitric acid and hydrogen peroxide are mixed, absorb nitrogen oxides from exhaust gas, the material after the blended absorbent enters next step;
(7) solution-air is separated: in the Sofitel air water separator, the material that previous step is obtained carries out the solution-air separation, the volume fraction of oxynitride≤0.024% in the gaseous phase materials, adopt the 60m chimney to discharge in a organized way, liquid phase material uses as nitration mixture batching in the first step chlorobenzene thermal insulation nitration process and the 6th absorption liquid that goes on foot oxynitride in the blended absorbent process recycles.
The innovation part of technology of the present invention is embodied in: made full use of NO
xBe dissolved in rare HNO
3And H
2O
2Stable and can oxidation NO be NO in acidic medium
2Characteristics, utilized remaining H simultaneously
2O
2At high temperature decompose, the characteristics of pollution-free generation, and the singularity of chlorobenzene thermal insulation nitration process and the mixed characteristic of solution-air static mixer organically combined the certain density HNO of containing that obtains after solution-air is absorbed
3With the additional HNO of organic circulation fluid as nitrifying process
3And H
2The raw material of O has the utilization of materials height, the outstanding advantage that three wastes discharge amount is few.
Remove the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.
Claims (3)
1, the removing process of the oxynitride that produces in a kind of chlorobenzene thermal insulation nitration process is characterized in that described method steps is as follows:
(1) adiabatic nitration: in the thermal insulation nitration device, chlorobenzene is mixed the generation nitration reaction with nitration mixture, the nitration mixture in the reaction process is to be mixed by nitric acid, sulfuric acid and water, and chlorobenzene mixes the generation nitration reaction with nitration mixture, and reacted material enters next step;
(2) vacuum flashing: in vacuum flashing equipment, the material behind the previous step chlorobenzene thermal insulation nitration is carried out vacuum flashing, the material after the vacuum flashing enters next step;
(3) solution-air is separated: in the solution-air separating device, the material that previous step is obtained carries out the solution-air separation, and liquid phase nitro-chlorobenzene crude product and aqueous sulfuric acid remove further separation and purification, and gaseous phase materials enters next step;
(4) cooling condensation: in the cooling condensing equipment, the gaseous phase materials that previous step is obtained carries out indirect heat exchange cooling condensation, and condensed material enters next step;
(5) solution-air is separated: in the solution-air separating device, the material that previous step is obtained carries out the solution-air separation, and liquid phase is that chlorobenzene and water go further to handle and recycle, and gaseous phase materials enters next step;
(6) blended absorbent: in the blended absorbent device, gas, aqueous nitric acid and hydrogen peroxide are mixed, absorb nitrogen oxides from exhaust gas, the material after the blended absorbent enters next step;
(7) solution-air is separated: in the solution-air separating device, the material that previous step is obtained carries out the solution-air separation, amount of nitrogen oxides adopts method discharging in a organized way after up to standard in the gaseous phase materials, and liquid phase material uses as nitration mixture batching in the first step chlorobenzene thermal insulation nitration process and the 6th absorption liquid that goes on foot oxynitride in the blended absorbent process recycles.
2, the removing process of the oxynitride that produces in a kind of chlorobenzene thermal insulation nitration process according to claim 1 is characterized in that: the device that uses in the blended absorbent of the 6th step is in hydraulic ejector or squirt pump or the static mixer any one.
3, the removing process of the oxynitride that produces in a kind of chlorobenzene thermal insulation nitration process according to claim 1, it is characterized in that: the massfraction of nitric acid is 15%-25% in the absorption liquid that uses in the 6th step blended absorbent, the massfraction of hydrogen peroxide is 0.1%-0.5%, and the temperature that absorbs operation is 10 ℃-40 ℃.
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|---|---|---|---|
| CN200910182288A CN101607910B (en) | 2009-07-07 | 2009-07-07 | Removal technology of nitrogen oxides generated in chlorobenzene thermal insulation nitration |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407068A (en) * | 2010-09-25 | 2012-04-11 | 潍坊信誉环境工程有限公司 | Acidic water solution for absorbing NOx and method for purifying NOx-containing waste gas by applying same |
| CN103495337A (en) * | 2013-10-16 | 2014-01-08 | 重庆紫光国际化工有限责任公司 | Device and method for removing residual ammonia in HCN synthesis gas |
| CN106032522A (en) * | 2015-03-16 | 2016-10-19 | 中国石油化工股份有限公司 | Combined method for culturing microalgae and denitration of industrial exhaust gas |
| CN106032521A (en) * | 2015-03-16 | 2016-10-19 | 中国石油化工股份有限公司 | Method for culturing microalgae and combined method for denitration of industrial exhaust gas |
| CN106031843A (en) * | 2015-03-16 | 2016-10-19 | 中国石油化工股份有限公司 | Wet denitration method for industrial waste gas |
| CN114539063A (en) * | 2022-02-11 | 2022-05-27 | 安徽东至广信农化有限公司 | Method for producing nitrochlorobenzene by vacuum concentration method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4453027A (en) * | 1982-12-10 | 1984-06-05 | Monsanto Company | Adiabatic process for the nitration of halobenzenes |
| DE4411064A1 (en) * | 1994-03-30 | 1995-10-05 | Bayer Ag | Process for the adiabatic production of mononitrohalobenzenes |
| CN1056829C (en) * | 1995-10-20 | 2000-09-27 | 清华大学 | Preparing nitro-chlorobenzene by catalytic nitration |
| DE10108979C1 (en) * | 2001-02-23 | 2002-05-08 | Bayer Ag | Continuous production of nitrochlorobenzene, used as intermediates for dye, pharmaceutical and pesticide production, uses specified adiabatic conditions and acid composition in nitration of chlorobenzene |
-
2009
- 2009-07-07 CN CN200910182288A patent/CN101607910B/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN102407068A (en) * | 2010-09-25 | 2012-04-11 | 潍坊信誉环境工程有限公司 | Acidic water solution for absorbing NOx and method for purifying NOx-containing waste gas by applying same |
| CN103495337A (en) * | 2013-10-16 | 2014-01-08 | 重庆紫光国际化工有限责任公司 | Device and method for removing residual ammonia in HCN synthesis gas |
| CN106032522A (en) * | 2015-03-16 | 2016-10-19 | 中国石油化工股份有限公司 | Combined method for culturing microalgae and denitration of industrial exhaust gas |
| CN106032521A (en) * | 2015-03-16 | 2016-10-19 | 中国石油化工股份有限公司 | Method for culturing microalgae and combined method for denitration of industrial exhaust gas |
| CN106031843A (en) * | 2015-03-16 | 2016-10-19 | 中国石油化工股份有限公司 | Wet denitration method for industrial waste gas |
| CN106032522B (en) * | 2015-03-16 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of combined method of cultivating microalgae and industrial waste gas denitration |
| CN106032521B (en) * | 2015-03-16 | 2019-03-08 | 中国石油化工股份有限公司 | The method of cultivating microalgae and its with the united method of industrial waste gas denitration |
| CN106031843B (en) * | 2015-03-16 | 2019-11-15 | 中国石油化工股份有限公司 | The wet denitration method of industrial waste gas |
| CN114539063A (en) * | 2022-02-11 | 2022-05-27 | 安徽东至广信农化有限公司 | Method for producing nitrochlorobenzene by vacuum concentration method |
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| CN101607910B (en) | 2012-10-17 |
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