CN1064253A - The commercial run of separation and recovery of chlorine - Google Patents
The commercial run of separation and recovery of chlorine Download PDFInfo
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- CN1064253A CN1064253A CN92101858A CN92101858A CN1064253A CN 1064253 A CN1064253 A CN 1064253A CN 92101858 A CN92101858 A CN 92101858A CN 92101858 A CN92101858 A CN 92101858A CN 1064253 A CN1064253 A CN 1064253A
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Abstract
Compress the gas mixture of chloride, carbonic acid gas and non-condensable gases, cooling is to be separated into it based on the residual gas of non-condensable gas with based on the phlegma of chlorine.Phlegma is sent into the stripping tower desorb be dissolved in wherein carbonic acid gas and a small amount of non-condensable gas, handle simultaneously further stripping gas, be about to stripping gas and mix, send into the absorption tower to a part of gas mixture of major general with residual gas based on chlorine and carbonic acid gas, absorb most remaining chlorine, reduce cl content.With the aqueous solution or the suspension washing of alkali metal containing sulphite and/or alkaline-earth metal sulfite, the pH value of controlling this aqueous solution or suspension simultaneously can remove the chlorine in the waste gas in this gas mixture or the aforesaid method between 1.9-6.3.
Description
The invention relates to the method for separation and recovery of chlorine from the gas mixture of chloride, carbonic acid gas and non-condensable gases.The present invention also is about remove the method for chlorine from this gas mixture.
Particularly, the invention relates to the method for from the gas mixture of chloride, carbonic acid gas and high density non-condensable gases separation and recovery of chlorine.The present invention also is about from chloride, carbonic acid gas with reclaim the method for chlorine at least the gas mixture of 50V% non-condensable gases.In addition, the present invention also relates to absorb and remove the method for the chlorine in the carbon dioxide gas that generates in chlorine production or the use.
Propose many methods that from chloride gas mixture, reclaim chlorine, comprised following patent literature.
(1) US3972691 discloses a kind of method that reclaims liquid chlorine from gas mixture, and this gas mixture comprises the chlorine of 20-90V%, the carbonic acid gas of 10-80V%, oxygen, nitrogen and carbon monoxide.This method is included under the 4-8atm, with gas mixture compression, cooling and in total reflux type rectifying tower with its liquefaction, then, regulate the temperature that is collected in rectifying tower still liquid chlorine, make the carbonic acid gas evaporation that is dissolved in the liquid chlorine.
(2) US2199797 discloses and has a kind ofly removed the method that concentration in the chlorine is 1wt% or lower organic impurity with liquid chlorine, this method be make chlorine in washing tower with the liquid chlorine counter current contact.
(3) U.K.938073 discloses a kind of method of separating incoagulability impurity from impure chlorine.The boiling point of this impurity is lower than the boiling point of chlorine, and with a kind of explosive mixture of its formation.This method is included in that substep reduces chlorine temperature in the liquefaction tower of liquefied chlorine gas, and makes that last residual gas and liquid chlorine are reverse to be contacted.The liquid chlorine temperature has been reduced to the condensing temperature of chlorine or lower, thus chlorine and lower-boiling impurity is separated.
(4) US3443902 discloses a kind of method, with the chlorine compression, impure chlorine is contacted with liquid chlorine is reverse in washing tower, impurity is fallen by the liquid chlorine absorbing and removing, a part of chlorine and liquid chlorine are liquefied because of heat exchange in tower, and the chlorine that will be liquefied like this is used for the purposes of above-mentioned liquid chlorine again.
(5) UK1164069 discloses a kind of method, will be by non-condensable gases, comprise that the mixed pressure that nitrogen and chlorine are formed is reduced to 6-10 normal atmosphere, cool off compressed gas in two steps, the gas mixture that will be cooled again further is cooled to-120 °F～-150 °F with heat exchange method, thereby liquid chlorine and non-condensable gases are separated.
(6) US2540905 discloses the not method of carbonated chlorine of a kind of recovery, this method comprises with the chlorating solvent and absorbs chlorine from liquefaction the residual gas, this residual gas obtains after by seawater electrolysis, include the chlorine of 5-10wt%, also have carbonic acid gas, carbon monoxide, hydrogen, nitrogen, oxygen and other gas composition simultaneously, again by the heating absorption tower by following part, the carbonic acid gas that absorbed is simultaneously evaporated being higher than under the temperature of absorption temperature.
(7) US2765873 discloses the method that a kind of recovery is substantially free of the chlorine of non-condensable gases.This method comprises: at pressure is 2.0-14.3atm, tower top temperature-22.8 ℃～32.2 ℃, and tower still temperature is higher than under the tower top temperature 27.8-52.8 ℃ condition, contains 30-50wt% chlorine and Air mixing gas with solvent absorbing.
(8) DE2413358 discloses a kind of method that absorbs chlorine from chlorine and carbon dioxide mix gas, utilize multi-stage countercurrent absorption unit and alkali metal hydroxide and/or alkaline earth metal hydroxides, when operating this device control eventually a level liquid phase PH valve be 7.5, with chlorine with basic metal and/or the independent absorption extraction of alkaline-earth metal chlorite form.
Patent documentation (1), (2), (3), (4), in method all be to be used in chlorine or chlorine and carbonic acid gas as under the quite high situation of one or more condensable gas and its concentration.If from containing chlorine and wherein reclaiming chlorine the about 50V% of non-condensable gases content or the higher gas mixture, owing to there are a large amount of non-condensable gasess, there are a lot of shortcomings in these methods.
These methods all are to make descending liquid chlorine and up raw material chlorine counter current contact in tower, though its purpose all is in order to liquefy, to wash and distill, also having any different to each other.When contained incoagulability component concentration was higher in the up raw material chlorine, the problem that avoid the gas liquid contacting efficiency of carrying phenomenon secretly and causing owing to the channel or the similar reason of descending liquid of promoting the circulation of qi to reduce was impossible.The problems referred to above make these methods be difficult to reach its predetermined separating effect.
If increase the amount of descending liquid for keeping efficient, distillation tower cooling load and heating load also will increase.In addition, must adopt main equipment such as tower body, condenser and reboiler, also bring problem economically.In method (4), it is very big that the circulating load of non-condensable gases becomes, and reduced the dew point of compressed gas, if the pressure of compression is very low, the potential problem is that chlorine can not be liquefied when washing tower carries out heat exchange.Even chlorine can be liquefied, owing to the compression ratio of compressor and circulating load increase power charge is increased, also cause this method to lose its favourable one side.
In addition, method (1) and (5) are basically at high density chlorine.With pending chloride gas mixture compression, cooling makes chlorine gas liquefaction and with its separation.But the purpose of these methods is to reclaim high-purity chlorine, thus the concentration of chlorine in the waste gas isolated from chlorine, that mainly form by non-condensable gases, in method (1) up to 5-9V%, in method (5) even up to 10V%.
Industrial recovery chlorine, the waste gas of high density chlorine causes topsoil owing to discharging contains so, as being discharged waste gas, wherein must be not chloride.But, let alone equipment, and caused the loss of chlorine for the chlorine that removes wherein needs a large amount of at least a pharmaceutical chemicalss.Therefore these methods do not have economy.Cl content in the waste gas will be reduced to insignificant lower concentration, must further improve compression pressure, further reduce cooling and liquefaction temperature simultaneously, this causes power charge and refrigeration expense to increase again.And the slave unit security standpoint is considered, does not also wish chloride mixed pressure is reduced to very high pressure.In addition, do not allow to cool off and liquefaction temperature is reduced to the freezing point temperature (during 5.2atm for-56.6 ℃) of carbonic acid gas or lower.With the dry ice occluding device of avoiding separating out.Therefore this liquifying method can not avoid containing in the waste gas certain density chlorine.
Solvent has all been used in method (6) and (7), and impurity is absorbed, and then desorb is to reclaim chlorine.Wherein method (6) comprises heating absorption tower still, makes by a part of chlorine of solvent absorbing and the evaporation of most carbonic acid gas, makes the chlorine that obtains higher degree in the evaporator tower.Therefore, it is inevitable containing chlorine in the waste gas that the absorption cat head is discharged.Especially, under the gas concentration lwevel condition with higher, the heating of corresponding reinforcement to the absorption tower still.Consequently, cl concn increases in the waste gas, and chlorine is lost, and solvent load heightens.
Method (7) requires quite to evaporate under the high pressure in evaporator tower, because will will reclaim after the chlorine liquefaction of desorb from solvent in tower.Systemic air will reduce the purity that reclaims chlorine above requiring if solvent is on the absorption tower, therefore will reduce the consumption of lyosorption.Because this requirement, under carbonic acid gas and non-condensable gases concentration condition with higher, can not fully absorb chlorine, cause that cl concn and quantity of solvent heighten in the waste gas.
Reduce cl content in the waste gas with solvent absorption, selection scheme comprises the increase solvent load, reduces solvent temperature or advances to improve absorption tower pressure.But no matter how, all will promote the absorption of carbonic acid gas and non-condensable gases, therefore be difficult to be recovered to high-purity chlorine.
Chlorine is a kind of useful starting material that are widely used.Industrial scale operation chlorine mainly is by seawater electrolysis, is attended by other gas by products in the production process and generates.These gas compositions and chlorine mix, because the toxicity of chlorine without further processing, can't be discharged in the atmosphere.
Therefore, absorb chlorine to remove the chlorine in this gas with alkaline matter usually.If but outside the dechlorination when also containing other gases such as another kind of sour gas (as carbonic acid gas), chlorine not only arranged by what basic solution absorbed, would also have carbonic acid gas.Like this, the expense of alkali should equal the total amount of carbonic acid gas and chlorine.When if the higher and cl content of carbon dioxide content is trace in the gas, the chlorine that remove traces with a large amount of alkali be very inconvenient.Therefore need provide a kind of method of selecting chlorine in the absorbing and removing carbonic acid gas.
The method that has proposed (8) is the method that removes chlorine from the gas mixture of carbonic acid gas and chlorine.But in this method, pH7.5 is higher than 6.35 these numerical value far away.As shown in Figure 4, the 6.35th, first dissociation constant (pka) of carbonic acid also is to drop on carbonic acid gas and alkali metal hydroxide and/or alkaline earth metal hydroxides reaction to form in the scope of corresponding supercarbonate.
In order in above-mentioned scope, from the gas mixture of carbonic acid gas and chlorine, only to absorb chlorine, need use alkali with the complete equimolar amount of chlorine.But under the situation that cl concn changes, be difficult to make the consumption of alkali and the content of chlorine to reach balance.
In addition, pH7.5 approaches hypochlorous dissociation constant.When pH was lower than above-mentioned value, hypochlorous acid existed with free acid form, so be easy to dissociate.Therefore, need accurately control pH value.Even but removed chlorine effectively.The hypochlorite solutions that is generated can not discharge because of very strong oxidisability and odour nuisance are arranged at this point, also need increase step reduction treatment step.
An object of the present invention is to provide a kind of from the gas mixture of chloride, carbonic acid gas and non-condensable gases the method for separation and recovery of chlorine, particularly from gas mixture, all reclaim chlorine basically and handle residual chlorine in the residual gas, make residual gas can enter atmospheric method.
First aspect of the present invention provide a kind of from the gas mixture of chloride, carbonic acid gas and non-condensable gases the method for separation and recovery of chlorine.This method comprises compression and cools off this gas mixture, and it is separated into based on the residual gas of non-condensable gases with based on the phlegma of chlorine, this phlegma sent into the stripping tower desorb be dissolved in wherein carbonic acid gas and noncondensable gas on a small quantity.
Second aspect of the present invention provided a kind of in separation and recovery system from the gas mixture of chloride, carbonic acid gas and non-condensable gases the method for separation and recovery of chlorine.This method comprises ⅰ) compress this gas mixture, with its cooling liquid, thus it is separated into based on the residual gas of non-condensable gas with based on the phlegma of chlorine, ⅱ) only phlegma is sent into stripping tower, carbonic acid gas and a small amount of non-condensable gas wherein dissolved in desorb, separation and recovery of chlorine thus, ⅲ) make from the stripping cat head and discharge, the gas of main chloride and carbonic acid gas with from ⅰ) residual gas that goes on foot mixes, ⅳ) send into the absorption tower of making solvent with halohydrocarbon to this gas mixture of a major general part, absorb most of residual chlorine at this, to reduce cl content, preferably cl content is reduced to 1V% or lower, the waste gas formed by carbonic acid gas and non-condensable gas of separate discharge simultaneously, ⅴ) solvent that will absorb chlorine is sent into the chlorine in the distillation tower separation halohydrocarbon.
Third aspect of the present invention has provided a kind of from the gas mixture that contains chlorine and carbonic acid gas, as the method ⅳ that provides from second aspect present invention) remove the method for chlorine the step in the exhaust gas discharged.This method comprises the aqueous solution or the suspension of sending into alkali metal containing sulphite and/or alkaline-earth metal sulfite, and when washing this gas mixture with it, controlling this solution or pH of suspension value is 1.9-6.3, can remove chlorine in the gas mixture fully thus.
In a first aspect of the present invention, with the gas mixture cooling liquid of chloride, carbonic acid gas and non-condensable gas, isolate non-condensable gas earlier, separately phlegma is sent into stripping tower again, chlorine is reclaimed in distillation.This method can reduce the load of stripping tower, thereby might reduce stripping tower diameter (comparing with used stripping tower among the US2765873) greatly, has therefore reduced the cost of stripping tower.This method of first aspect present invention has important industrial value.
In a second aspect of the present invention, will combine with the method for first aspect with the step that halogenated hydrocarbon solvent reclaims chlorine, can be basically all reclaim chlorine in the processed gas with high-purity chlorine form.Therefore, the method for this separation and recovery of chlorine of second aspect is seen very useful from industrial point of view.
The 3rd aspect of the present invention can only remove chlorine from the gas of carbonated and chlorine.When the method that adopts second aspect, when having waste gas to discharge, can handle this by the method for the third aspect be the waste gas that 1wt% or lower chlorine are formed by carbonic acid gas, non-condensable gas and content, this trace amounts of chlorine can not remove with the second aspect method, and available this third aspect method almost completely removes.Therefore this method can make factory not have pollution problem substantially.
As mentioned above, in the suitability for industrialized production of chlorine, the present invention is very with practical value.
Fig. 1 illustrates the equipment flowsheet that is used for implementing the method for separation and recovery of chlorine from the gas mixture of chloride, carbonic acid gas and non-condensable gas by way of example.This method is: (1) compression and cooling mixing gas, and (2) become this mixed gas separation based on the residual gas of non-condensable gas with based on the phlegma of chlorine, and (3) are only sent into phlegma stripping tower and are dissolved in wherein carbonic acid gas and non-condensable gas on a small quantity with desorb.
Fig. 2 illustrates the equipment flowsheet of comparative example, and this method is the ordinary method suitable with Fig. 1 method.
Fig. 3 illustrates the shop equipment flow process that adopts industrial separation and recovery of chlorine method by way of example.This method comprises ⅰ) compression contains 10-60V% chlorine, the gas mixture of carbonic acid gas and non-condensable gas, cool off then and liquefy it, ⅱ) it is separated into based on the residual gas of non-condensable gas with based on the phlegma of chlorine, ⅲ) only phlegma is sent into stripping tower, desorb is dissolved in carbonic acid gas and a small amount of non-condensable gas wherein, separation and recovery of chlorine thus, ⅳ) will discharge from the stripping cat head, main discharging gas and the step ⅰ that forms by chlorine and carbonic acid gas), in residual gas mix, ⅴ) send into the absorption tower to this gas mixture of a major general part, absorb most of residual chlorine with halohydrocarbon, ⅵ) separate by carbonic acid gas, non-condensable gas, the waste gas of forming less than 1V% chlorine, with its discharge system, ⅶ) solvent that will absorb chlorine is sent into distillation tower, be separated into main chloride recovery gas and halohydrocarbon, ⅷ) this solvent cycle is got back to the absorption tower,, ⅸ) should reclaim gas and loop back compression step as absorption agent.
Fig. 4 illustrates and helps to implement absorption agent of the present invention, in its aqueous solution, and the ionic species of different pH values.
Fig. 5 illustrates the schema that absorbs chlorine in the example 8.
Fig. 6 illustrates the shop equipment flow process that the present invention's one, two, three, three aspect methods are implemented in combination.
Each aspect in the 1-3 of the present invention aspect, this method are applicable to by carbonic acid gas and non-condensable gas to be formed and chloride gas mixture, or chloride carbon dioxide gas.
As an example, following suitable gas can be proposed
A) produce gas mixture in the chlorine process by oxidation chlorination hydrogen, wherein chloride, carbonic acid gas and non-condensable gases;
B) remove the gas mixture that obtains behind most of chlorine in the gas mixture (a), wherein contain residual chlorine, carbonic acid gas and non-condensable gases;
C) gas mixture of chloride and carbonic acid gas.
In organic compound chlorination or phosgenation reaction, generate a large amount of paying and produce hydrogenchloride, because its growing amount is considerably beyond the demand that is used to produce hydrochloric acid, so a large amount of hydrogenchloride is not utilized, just handled, and this processing needs a large amount of expenses as waste gas.
Therefore, a kind of method wish to be proposed always, can be effectively from being reclaimed chlorine a large amount of depleted hydrogenchloride as mentioned above, and can be used for the suitability for industrialized production of chlorine.
People have known and can produce chlorine by oxidation chlorination hydrogen for many years, but the suitability for industrialized production that also is unrealized.
Recent findings, the chromium oxide catalyst that obtains of roasting chromium hydroxide under certain condition is even under suitable low temperature, also have very high reactivity.This just provides prerequisite for the industrialization that oxidation chlorination hydrogen is produced the method for chlorine.
The gas mixture of handled chloride, carbonic acid gas of the arbitrary method in the 1-3 of the present invention aspect and non-condensable gas can be the gas mixture of discharging as in the chlorine production method of developing recently.That is, the present invention is as a kind of method that reclaims chlorine effectively, or removes the method for chlorine as from above-mentioned industrial production chlorine the time the exhaust gas discharged, all is very useful.
Describe some included more concrete schemes of the present invention below in detail.
Fig. 1 illustrates compressor 101, separation column or packing tower that stripping tower 102, this tower are conventional, heat exchanger 103, separator 104 and reboiler 105.
Make the gas mixture that generally contains 10-60V% chlorine, 40-90V% carbonic acid gas and non-condensable gas through managing 106 inputs, be compressed to predetermined pressure by compressor 101.
As non-condensable gases, can exemplify out nitrogen, oxygen or carbon monoxide.
By heat exchanger 103 compressed gas mixture is cooled to give fixed temperature, and makes the liquefaction of a part of chlorine, the liquid vapour mixture that obtains sent into separator 104, it is separated into based on the residual gas of non-condensable gas with based on the phlegma of chlorine through managing 112.
Through managing 107 phlegma sent into stripping tower top, in its dirty process, contact with chlorine vapor by reboiler 105 heating evaporations, make the carbonic acid gas and the non-condensable gas evaporation that are dissolved in the phlegma, thereby collect high-purity liquid chlorine phlegma at the stripping tower still, and discharge through managing 111 as product chlorine.
As with the gas mixture compression of chloride, carbonic acid gas and non-condensable gas, send into stripping tower liquefaction and distillation then, stripping tower will have big straight warp, to satisfy the requirement of adopting conventional superfacial velocity.But like the present invention like this, isolates non-condensable gas earlier, only phlegma sent into stripping tower, just might carry out stripping in than little about 30% the tower of above-mentioned tower diameter at diameter.
Carbonic acid gas that stripping goes out from phlegma and non-condensable gas through managing 109 from the discharge of stripping cat head, converge through managing 108 residual gases of discharging again with from separator, discharge from system as waste gas.
For from gas mixture, reclaiming chlorine as much as possible, improve the compression pressure of compressor as far as possible, reduce the cooling temperature of heat exchanger simultaneously as far as possible.But consider from security standpoint, do not recommend arbitrarily to increase the compression pressure of chlorine-containing gas.In addition, also have a restriction, promptly the liquefaction process of cooling of carbonated gas mixture should be higher than carbonic acid gas fusing point (CO
2During dividing potential drop 5.2atm for-56.6 ℃) carry out under the temperature.Blocked for preventing equipment because of producing dry ice, also to be limited cooling temperature.Should suitably determine the cooling and the liquefaction temperature of compressor compresses pressure and heat exchanger according to factor economically.These economic factorss such as compressor required drive, the heat exchanger cooling load, reboiler thermal load and waste gas disposal costs etc. will be considered simultaneously.
Usually, preferably the compression pressure of gas mixture is decided to be 3-15kg/cm
2-G, cooling and liquefaction temperature are-10 ℃～-50 ℃, stripping tower is at 3-15Kg/cm
2Operate between-G the pressure, 20-45 ℃ of still temperature.
The purity of the chlorine that this operation obtains is 99V% or higher.
Fig. 3 illustrates compressor 301, water cooler 302, condenser 303, gas/liquid separation 304, stripping tower 305, reboiler 306, absorption tower 307, heat exchanger 308, reducing valve 309, distillation tower 310, condenser 311, gas/liquid separation 312, reboiler 313, water cooler 314, and pump 315 and 316.Optionally, general separately packing tower or the separation column of tower 305,307 and 310.
The gas mixture 317 of chloride, carbonic acid gas and non-condensable gas is compressed to give level pressure power by compressor 301 with it with after the recovery gas 326 from gas/liquid separation 312 mixes.
Can handle the gas mixture that contains 10-60V% chlorine in this way.Owing in the presence of special chromium oxide catalyst, produce the gas mixture that also can obtain this cl content the chlorine process from chloration hydro-oxidation, so available this method is handled this gas mixture.
As the non-condensable gas in the gas mixture, can exemplify out nitrogen, oxygen carbon monoxide and/or similar gas.
Compression pressure can be 3-15kg/cm
2-G, preferably 5-12kg/cm
2-G.With water cooler 302 cooling mixing gas.With after condenser 303 liquefaction, have at least 2/3rds to be liquefied in the chlorine that from gas mixture, obtains at this.
Cooling and liquefaction temperature are-10 ℃～-50 ℃, best-20 ℃～-40 ℃.
After by separator 304 gas-liquid mixture that obtains being separated into residual gas 319 and the phlegma 318 based on chlorine based on non-condensable gas, this phlegma is sent into stripping tower.
Stripping tower 305 can be at 3-15kg/cm
2-G, preferably 5-12kg/cm
2-G pressure is operation down.
The phlegma of sending into the top flows down along tower, and is main by the rising steam of being formed by the chlorine of reboiler 306 ebuillition of heated of 20-45 ℃ of still temperature therebetween, and the carbonic acid gas and the non-condensable gas that are dissolved in this phlegma are evaporated.Therefore, the tower still is collected the phlegma of liquid chlorine form, as product chlorine 321.Carbonic acid gas that steams from phlegma and non-condensable gas are discharged as the stripping gas 320 from the stripping cat head with chlorine, and mix with residual gas 319.This gas mixture of at least a portion is sent into absorption tower 307.The absorption tower be preferably in the stripping tower uniform pressure under move because under the temperature-resistant condition of absorption agent, sorption improves with absorption tower pressure and strengthens.
Send into that almost all chlorine and partial CO 2 and non-condensable gas are all absorbed from the dirty solvent 330 of cat head in the gas 323 on absorption tower 307.Therefore, when gas 323 is used as waste gas 324 when discharging from system, this waste gas is made up of carbonic acid gas and non-condensable gas, and contains the chlorine less than 1V%.The aforesaid method solvent for use is a kind of halohydrocarbon, as tetracol phenixin or chloroform.Solvent load be send into absorption tower gas 2-100 doubly, best 3-30 doubly (by weight).
The solvent 325 that has absorbed chlorine, carbonic acid gas and non-condensable gas is discharged at the bottom of still, sends into heat exchanger 308 by pump 315.After its preheating, send into distillation tower 310 again.
The solvent of sending into distillation tower 310 is by the reboiler ebuillition of heated, through condenser condenses, 327 distills back tower through refluxing, and makes absorbed gas evaporation, and isolates the recovery gas based on chlorine.
Be not higher than 5000PPM by cl content in the solvent 328 of tower still discharge, preferably be not higher than 500PPM(wt), this solvent is sent into heat exchanger 308.By heat exchanger 308 make heat from solvent, emit after, add fresh solvent 329 again, supply the part of being lost.Afterwards, with this solvent cooling, send absorption tower 307 by water cooler 314 again back to.Though because of the absorption tower temperature in is lower the receptivity on absorption tower is uprised, can not make temperature be lower than the melting temperature (being-22.6 ℃) of solvent as tetracol phenixin.Hope is reduced to the distillation column condenser temperature temperature that does not make the solvent evaporation diffusion.Cause that chlorine liquefies but temperature is low excessively, cause cl content increase in the solvent, the receptivity of circulating solvent in the absorption tower is descended, so do not select this low excessively temperature for use.
Therefore must on the basis of considering foregoing, suitably determine the top condition of ingress, absorption tower solvent temperature and distillation column condenser temperature.Ingress, absorption tower solvent temperature is preferably-20 ℃～0 ℃, and the distillation column condenser temperature is-20 ℃～-10 ℃.
Introduce the method that from the gas mixture of chloride and carbonic acid gas, removes chlorine below.This method comprises: the aqueous solution or the suspension of sending into alkali metal containing sulphite and/or alkaline-earth metal sulfite, or send into the aqueous solution or the suspension of alkali metal containing sulphite and/or alkaline-earth metal sulfite and alkali metal hydroxide and/or alkaline earth metal hydroxides, wherein the oxyhydroxide add-on is not higher than the twice (mol ratio) of alkali metal sulfite and/or alkaline-earth metal sulfite consumption, during with this aqueous solution or suspension washing gas mixture, its pH value is controlled at 1.9-6.3, removes chlorine in the gas mixture with this.
The example that can be used to implement the alkali metal hydroxide of aforesaid method comprises the oxyhydroxide as alkali metal lithium, sodium, potassium, but the oxyhydroxide of alkaline earth metal hydroxides magnesium, calcium, barium etc.
On the other hand, the metal in the sulphite can be alkaline-earth metal such as magnesium, calcium or barium.But use the high basic metal of solubleness in water on a selective basis.
When alkali metal sulfite and/or alkaline-earth metal sulfite with alkali metal hydroxide and/or alkaline earth metal hydroxides time spent, basic a bit is the twice that hydroxide quantity is no more than the sulphite amount in the proportioning (mol ratio).
Because will be in this law with in the alkali and chlorine, also to reduce chlorine with sulphite, therefore, in per 2 equivalents and the alkali of usefulness need 1 equivalent reductibility sulphite at least.
If alkali number surpasses sulphite amount twice (mol ratio) in the proportioning,, because of lacking enough reductibility sulphite, and can't absorb chlorine even the pH value is controlled between the 1.9-6.3.
If the amount of alkali does not surpass the twice (mol ratio) of sulphite amount, sulphite will work as the surrogate of oxyhydroxide, and, sulfite concentration is high more, the acidic sulfurous acid ion is many more in the absorbent solution, under its shock absorption, and easier control pH value.
Therefore, neither alkali metal containing oxyhydroxide, alkali-free earth metals oxyhydroxide again in the washing soln.Just can absorb chlorine in the waste gas with the aqueous solution of an alkali metal containing and/or alkaline-earth metal sulfite or suspension.
The pH value that is fit to the chlorine absorption reaction is 1.9-6.3, and pH is higher than 6.3 can be transformed into the acid carbonate ion with carbon dioxide gas, as shown in Figure 4, thereby has consumed alkali.Many consumption alkali will make this method become uneconomical.
The pH value is lower than at 1.9 o'clock, forms free sulfurous acid, and decomposes, and therefore is easy to produce sulfur dioxide gas.So do not select low like this pH value for use.
PH value of water solution is controlled at 1.9-6.3 is by the alkali metal sulfite that regulate to add and/or the amount of alkaline-earth metal sulfite, and the amount of alkali metal hydroxide that is not higher than sulphite twice (mol ratio) that adds and/or alkaline earth metal hydroxides reaches.
In this case, can add oxyhydroxide and sulphite with solid or aqueous solution form respectively, preferably add with aqueous solution form.Both can be fitted over together, self-evident, also can add with aqueous solution form respectively.
The concentration range of every kind of aqueous solution using on a selective basis under the situation with an alkali metal salt or alkaline earth salt, the salt of raw material and generation and vitriol are all dissolved, even but they add with the slurries form separately, still can operate.
As operating under the solubility condition of concentration in homogeneous system near salt, should consider to determine under the solubleness factor temperature of reaction at the same time.Because basic metal and alkaline-earth metal sulfite and muriatic solubleness very do not depend on temperature, institute thinks its concentration of increase and uses comparatively high temps, can't produce much effects.
Speed of response between chlorine and the sulphite raises with temperature and accelerates, but considers the corrosion and the damage problem of reactor material, the best 0-70 of temperature of reaction ℃.
About reactive mode, can adopt in stirring tank bubbling or in washing tower the drip washing mode absorb gas.
Though progression changes the safe level that depends on chlorine in the processed gas, does not need to increase too many progression, because reaction or absorption rate are very fast.
Below with reference to Fig. 5 above-mentioned embodiment is described.
Carbonated and chlorine, the gas mixture 401 that also can contain nitrogen, oxygen and other similar gases in some cases, 407 by partly sending in the tower down from the absorption tower, with washing lotion 402 these gas mixtures 401 of washing that are circulated back to tower top, washings 402 is the aforesaid aqueous solution or suspension, alkali metal containing sulphite and/or alkaline-earth metal sulfite, or alkali metal containing sulphite and/or alkaline-earth metal sulfite and alkali metal hydroxide and/or alkaline earth metal hydroxides, its pH value is controlled at 1.9-6.3.
Washings recycles after being diluted with water to desired concn, controls its pH value simultaneously and keeps its flow velocity constant by overflow 404.
After the processing, will remove waste gas 406 behind the chlorine, discharge this system with washing lotion.
The method of 1-3 of the present invention aspect is used in combination, can constitutes the important component part in the method for industrial production chlorine.
That is, the 1st, 2,3 aspects can be combined, set up a combined method, as shown in Figure 6.Use this combined method, can from the gas mixture of carbonated, non-condensable gas and chlorine, reclaim chlorine efficiently, can further almost completely remove simultaneously the chlorine in the waste gas of discharge system, thereby solve pollution problem.
Below with reference to Fig. 6 this combined method is described.
As such scheme, make carbonated and non-condensable gas, chloride gas mixture is sent into compressor 501 through managing 531 simultaneously, is compressed to predetermined pressure.By water cooler 502 this gas mixture is cooled to give fixed temperature,, makes a part of chlorine liquefaction again through condenser 503 liquefaction.The gas-liquid mixture that obtains is sent into separator 504, be separated into based on the residual gas of non-condensable gas with based on the phlegma of chlorine at this.This phlegma is sent into tower from stripping tower 505 tops, along tower when dirty, contact with chlorine vapor by reboiler 506 ebuillition of heated, make the carbonic acid gas and the non-condensable gas evaporation that are dissolved in the phlegma, collect the high purity liquid chlorine from the stripping tower still, discharge through managing 511 as product chlorine.The purity of the chlorine that obtains after above-mentioned processing is generally 99V% or higher.
After carbonic acid gas that steams from phlegma and non-condensable gas are discharged by the stripping cat head, through manage 509 with from separator, converge through managing 508 residual gases of discharging.
This gas mixture of at least a portion is sent into absorption tower 512.Send in the gas mixture on absorption tower almost all that chlorine and partial CO 2 and non-condensable gas are absorbed by the solvent under overhead streams 513, thus gas mixture is transformed into waste gas 514, form by carbonic acid gas and non-condensable gas in this waste gas, and contain chlorine less than 1V%.
The solvent 515 that has absorbed chlorine, carbonic acid gas and non-condensable gas is discharged at the bottom of tower, sends into heat exchanger 517 with pump 516.After heat exchanger 517 gives heat, send into distillation tower 518 again.
The solvent of sending into distillation tower 518 is by reboiler 519 ebuillition of heated, with condenser 533 condensations, gets back to distillation tower through 520 distillations that reflux, and makes absorbed gas evaporation and isolates recovery gas based on chlorine.
Cl content is not higher than 5000PPM(wt), preferably be not higher than 500PPM(wt) solvent 521 discharge by the tower still, send into heat exchanger 517 by pump 522.This solvent is after heat exchanger 517 is removed heat, and restock part fresh solvent 523 is to compensate its loss part.This solvent cools off through cooling tower 524 again, and sends absorption tower 512 back to.
To form and contain less than the waste gas 514 of 1V% chlorine by carbonic acid gas and non-condensable gas and send into absorption tower 525, use circulation washing lotion 526 washings from tower top by the lower section.Washing lotion is the aforesaid aqueous solution or suspension, contain alkali metal sulfite and/or alkaline-earth metal sulfite, or contain alkali metal sulfite and/or alkaline-earth metal sulfite and alkali metal hydroxide and/or alkaline earth metal hydroxides, its pH value is controlled at 1.9-6.3, this washing lotion is diluted with water to desired concn, recycle, control its pH value and keep its flow velocity constant by overflow 527.
After the processing, will remove waste gas 528 discharge systems behind the chlorine with washing lotion.
Washing lotion is mixed with by water 530 and sodium sulfite aqueous solution.
Describe the present invention in detail with example below.
Example 1
The equipment that provides according to Fig. 1 flow process.
Stripping tower, heat exchanger and separator specification are as follows
Stripping tower:
Material SUS316L
The size 50mm diameter * 1000mm height of tower
The size 50mm diameter * 385mm height of filler part
Filler " Sulzer Labopack " (trade mark; The product of Sumitomo Ishikawajima-Harima Heavy Industries Ltd.)
Reboiler part electric heater, maximum 1.0KW
Heat exchanger
Material SUS316L
Heat transfer area 1.5m
2
Separator
Material SUS316L
Capacity 3.5l
To be reduced to 7kg/cm by the mixed pressure that 50V% chlorine, 15V% carbonic acid gas, 10V% nitrogen and 25V% oxygen are formed with compressor
2Behind-the G, make it flow through heat exchanger, be cooled to-24 ℃ with 1.050kg mol/hr flow velocity.This gas mixture is sent into separator after heat exchanger cooling, be separated into liquids and gases, and liquid is flowed down along stripping tower.The electric weight of control input electric heater uses this electric heater that the temperature of stripping tower reboiler is remained on 25 ℃, discharges liquid chlorine continuously to keep in the reboiler liquid chlorine amount constant.
When equipment reached stable state, stripping tower top temperature was-8 ℃, 25 ℃ of reboiler temperature, tower top pressure 7.0kg/cm
2-G at this moment, obtains product chlorine, purity 99.2V% from the stripping tower still with 0.3kg mol/hr speed.
Example 2
The equipment of use-case 1.To be reduced to 10kg/cm by the mixed pressure that 39V% chlorine, 13V% carbonic acid gas, 9V% nitrogen and 39V% oxygen are formed with compressor
2Behind-the G, make it pass through heat exchanger, be cooled to-40 ℃ with the 1.050kgmol/hr flow velocity.
Gas mixture is sent into separator and is divided into gas and liquid after heat exchanger cooling.Liquid is flowed down by stripping tower, and the electric weight of control input electric heater uses this electric heater that stripping tower reboiler temperature is partly remained on 37 ℃.Discharge liquid chlorine continuously, constant with liquid chlorine amount in the maintenance reboiler.
When equipment reached stable state, stripping tower top temperature was-12 ℃, 37 ℃ of reboiler temperature, tower top pressure 10kg/cm
2-G at this moment, obtains product chlorine from the stripping tower still with 0.35kg mol/hr speed, and purity is 99.2V%.
Example 3
The equipment of use-case 1.Will be with compressor by 10V% chlorine, 17V% carbonic acid gas, the mixed pressure that 30V% nitrogen and 43V% oxygen are formed is reduced to 12kg/cm
2-G makes it pass through heat exchanger with 1.050kg mol/hr flow velocity, is cooled to-40 ℃.
This gas mixture by heat exchanger cooling after, send into separator, be divided into gas and liquid.Liquid is flowed down along stripping tower.The electric weight of control input electric heater uses this electric heater that the temperature of stripping tower reboiler part is remained on 45 ℃.Discharge liquid chlorine continuously, constant with liquid chlorine amount in the maintenance reboiler.
When equipment reached stable state, stripping tower top temperature was-8 ℃, 45 ℃ of reboiler temperature, tower top pressure 12kg/cm
2-G at this moment, obtains product chlorine, purity 99.2V% from stripping tower still top 0.04kgmol/hr speed.
Comparative example 1
According to flow process shown in Figure 2, the stripping tower and the heat exchanger of use-case 1 are operated.Should note stripping tower is changed into from its bottom, rather than send into gas mixture from the top.To be reduced to 7kg/cm by the mixed pressure that 50V% chlorine, 15V% carbonic acid gas, 10V% nitrogen and 25V% oxygen are formed by compressor 201
2-G enters stripping tower 202 bottoms with 0.24kg mol/hr flow velocity then.With heat exchanger 203 control Outlet Gas Temperatures is-24 ℃.The electric weight of control input electric heater uses this electric heater that the temperature of stripping tower reboiler part is remained on 18 ℃, discharges liquid chlorine continuously, to keep reboiler 205 interior liquid chlorine amounts constant.
When equipment reached stable state, heat exchanger 203 Outlet Gas Temperatures were-24 ℃, and the temperature of reboiler 205 is 18.4 ℃, tower top pressure 7kg/cm
2-G.At this moment, obtain product chlorine, purity 99.0V% from the stripping tower bottom with 0.09kg mol/hr speed.Obviously, using as 1 the sort of of example phlegma is carried out the ability that method that stripping handles is handled gas mixture, is 4 times of ordinary method processing power in the comparative example 1 at least.
Comparative example 2
Equipment with comparative example 1 carries out similar test, and just the speed of supplying gas with the stripping tower bottom changes 0.60kg mol/hr into.But can not under stable state, operate, because it is heat exchanger import and export gas temperature changes, unsettled.Obviously can not under the condition of the processing power that improves this ordinary method, operate.
Example 4
Equipment in Fig. 3 flow process is provided.
Carry the gas mixture of forming by 38.9V% chlorine, 12.9V% carbonic acid gas and 48.2V% nitrogen oxygenation to this equipment.When the compression pressure of compressor and the cooling liquid temperature of condenser are decided to be 7kg/cm respectively
2When-G and-24 ℃, 27.3% gas mixture.Be that 67.5% chlorine is condensed in the gas mixture.Phlegma is sent into by top from stripping tower.Respectively tower top pressure and tower still temperature are controlled at 7kg/cm
2-G and 25.4 ℃ obtain containing the liquid chlorine of 99.5% chlorine thus.
The gas that distillates of discharging from stripping tower top contains 18.6V% chlorine, 17.1V% carbonic acid gas and 64.3V% nitrogen and oxygen.The tetracol phenixin that to quite send into 3.6 times of (wt) amounts of absorption tower unstripped gas is cooled to-15 ℃, as lyosorption.Roof pressure 7kg/cm is being kept on the absorption tower
2Move under-G the condition.The waste gas composition that absorbs the cat head discharge is 47ppm(v) chlorine, 19.7V% carbonic acid gas, 80.1V% nitrogen oxygenation, 0.2V% tetracol phenixin.
The tetracol phenixin that will absorb chlorine with pump is sent into distillation tower from the bottom.Distillation tower is at roof pressure 1.3kg/cm
2-G, condenser temperature-15 ℃ moves under 105.6 ℃ of conditions of still temperature, is 89.4V% chlorine from the gas composition of distillation recovered overhead, 7.3V% carbonic acid gas, 3.3V% nitrogen oxygenation, and 500ppm(v) tetracol phenixin.Cl concn is 5ppm(wt in the solvent), the chlorine rate of recovery is 99.99%.
Example 5
Usual practice 4 equipment useds are sent into the gas mixture of being made up of 25V% chlorine, 11V% carbonic acid gas and 64V% nitrogen oxygenation.When compression pressure and cooling temperature are respectively 9kg/cm
2When-G and-37 ℃, 20% gas mixture, promptly 71% chlorine is condensed in the gas mixture.
Then, only phlegma is sent into stripping tower.The stripping tower operational conditions is controlled at roof pressure and the still temperature is respectively 9kg/cm
2-G and 28.9 ℃.Obtain containing the liquid chlorine of 96.3% chlorine thus.Ingress, absorption tower gas is by 9.9V% chlorine, and 12.9V% carbonic acid gas and 77.2V% nitrogen oxygenation are formed.The tetracol phenixin that will be equivalent to send into 4.1 times of (wt) amounts of absorption tower gas is cooled to-17 ℃, as absorption agent.The absorption tower is at roof pressure 9kg/cm
2-G is operation down.Forming from the waste gas that absorbs the cat head discharge is 16ppm(v) chlorine, 12.4V% carbonic acid gas, 87.4V% nitrogen oxygenation, 0.2V% tetracol phenixin.On the other hand, with pump lyosorption is sent into distillation tower from the top, absorption tower.The distillation tower operational conditions is roof pressure 3.5kg/cm
2-G, 2 ℃ of condenser temperatures, 132.9 ℃ of still temperature.The gas composition that steams from the distillation cat head is a 75.7V% chlorine, 15.8V% carbonic acid gas, 8.5V% nitrogen oxygenation and 480ppm tetracol phenixin.Cl concn 36ppm(wt in the solvent), the chlorine rate of recovery is 99.99%.
Example 6
In flask, add 1l10(wt) sodium sulfite aqueous solution of %, load onto the return line of lower ending opening, feed the gas mixture of 1l/min carbonic acid gas and 100ml/min chlorine, make bubbling.Monitoring pH value changing conditions, during beginning, the gas of feeding all is absorbed.The pH value descends with continuous ventilation.When pH drops to 6 or when lower, a part of gas begins to flow out.The pH value drops at 4 o'clock, and beginning feeds sodium sulfite aqueous solution with the 15.7cc/min flow velocity, makes the pH value remain on 4.
In these cases, make effusive, not by the gas of solution absorption by the collector of (N)/2 liquor kalii iodide is housed, flow through the collector that another is equipped with (N)/2 soda lye again, with above-mentioned two solution of (N)/10 Sulfothiorine titration, make indicator with amidin simultaneously.Use cl content in the titration measuring collector with this.Find that cl content is not higher than 1ppm(v in the tail gas).
In addition, use (N)/10 NaOH and (N)/10 HCl titration quilt (N)/2 liquor kalii iodide and (N)/2 carbonic acid of soda lye absorption respectively, make indicator with tropeolin-D.The result confirms that the carbon dioxide gas of feeding is not absorbed fully, has a certain amount of carbonic acid gas to flow out flask.
Example 7
Add the aqueous solution that contains 8.6wt% S-WAT and 1.4wt% caustic soda to being similar to example 6 in reactor used, feed the gas mixture of 1l/min carbonic acid gas and 100cc/min chlorine equally.When pH reached 4, beginning added the aqueous solution identical with top solution composition with the 12.1ml/min flow velocity, and the pH value is remained on 4.Flow out the gas of above-mentioned flask with the methods analyst identical with example 6, the result confirms that cl content is not higher than 1ppm(v), and carbonic acid gas flows out fully.
Example 8
According to the flow process of Fig. 5, will contain 30V% carbonic acid gas, 70V% nitrogen oxygenation and 1000ppm(v) gas mixture 401 of chlorine, with 500Nm
3/ hr flow velocity is sent into from the bottom, absorption tower.Absorption tower diameter 0.8m is filled with 1 inch high Raschig ring of 2.2m.The absorption liquid 402 that comes with circulating from cat head is with 10m
3/ hr flow velocity washing gas mixture 401 remains on 4.0 with about 94.5kg/hr flow velocity with pH value in the tower with the aqueous solution 403 that contains the 10wt% S-WAT, adds water 405 with the 278kg/hr flow velocity simultaneously.Meanwhile, it is constant to utilize upflow tube 404 to keep liquid level.From processed gas 406 samplings that cat head is discharged, with (N)/10 potassium iodide aqueous solution absorption analysis, measuring cl content is 1ppm(v) or lower.
Example 9
This routine equipment used flow process as shown in Figure 6.
Send into the gas mixture of forming by 38.9V% chlorine, 12.9V% carbonic acid gas and 48.2V% nitrogen oxygenation to this equipment.When the compression pressure of compressor and the cooling condensation temperature of condenser are respectively 7kg/cm
2When-G and-24 ℃, 27.3% gas mixture, promptly 67.5% chlorine is condensed in the gas mixture.Only phlegma is sent into by top from stripping tower.Stripping tower roof pressure and still temperature are controlled at 7kg/cm respectively
2Under-G and 25.4 ℃, obtain containing the liquid chlorine of 99.5% chlorine thus.
The distillate gas of discharging from stripping tower top contains 18.6V% chlorine, 17.1V% carbonic acid gas and 64.3V% nitrogen oxygenation.
The tetracol phenixin that will be equivalent to send into 3.6 times of (wt) amounts of gas in the stripping tower is cooled to-15 ℃, as lyosorption.Roof pressure 7kg/cm is being kept on the absorption tower
2Move under-G the condition.From absorbing that waste gas that cat head discharges forms is 47ppm(v) chlorine, 19.7V% carbonic acid gas, 80.1V% nitrogen oxygenation, 0.2V% tetracol phenixin.
The tetracol phenixin that will absorb chlorine with pump is sent into distillation tower from the top.Distillation tower is at roof pressure 1.3kg/cm
2-G, condenser temperature-15 ℃ moves under 105.6 ℃ of conditions of still temperature.From the gas composition of distillation recovered overhead is 89.4V% chlorine, 7.3V% carbonic acid gas, 3.3V% nitrogen oxygenation, and 500ppm(V) tetracol phenixin.Cl content is 5ppm(wt in the solvent), the chlorine rate of recovery is 99.99%.
From absorbing gas mixture that cat head discharges by 47ppm(v) chlorine, 19.7v% carbonic acid gas, 80.1v% nitrogen oxygenation and 0.2v% tetracol phenixin form.This gas mixture is sent into scrubber tower remove chlorine.Send into gas mixture from the bottom, make round-robin absorb liquid under overhead stream simultaneously, absorb chlorine in the gas mixture with this.
Make as absorbing under water solution flow liquid, that contain the 10wt% S-WAT, and to control its pH value be 4.2, absorption liquid is contacted with gas mixture and absorb chlorine.
Cl content is not higher than 1ppm(v from the cat head expellant gas).
Claims (3)
1, a kind of method that from the mixed gas that contains chlorine and carbon dioxide gas, removes chlorine, this method comprise supply alkali metal containing sulphite and (or) aqueous solution or the suspension of alkaline-earth metal sulfite, wash this gas mixture with this solution or suspension, the pH value of controlling this aqueous solution or suspension simultaneously is 1.9-6.3, thereby removes the chlorine in this gas mixture separately.
2, a kind of method that from the mixed gas that contains chlorine and carbon dioxide gas, removes chlorine, this method comprise supply alkali metal containing sulphite and (or) alkaline-earth metal sulfite, simultaneously alkali metal containing oxyhydroxide and (or) aqueous solution or the suspension of alkaline earth metal hydroxides, its mole proportioning is the twice that hydroxide quantity is not higher than the sulphite amount, wash this gas mixture with this solution or suspension, the pH value of controlling this aqueous solution or suspension simultaneously between 1.9-6.3, thereby remove chlorine in this gas mixture separately.
3, a kind of from chloride, remove the method for chlorine in the gas mixture of carbonic acid gas and non-condensable gases, this method comprise supply alkali metal containing sulphite and (or) aqueous solution or the suspension of alkaline-earth metal sulfite, or alkali metal containing sulphite and (or) alkaline-earth metal sulfite and alkali metal hydroxide and (or) aqueous solution or the suspension of alkaline earth metal hydroxides, wherein the amount of oxyhydroxide is not higher than the twice of sulphite amount in molar ratio, wash described gas mixture with this aqueous solution or suspension, the pH value of controlling this aqueous solution or suspension simultaneously is between 1.9-6.3, thereby remove the chlorine in the gas mixture separately, and be discharged to outside the system.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31792/88 | 1988-02-16 | ||
| JP3179288A JPH028683A (en) | 1988-02-16 | 1988-02-16 | Method for separating and recovering chlorine |
| JP32837/88 | 1988-02-17 | ||
| JP63059428A JP2567023B2 (en) | 1988-03-15 | 1988-03-15 | Method of removing chlorine |
| JP59428/88 | 1988-03-15 | ||
| CN 89101852 CN1017414B (en) | 1988-02-16 | 1989-02-16 | Industrial process for separation and recovery of chlorine |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89101852 Division CN1017414B (en) | 1988-02-16 | 1989-02-16 | Industrial process for separation and recovery of chlorine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1064253A true CN1064253A (en) | 1992-09-09 |
| CN1027313C CN1027313C (en) | 1995-01-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92101858 Expired - Lifetime CN1027313C (en) | 1988-02-16 | 1992-03-16 | Industrial process for separation and recovery of chlorine |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329288C (en) * | 1995-10-04 | 2007-08-01 | 巴斯福股份公司 | Method for separating and recovering chlorine from service gas containing chlorine |
| CN102161544A (en) * | 2010-02-24 | 2011-08-24 | 三洋电机株式会社 | Ballast water processing device |
| US8147673B2 (en) | 2005-01-18 | 2012-04-03 | Severn Trent De Nora, Llc | System and process for treatment and de-halogenation of ballast water |
| US8152989B2 (en) | 2005-01-18 | 2012-04-10 | Severn Trent De Nora, Llc | System and process for treating ballast water |
| CN101068750B (en) * | 2004-11-29 | 2012-07-04 | 赛温德罗有限公司 | System and method for treatment of ballast water |
| CN105363318A (en) * | 2015-10-20 | 2016-03-02 | 安徽广信农化股份有限公司 | Diuron intermediate body production tail gas processing technology |
| CN107715491A (en) * | 2017-11-21 | 2018-02-23 | 滨化集团股份有限公司 | A kind of chlorine refines process units |
-
1992
- 1992-03-16 CN CN 92101858 patent/CN1027313C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329288C (en) * | 1995-10-04 | 2007-08-01 | 巴斯福股份公司 | Method for separating and recovering chlorine from service gas containing chlorine |
| CN101068750B (en) * | 2004-11-29 | 2012-07-04 | 赛温德罗有限公司 | System and method for treatment of ballast water |
| US8147673B2 (en) | 2005-01-18 | 2012-04-03 | Severn Trent De Nora, Llc | System and process for treatment and de-halogenation of ballast water |
| US8152989B2 (en) | 2005-01-18 | 2012-04-10 | Severn Trent De Nora, Llc | System and process for treating ballast water |
| CN102161544A (en) * | 2010-02-24 | 2011-08-24 | 三洋电机株式会社 | Ballast water processing device |
| CN105363318A (en) * | 2015-10-20 | 2016-03-02 | 安徽广信农化股份有限公司 | Diuron intermediate body production tail gas processing technology |
| CN107715491A (en) * | 2017-11-21 | 2018-02-23 | 滨化集团股份有限公司 | A kind of chlorine refines process units |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1027313C (en) | 1995-01-04 |
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