CN106731566A - The method and its catalyst of chlorine in milk of lime removal industrial tail gas - Google Patents
The method and its catalyst of chlorine in milk of lime removal industrial tail gas Download PDFInfo
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- CN106731566A CN106731566A CN201611146256.9A CN201611146256A CN106731566A CN 106731566 A CN106731566 A CN 106731566A CN 201611146256 A CN201611146256 A CN 201611146256A CN 106731566 A CN106731566 A CN 106731566A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2025—Chlorine
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- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention belongs to chlorine absorption technical field, the method and its catalyst of chlorine in specifically related to a kind of milk of lime removal industrial tail gas.Because the generation of calcium hypochlorite is unable to reach absorption terminal when absorbing chlorine for existing milk of lime process, and the problems such as etching apparatus, the method that the present invention provides chlorine in a kind of milk of lime removal industrial tail gas, mixing contact catalyst is added when milk of lime absorbs chlorine, described mixing contact catalyst is the mixture of nickel chloride and ferric trichloride.The inventive method is by adding catalyst, reduce the generation of calcium hypochlorite, newly-generated calcium hypochlorite is promoted to decompose, so that calcium hypochlorite concentration is below 1.0% in milk of lime, ensure that milk of lime absorbs the production direct motion of chlorine, uptake is big, also extends service life of equipment, has saved production cost；Simultaneously, moreover it is possible to reduce calcium hypochlorite and decompose the chlorine for the producing influence healthy to staff, with obvious economic benefit and social benefit.
Description
Technical field
The invention belongs to chlorine recovery technology field, the method for chlorine in specifically related to a kind of milk of lime removal industrial tail gas
And its catalyst.
Background technology
In the production such as titanium tetrachloride, PVC, to make reaction more fully typically want chlorine suitably excessive.Therefore system can be caused
Take Cl in the tail gas such as titanium tetrachloride2It is exceeded.To make tail gas qualified discharge, Cl in tail gas should be removed before discharge2, most of enterprise adopts
With removal tail gas in the method for chlorine be to prepare CaCl with milk of lime absorption2Series of products.According to 2Ca (OH)2+2Cl2=
CaCl2+Ca(ClO)2+2H2O, calcium hypochlorite easily decomposes generation oxygen in process of production makes absorption system foam cause to absorb
Terminal can not be reached, operation is difficult to control to；Another aspect calcium hypochlorite oxidisability is strong, serious to equipment corrosion.
The content of the invention
The technical problem to be solved in the present invention is：Because the generation of calcium hypochlorite cannot during existing milk of lime process absorption chlorine
Reach absorption terminal, and etching apparatus problem.
The present invention solve technical problem technical scheme be：A kind of side of chlorine in milk of lime removal industrial tail gas is provided
Method, the generation that can suppress calcium hypochlorite and the decomposition of the calcium hypochlorite that can promote generation, make calcium hypochlorite in calcium chloride solution
Concentration is below 1.0%.
The method that the present invention provides chlorine in a kind of milk of lime removal industrial tail gas, comprises the following steps：
Load milk of lime absorbing in groove, being passed through industrial chloride tail gas to absorption groove is reacted, and adds mixing contact
Catalyst, continues to react 2~3h；Described mixing contact catalyst is the mixture of nickel chloride and ferric trichloride.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, chlorine contains in described industrial chloride tail gas
It is 10~99vol% to measure.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, described mixing contacts the addition of catalyst
Measure and be：Per m30.13~0.15kg/m is added in milk of lime3Mixing contact catalyst.
Further, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, described nickel chloride and ferric trichloride
Weight ratio be 2.8~3.2 ﹕ 0.8~1.0.
Preferably, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, described nickel chloride and ferric trichloride
Weight ratio is 3.2 ﹕ 1.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, reaction temperature is 60~70 DEG C.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, when described mixing contact catalyst is added
Machine is：First after 1~1.5h of reaction, mixing contact catalyst is added.
The present invention also provides a kind of mixing contact catalyst of chlorine in milk of lime removal industrial tail gas, consisting of：2.8
The ferric trichloride of the nickel chloride of~3.2 weight portions and 0.8~1.0 weight portion.
The present invention also provides the application method that a kind of above-mentioned mixing contacts catalyst, in milk of lime removal industrial tail gas
Chlorine absorption.
The present invention also provides the preparation method that a kind of above-mentioned mixing contacts catalyst, by nickel chloride and ferric trichloride in proportion
After mixing, it is added to the water and stirs, the water is just to dissolve nickel chloride and ferric trichloride, no solid particle
It is accurate.
Beneficial effects of the present invention are：The present invention is mixed by adding in chlorine in removing industrial tail gas using milk of lime
Splice grafting touches catalyst, reduces the generation of calcium hypochlorite, promotes newly-generated calcium hypochlorite to decompose so that calcium hypochlorite in milk of lime
Concentration is below 1.0%, it is ensured that milk of lime absorbs the production direct motion of chlorine, and uptake is big, also extends service life of equipment,
Production cost is saved；Simultaneously, moreover it is possible to reduce calcium hypochlorite and decompose the chlorine for the producing influence healthy to staff, tool
There are obvious economic benefit and social benefit.
Specific embodiment
The invention provides the method for chlorine in a kind of milk of lime removal industrial tail gas, comprise the following steps：
Load milk of lime absorbing in groove, being passed through industrial chloride tail gas to absorption groove is reacted, and adds mixing contact
Catalyst, continues to react 2~3h；Described mixing contact catalyst is the mixture of nickel chloride and ferric trichloride.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, chlorine contains in described industrial chloride tail gas
It is 10~99vol% to measure.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, described mixing contacts the addition of catalyst
Measure and be：Per m30.13~0.15kg/m is added in milk of lime3Mixing contact catalyst.
Further, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, described nickel chloride and ferric trichloride
Weight ratio be 2.8~3.2 ﹕ 0.8~1.0.
Preferably, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, described nickel chloride and ferric trichloride
Weight ratio is 3.2 ﹕ 1.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, reaction temperature is 60~70 DEG C.
Wherein, in above-mentioned milk of lime removal industrial tail gas in the method for chlorine, when described mixing contact catalyst is added
Machine is：First after 1~1.5h of reaction, mixing contact catalyst is added.
The present invention also provides a kind of mixing contact catalyst of chlorine in milk of lime removal industrial tail gas, consisting of：2.8
The ferric trichloride of the nickel chloride of~3.2 weight portions and 0.8~1.0 weight portion.
The present invention also provides the application method that a kind of above-mentioned mixing contacts catalyst, in milk of lime removal industrial tail gas
Chlorine absorption.
The present invention also provides the preparation method that a kind of above-mentioned mixing contacts catalyst, by nickel chloride and ferric trichloride in proportion
After mixing, it is added to the water and stirs, the water is just to dissolve nickel chloride and ferric trichloride, no solid particle
It is accurate.
The method of chlorine in milk of lime of the invention removal industrial tail gas, described industrial tail gas are production titanium tetrachloride,
The tail gas of the industrial products with chlorine as raw material such as PVC, general chlorine content is 10~30vol%, but is also applied for simultaneously each
The chlorine (percent by volume is 10~99vol%) for planting concentration absorbs.
In the present invention, the key reaction of chlorine is in milk of lime removal industrial tail gas：2Ca(OH)2+2Cl2=CaCl2+Ca
(ClO)2+2H2O, after adding mixing contact catalyst, promotes reaction Ca (ClO)2=CaCl2+O2Carrying out, suppress reaction Ca
(ClO)2+ 4HClO=Ca (ClO3)2+4HCl(Cl2+H2O → HClO+HCl) carrying out so that Ca (ClO) in system2Contain
Amount is reduced, it is ensured that production direct motion, reduces equipment corrosion, saves production cost.
The present invention contacts catalyst using the mixture of nickel chloride and ferric trichloride as mixing, and defines both match somebody with somebody
Than, new mixing contact catalyst is obtained, catalytic effect substantially, can significantly reduce the calcium hypochlorite content in system.
Further, the present invention also determines above-mentioned mixing and contacts the broiler diets of catalyst and is by experiment：Per m3
0.13~0.15kg/m is added in milk of lime3Mixing contact catalyst.In screening experiment, respectively in every m3Added in milk of lime
0.09kg/m3, 0.11kg/m3, 0.13kg/m3, 0.15kg/m3Mixing contact catalyst, detect anti-under the conditions of equivalent responses
Answer calcium hypochlorite content in groove milk of lime, respectively 10.56%, 6.33%, 0.82%, 0.75%；It thus is seen that when mixing connects
It is 0.13kg/m to touch catalyst loading3When, effectively calcium hypochlorite content in milk of lime can be controlled within 1%, and with
The continuation for mixing contact catalyst increases, and calcium hypochlorite content is not reduced significantly, considers effect and cost, this hair
In bright mixing contact catalyst broiler diets be：Per m30.13~0.15kg/m is added in milk of lime3Mixing contact catalysis
Agent.
In order to investigate the suitable use condition of catalyst of the present invention, inventor respectively at 30~40 DEG C, 50~60 DEG C, 60~
, catalytic reaction is carried out using catalyst of the invention at a temperature of more than 70 DEG C, the addition of catalyst is used by 70 DEG C
0.13kg/m3, catalyst is added after absorption 1.5h absorbing in groove, 30~40 DEG C, 50~60 DEG C, 60~70 are warmed up to respectively
DEG C, more than 70 DEG C reactions, the content for absorbing the calcium hypochlorite in groove is respectively 13.8%, 5.2%, 0.85%, 0.78%, it is seen that
As temperature is raised, more preferably, but to after 70 DEG C, the reduction of calcium hypochlorite content is not substantially, comprehensive for the catalytic effect of catalyst
Consider effect and cost, suitable reaction temperature of the invention is 60~70 DEG C.
In order to further optimize the catalytic effect of catalyst, whether inventor has also investigated catalyst addition opportunity can be to urging
Change effect and produce influence.0h, 1.5h, the 2.5h for being carried out in reaction respectively add mixing contact catalyst, obtain following result：
Reaction carries out 0h (reaction just starts) and adds mixing contact catalyst, a large amount of bubbles occurs very in phase absorbing reaction groove after manufacture
Largely overflowed to there is milk of lime, calcium hypochlorite content reaches 8.2%；Added when 1.5h is reacted, reaction is very steady, to reaction
Calcium hypochlorite content 0.83% is detected during terminal, catalytic effect is notable；There are a large amount of gas when reaction proceeds to 2.5h, in reactive tank
Bubble, reaction solution largely overflows, and production cannot proceed, and now adds catalyst without positive effect.Therefore, present invention selection
It is 1.0~1.5h that reaction starts that mixing contact catalyst adds the time.
Explanation is further explained to specific embodiment of the invention below by embodiment, but is not indicated that and will be protected
Scope is limited in scope described in embodiment.
The inventive method of embodiment 1 removes chlorine in production titanium tetrachloride tail gas
Load milk of lime 8m in groove absorbing3, weigh 1.04 kilograms of mixed catalyst (catalyst weight is than 2.8 ﹕ 0.8) and put
Enter in 10 kilograms of Plastic Drums, then add 4~6 kilograms of running water to bucket the inside and do not stop stirring with waddy until in bucket with the naked eye
Untill not seeing catalyst solid particle, catalyst liquid bucket will be contained and put standby beside absorption groove, then be passed through tetrachloro to absorption groove
Change titanium and produce tail gas (chlorine content 10.3% in tail gas) while being heated to absorbing reaction groove, reaction to be absorbed is carried out to 1.0h
When, added in groove mixing contact catalyst to absorbing, controlling reaction temperature continues to react 2h at 60 ± 2 DEG C；Whole reaction can be suitable
Profit is carried out, and the content that detection absorbs calcium hypochlorite in groove is 0.93%, meets requirement of the calcium hypochlorite less than 1% in product.
The inventive method of embodiment 2 removes production ion film caustic soda by-product chlorine
Load milk of lime 8m in groove absorbing3, weigh 1.2 kilograms of mixed catalyst (catalyst weight is than 3.0 ﹕ 0.9) and put
Enter in 10 kilograms of Plastic Drums, then add 6~8 kilograms of running water to bucket the inside and do not stop stirring with waddy until in bucket with the naked eye
Untill not seeing catalyst solid particle, catalyst liquid bucket will be contained and put standby beside absorption groove, then be passed through ion to absorption groove
Film caustic soda by-product chlorine (chlorine content 98.6% in tail gas) is while heat to absorbing reaction groove, reaction to be absorbed is carried out to 1.5h
When, added in groove all mixing contact catalyst to absorbing, controlling reaction temperature continues to react 3h at 68 ± 2 DEG C；Whole reaction
Can be smoothed out, the content that detection absorbs calcium hypochlorite in groove is 0.78%, meet calcium hypochlorite wanting less than 1% in product
Ask.
The inventive method of embodiment 3 removes chlorine in production titanium tetrachloride tail gas
Load milk of lime 8m in groove absorbing3, weigh 1.04 kilograms of mixed catalyst (catalyst weight is than 3.2 ﹕ 1.0) and put
Enter in 10 kilograms of Plastic Drums, then add 4~6 kilograms of running water to bucket the inside and do not stop stirring with waddy until in bucket with the naked eye
Untill not seeing catalyst solid particle, catalyst liquid bucket will be contained and put standby beside absorption groove, then be passed through production to absorption groove
The industrial tail gas (chlorine content 15.1% in tail gas) of titanium tetrachloride while give the heating of absorbing reaction groove, reaction to be absorbed carry out to
During 1.5h, added in groove all mixing contact catalyst to absorbing, controlling reaction temperature continues to react 3h at 60~70 DEG C；It is whole
Individual reaction can be smoothed out, and the content that detection absorbs calcium hypochlorite in groove is 0.72%, and calcium hypochlorite is less than 1% in meeting product
Requirement.
Comparative example 1 is added without chlorine in catalyst removal industrial tail gas
Load milk of lime 8m in groove absorbing3, produce the industrial tail gas (chlorine content 15.1% in tail gas) of titanium tetrachloride
Giving the heating of absorbing reaction groove, reaction to be absorbed simultaneously is carried out during to 45 minutes, occurs a large amount of bubbles, milk of lime liquid level in reactive tank
Start to go up, absorb within about 10 minutes or so groove reaction solution and start to overflow, experiment cannot continue, can only close down.
Comparative example 2 adds chlorine in a small amount of catalyst removal industrial tail gas
Load milk of lime 8m in groove absorbing3, weigh 0.72 kilogram of mixed catalyst (catalyst weight is than 2.8 ﹕ 0.8) and put
Enter in 10 kilograms of Plastic Drums, then add 3~5 kilograms of running water to bucket the inside and do not stop stirring with waddy until in bucket with the naked eye
Untill not seeing catalyst solid particle, catalyst liquid bucket will be contained and put standby beside absorption groove, then be passed through tetrachloro to absorption groove
Change titanium and produce tail gas (chlorine content 10.3% in tail gas) while being heated to absorbing reaction groove, reaction to be absorbed is carried out to 1.5h
When, added in groove all mixing contact catalyst to absorbing, controlling reaction temperature continues to react 3h at 60~70 DEG C；It is whole anti-
Should be able to be smoothed out, the content that detection absorbs calcium hypochlorite in groove is 1.25%, it is impossible to which calcium hypochlorite is less than 1% in meeting product
Requirement.
From embodiment and comparative example, when mixing contact catalyst of the invention is not used, the hypochlorous acid in system
Calcium causes the production cannot to be smoothed out, and catalyst loading is very few, does not also reach requirement of the calcium hypochlorite less than 1% in product.
The inventive method contacts catalyst by adding the mixing of Sq, can reduce the generation of calcium hypochlorite, promotes newly-generated time
Calcium chlorate is decomposed so that calcium hypochlorite concentration is below 1.0% in milk of lime, it is ensured that the production that milk of lime absorbs chlorine is suitable
OK, uptake is big, also extends service life of equipment, has saved production cost.
Claims (10)
1. the method that milk of lime removes chlorine in industrial tail gas, it is characterised in that comprise the following steps：
Load milk of lime absorbing in groove, being passed through industrial chloride tail gas to absorption groove is reacted, add mixing contact catalysis
Agent, continues to react 2~3h；Described mixing contact catalyst is the mixture of nickel chloride and ferric trichloride.
2. the method that milk of lime according to claim 1 removes chlorine in industrial tail gas, it is characterised in that：Described industry
Chlorine content is 10~99vol% in chloride tail gas.
3. the method that milk of lime according to claim 1 removes chlorine in industrial tail gas, it is characterised in that：Described mixing
Contact catalyst addition be：Per m30.13~0.15kg/m is added in milk of lime3Mixing contact catalyst.
4. the method that milk of lime according to claim 1 removes chlorine in industrial tail gas, it is characterised in that：Described chlorination
Nickel is 2.8~3.2 ﹕ 0.8~1.0 with the weight ratio of ferric trichloride.
5. the method that milk of lime according to claim 1 removes chlorine in industrial tail gas, it is characterised in that：Described chlorination
Nickel is 3.2 ﹕ 1 with the weight ratio of ferric trichloride.
6. the method that milk of lime according to claim 1 removes chlorine in industrial tail gas, it is characterised in that：Reaction temperature is
60~70 DEG C.
7. the method that milk of lime according to claim 1 removes chlorine in industrial tail gas, it is characterised in that：Described mixing
Contact catalyst add opportunity be：First after 1~1.5h of reaction, mixing contact catalyst is added.
8. the mixing described in any one of claim 1~7 contacts catalyst, it is characterised in that consisting of：2.8~3.2 weight
The nickel chloride of part and the ferric trichloride of 0.8~1.0 weight portion.
9. the mixing described in claim 8 contacts the application method of catalyst, it is characterised in that：Industrial tail is removed for milk of lime
Chlorine absorption in gas.
10. the mixing described in claim 7 contacts the preparation method of catalyst, it is characterised in that：By nickel chloride and ferric trichloride
After mixing in proportion, it is added to the water and stirs, the water is just to dissolve nickel chloride and ferric trichloride, without solid
Particle is defined.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611146256.9A CN106731566B (en) | 2016-12-13 | 2016-12-13 | Milk of lime removes the method and its catalyst of chlorine in industrial tail gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611146256.9A CN106731566B (en) | 2016-12-13 | 2016-12-13 | Milk of lime removes the method and its catalyst of chlorine in industrial tail gas |
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| CN106731566B CN106731566B (en) | 2019-09-27 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108079771A (en) * | 2017-12-29 | 2018-05-29 | 攀枝花钢企欣宇化工有限公司 | The absorption processing method of chlorinated exhaust |
| CN110872716A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院过程工程研究所 | Method for removing chloride ions in sulfuric acid solution containing chlorine by adopting photocatalytic fluidized bed |
| CN115738640A (en) * | 2023-01-10 | 2023-03-07 | 云南中陇市政环保工程有限公司 | Chlorine absorption system for electrolytic lithium production |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108079771A (en) * | 2017-12-29 | 2018-05-29 | 攀枝花钢企欣宇化工有限公司 | The absorption processing method of chlorinated exhaust |
| CN110872716A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院过程工程研究所 | Method for removing chloride ions in sulfuric acid solution containing chlorine by adopting photocatalytic fluidized bed |
| CN110872716B (en) * | 2018-09-04 | 2021-01-08 | 中国科学院过程工程研究所 | Method for removing chloride ions in sulfuric acid solution containing chlorine by adopting photocatalytic fluidized bed |
| CN115738640A (en) * | 2023-01-10 | 2023-03-07 | 云南中陇市政环保工程有限公司 | Chlorine absorption system for electrolytic lithium production |
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| Publication number | Publication date |
|---|---|
| CN106731566B (en) | 2019-09-27 |
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