CN103550989B - The integrated conduct method of tail gas in a kind of mercury chloride production process - Google Patents
The integrated conduct method of tail gas in a kind of mercury chloride production process Download PDFInfo
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- CN103550989B CN103550989B CN201310484440.4A CN201310484440A CN103550989B CN 103550989 B CN103550989 B CN 103550989B CN 201310484440 A CN201310484440 A CN 201310484440A CN 103550989 B CN103550989 B CN 103550989B
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- tail gas
- hydrochloric acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention relates to the integrated conduct method of tail gas in a kind of mercury chloride production process, comprise the following steps: passed into by tail gas in sedimentation dashpot, carry out natural subsidence, the material settled down, as Product recycling; Tail gas after sedimentation is passed in hydrochloric acid absorption tower, absorbs in tail gas and remain mercury chloride, then the dissolving Recycling Mother Solution of the hydrochloric acid solution being dissolved with mercury chloride as catalyst is used; Tail gas after absorption by Hydrochloric Acid is passed in acid mist trapping tower, formed after acid droplet is concentrated and flow automatically in hydrochloric acid absorption tower, recycle; Pumped in alkali liquor absorption groove by jet pump by tail gas after trapping and react, obtain byproduct clorox, residual exhaust detects rear outer row up to standard.The present invention not only eliminates mercury chloride in tail gas and chlorine, downstream absorption liquid can also be made to be fully utilized, obtain byproduct clorox, add economic well-being of workers and staff, environmental protection simultaneously, can decrease mercury chloride and chlorine to the pollution of environment.
Description
Technical field
The present invention relates to the integrated conduct method of tail gas in a kind of mercury chloride production process, belong to mercury chloride production field.
Background technology
The mercury of China 60% is mainly used in generated by polyvinyl chloride by calcium carbide industry.Mainly generate mercury chloride (Mercuric chloride) with mercury and chlorine reaction, being commonly called as mercuric chloride is occupation mode.Mercury chloride utilizes mercury metal to burn in chlorine to generate mercury chloride steam, obtains through cooling spontaneous nucleation.
Principle: Hg+Cl
2=HgCl
2
Mercury metal (purity>=99.99%) is placed in high-order measuring tank, regulate its flow, naturally flow in the quartz combustion stove of preheating, (excessive with the chlorine of high temperature, guarantee mercury metal total overall reaction) catalytic combustion, reaction temperature controls between 460 ~ 600 DEG C, the mercury chloride (HgCl of generation
2) steam (white cigarette) and suitably excessive chlorine enters refractory ceramics cooling tower, carries out downflow type cooling with natural cold air.Mercury chloride steam generates crystalloid solids immediately through cooling, naturally drop in collecting pit high temperature resistant, acidproof at the bottom of tower and cool further, when it is close to room temperature (25 ~ 30 DEG C), sample analysis, the qualified product polybag metering packing (carrying out under being packaged in negative pressure state) of two-layer >=8 thread, reinstall in metal drum or woven bag, labelled check and accepting storing.In production process, the control of temperature, negative pressure, flow decides the content of mercury chloride in tail gas.Traditional technique passes in lime aqueous solution by tail gas, makes chlorine become calcium hypochlorite and calcium chloride.Then discharge.The decomposition of such one side calcium hypochlorite can produce a large amount of poisonous and hazardous chlorine, and on the other hand, chlorine can bring the mercury chloride of part to be dissolved in limewash, and the mercury content of solution is exceeded standard.Serious harm is brought to environment.
Summary of the invention
Technical problem to be solved by this invention is to provide the integrated conduct method of tail gas in a kind of mercury chloride production process, and downstream absorption liquid can be made to be fully utilized, simultaneously can better protection of the environment.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: the integrated conduct method of tail gas in a kind of mercury chloride production process, comprises the following steps:
(1) natural subsidence: tail gas is passed in sedimentation dashpot, mercury chloride powder in tail gas is after Temperature fall enrichment, utilize bottom himself gravity natural subsidence to sedimentation dashpot, then the object-discharging pipe bottom sedimentation dashpot drops in airtight concentrated groove, the material in groove is concentrated in regular removing, as Product recycling;
(2) dissolving with hydrochloric acid: the tail gas after sedimentation is passed in hydrochloric acid absorption tower, absorb in tail gas and remain mercury chloride, then pump in the catalyst soaking compartment in mercuric chloride catalyst workshop by the hydrochloric acid solution being dissolved with mercury chloride, the dissolving Recycling Mother Solution as catalyst uses;
(3) acid mist is trapped: passed into by the tail gas after absorption by Hydrochloric Acid in acid mist trapping tower, the hydrochloric acid mist be mixed in trapping tail gas, formation acid flows automatically in hydrochloric acid absorption tower after dripping and concentrating, and recycles;
(4) alkali liquor absorption: pumped in alkali liquor absorption groove by jet pump by the tail gas after trapping and react, obtain byproduct clorox, residual exhaust detects rear outer row up to standard.
On the basis of technique scheme, the present invention can also do following improvement.
Further, in described step (2), hydrochloric acid absorption tower adopts the mode of top spray hydrochloric acid counterflow exchange to absorb.
Further, in described step (4), alkali liquor absorption groove is the sodium hydroxide solution of 15% built with mass fraction.
Further, reaction temperature≤40 DEG C in described step (4) in alkali liquor absorption groove.
Beneficial effect of the present invention is: the present invention not only eliminates mercury chloride in tail gas and chlorine, downstream absorption liquid can also be made to be fully utilized, obtain byproduct clorox, add economic well-being of workers and staff, simultaneously environmental protection, can decrease mercury chloride and chlorine to the pollution of environment.
The present invention adopts comprehensive treatment technique, first from tail gas, reclaims mercury chloride by natural subsidence, and as Product recycling, greatly reduces the Hg chloride content in tail gas, and according to statistics in the past, from cooling tower tail gas out, Hg chloride content is 5 ~ 10g/m
3(standard state), and collect after sedimentation through subsider, the Hg chloride content in tail gas drops to 0.3 ~ 0.5g/m
3(standard state), the rate of recovery reaches more than 94%.
Utilize the remaining mercury chloride cleaning of off-gas of dissolving with hydrochloric acid subsequently, this improving technique utilizes mercury chloride solubility property better principle that chlorine discord hydrochloric acid reacts in hydrochloric acid, by the level Four column plate of tail gas by two hydrochloric acid bubble absorbing towers, utilize air-flow and hydrochloric acid repeatedly counterflow exchange, hydrochloric acid is roused into film and mercury chloride contact lysis by column plate pore, circulation solution absorption beaten by hydrochloric acid pump, when meltage reaches 50-80g/L, this hydrochloric acid solution is pumped into mercuric chloride catalyst workshop, and the dissolving mother liquor as catalyst uses.The tail gas completing this step is mainly chlorine, but also containing hydrochloric acid mist, so utilize acid mist to trap tower, the hydrochloric acid mist be mixed in trapping tail gas, formation acid flows automatically in absorption tower after dripping and concentrating, and recycles.
Now main in tail gas composition is chlorine, pump into sodium hydroxide solution absorption cell by alkali lye jet pump, in absorption cell, be provided with titanium cooling coil, with 5 DEG C of indirect cooling and absorbing liquid of cooling water, control absorption reaction temperature≤40 DEG C, allow absorption reaction be undertaken by following reaction equation: NaOH+Cl
2===NaClO+HCl.In NaOH absorption reaction process, NaClO easily decomposes, simultaneously, when absorption is close to time saturated, have a small amount of chlorine and overflow, the absorption cell that this technique adopts is closed cell, top is provided with gas diversion tube, close to time saturated overflow a small amount of chlorine, detect up to standard after, be directed at 25m chimney stack through mozzle and arrange outward.
The byproduct liquor natrii hypochloritis obtained, wherein available chlorine content is 10 ~ 15%, reaches the standard in national clorox product standard GB1906-2003, possesses the condition as general industry raw material.So, this clorox can be fully utilized further, auxiliary construction hydrazine hydrate production line liquor natrii hypochloritis for the production of the hydrazine hydrate product of high added value, as producing polyvinyl chloride polymerization terminator ATSC(acetone semicarbazone thiocarbamide) raw material.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart.
Detailed description of the invention
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
As shown in Figure 1, the integrated conduct method of tail gas in a kind of mercury chloride production process, comprises the following steps:
(1) natural subsidence: tail gas is passed in sedimentation dashpot, mercury chloride powder in tail gas is after Temperature fall enrichment, utilize bottom himself gravity natural subsidence to sedimentation dashpot, then the object-discharging pipe bottom sedimentation dashpot drops in airtight concentrated groove, the material in groove is concentrated in regular removing, as Product recycling;
(2) dissolving with hydrochloric acid: the tail gas after sedimentation is passed in hydrochloric acid absorption tower, adopt the mode of top spray counterflow exchange, absorb in tail gas and remain mercury chloride, then pump in the catalyst soaking compartment in mercuric chloride catalyst workshop by the hydrochloric acid solution being dissolved with mercury chloride, the dissolving Recycling Mother Solution as catalyst uses;
(3) acid mist is trapped: passed into by the tail gas after absorption by Hydrochloric Acid in acid mist trapping tower, the hydrochloric acid mist be mixed in trapping tail gas, formation acid flows automatically in hydrochloric acid absorption tower after dripping and concentrating, and recycles;
(4) alkali liquor absorption: the tail gas after trapping is pumped in alkali liquor absorption groove (alkali liquor absorption groove is the sodium hydroxide solution of 15% built with mass fraction) by jet pump and reacts, reaction temperature≤40 DEG C, obtain byproduct clorox, after residual exhaust detection is up to standard, is directed at 25m chimney stack through mozzle and arranges outward.
Embodiment 1
7.2 × 10 are created in mercury chloride production process
7m
3tail gas, wherein Hg chloride content is 0.00986g/m
3, chlorine content is 0.83g/m
3, passed into by tail gas in sedimentation dashpot, reclaimed the mercury chloride of 709.29kg after natural subsidence, now in tail gas, the content of mercury chloride is 9.9 × 10
-6g/m
3; Pass in hydrochloric acid absorption tower by the tail gas after sedimentation again, absorb in tail gas and remain mercury chloride, then pump in the catalyst soaking compartment in mercuric chloride catalyst workshop by the hydrochloric acid solution being dissolved with mercury chloride, the dissolving Recycling Mother Solution as catalyst uses; Tail gas after absorption by Hydrochloric Acid is passed in acid mist trapping tower, the hydrochloric acid mist be mixed in trapping tail gas, formed after acid droplet is concentrated and flow automatically in absorption tower, recycle; Tail gas after trapping is pumped in alkali liquor absorption groove (alkali liquor absorption groove is the sodium hydroxide solution of 15% built with mass fraction) by jet pump and reacts, reaction temperature≤40 DEG C, in course of reaction, use 444.79 tons, NaOH altogether, obtain byproduct clorox 507.004 tons, also containing chlorine 0.008g/m in remaining tail gas
3, tail gas clean-up rate is 99.04%, detect up to standard after, 25m chimney stack is arranged outward.
Embodiment 2
2.592 × 10 are created in mercury chloride production process
7m
3tail gas, wherein Hg chloride content is 1 × 10
-5g/m
3, chlorine content is 0.05g/m
3, passed into by tail gas in sedimentation dashpot, reclaimed the mercury chloride of 259kg after natural subsidence, now in tail gas, the content of mercury chloride is 7.716 × 10
-6g/m
3; Pass in hydrochloric acid absorption tower by the tail gas after sedimentation again, absorb in tail gas and remain mercury chloride, then pump in the catalyst soaking compartment in mercuric chloride catalyst workshop by the hydrochloric acid solution being dissolved with mercury chloride, the dissolving Recycling Mother Solution as catalyst uses; Tail gas after absorption by Hydrochloric Acid is passed in acid mist trapping tower, the hydrochloric acid mist be mixed in trapping tail gas, formed after acid droplet is concentrated and flow automatically in absorption tower, recycle; Tail gas after trapping is pumped in alkali liquor absorption groove (alkali liquor absorption groove is the sodium hydroxide solution of 15% built with mass fraction) by jet pump and reacts, reaction temperature≤40 DEG C, in course of reaction, use 1.46 tons, NaOH altogether, obtain byproduct clorox 11 tons, also containing chlorine 9.645 × 10 in remaining tail gas
-6g/m
3, tail gas clean-up rate is 99.98%, detect up to standard after, 25m chimney stack is arranged outward.
Embodiment 3
5.9 × 10 are created in mercury chloride production process
7m
3tail gas, wherein Hg chloride content is 0.00486g/m
3, chlorine content is 0.53g/m
3, passed into by tail gas in sedimentation dashpot, reclaimed the mercury chloride of 285.3063kg after natural subsidence, now in tail gas, the content of mercury chloride is 2.43 × 10
-6g/m
3; Pass in hydrochloric acid absorption tower by the tail gas after sedimentation again, absorb in tail gas and remain mercury chloride, then pump in the catalyst soaking compartment in mercuric chloride catalyst workshop by the hydrochloric acid solution being dissolved with mercury chloride, the dissolving Recycling Mother Solution as catalyst uses; Tail gas after absorption by Hydrochloric Acid is passed in acid mist trapping tower, the hydrochloric acid mist be mixed in trapping tail gas, formed after acid droplet is concentrated and flow automatically in absorption tower, recycle; Tail gas after trapping is pumped in alkali liquor absorption groove (alkali liquor absorption groove is the sodium hydroxide solution of 15% built with mass fraction) by jet pump and reacts, reaction temperature≤40 DEG C, in course of reaction, use 34.6 tons, NaOH altogether, obtain byproduct clorox 262 tons, also containing chlorine 0.008g/m in remaining tail gas
3, tail gas clean-up rate is 98.17%, detect up to standard after, 25m chimney stack is arranged outward.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. the integrated conduct method of tail gas in mercury chloride production process, is characterized in that, comprise the following steps:
(1) natural subsidence: tail gas is passed in sedimentation dashpot, mercury chloride powder in tail gas is after Temperature fall enrichment, utilize bottom himself gravity natural subsidence to sedimentation dashpot, then the object-discharging pipe bottom sedimentation dashpot drops in airtight concentrated groove, the material in groove is concentrated in regular removing, as Product recycling;
(2) dissolving with hydrochloric acid: the tail gas after sedimentation is passed in hydrochloric acid absorption tower, absorb in tail gas and remain mercury chloride, then pump in the catalyst soaking compartment in mercuric chloride catalyst workshop by the hydrochloric acid solution being dissolved with mercury chloride, the dissolving Recycling Mother Solution as catalyst uses;
(3) acid mist is trapped: passed into by the tail gas after absorption by Hydrochloric Acid in acid mist trapping tower, the hydrochloric acid mist be mixed in trapping tail gas, formation acid flows automatically in hydrochloric acid absorption tower after dripping and concentrating, and recycles;
(4) alkali liquor absorption: pumped in alkali liquor absorption groove by jet pump by the tail gas after trapping and react, obtain byproduct clorox, residual exhaust detects rear outer row up to standard.
2. the integrated conduct method of tail gas in mercury chloride production process according to claim 1, it is characterized in that, in described step (2), hydrochloric acid absorption tower adopts the mode of top spray hydrochloric acid counterflow exchange to absorb.
3. the integrated conduct method of tail gas in mercury chloride production process according to claim 1, it is characterized in that, in described step (4), alkali liquor absorption groove is the sodium hydroxide solution of 15% built with mass fraction.
4. the integrated conduct method of tail gas in mercury chloride production process according to claim 1, is characterized in that, reaction temperature≤40 DEG C in described step (4) in alkali liquor absorption groove.
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| CN103550989B true CN103550989B (en) | 2015-10-28 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085904A (en) * | 2014-07-18 | 2014-10-08 | 贵州大龙银星汞业有限责任公司 | Method for decomposing sodium hypochlorite |
| CN104084026B (en) * | 2014-07-18 | 2016-01-27 | 贵州大龙银星汞业有限责任公司 | The processing method of chloride tail gas in a kind of mercury chloride production |
| CN104971552A (en) * | 2015-07-10 | 2015-10-14 | 四川宏达股份有限公司 | Method for removing dust from ammonium dihydrogen phosphate tail gas during wet phosphoric acid guniting production |
| CN114682243A (en) * | 2022-04-12 | 2022-07-01 | 内蒙古圣龙大地科技有限公司 | Method for preparing mercury-free catalyst by adding dichloroethane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101053752A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method for removing mercury in flue gas |
| CN101455974A (en) * | 2008-12-29 | 2009-06-17 | 万山特区红晶汞业有限公司 | Tail-gas comprehensive utilization method in mercuric chloride catalyst |
| CN202555136U (en) * | 2012-05-05 | 2012-11-28 | 长葛市九州化工有限公司 | Tail gas purification device for mercuric chloride catalyst production |
| CN102942211A (en) * | 2012-11-19 | 2013-02-27 | 新疆天业（集团）有限公司 | Method for recycling mercury from mercury-containing solid wastes |
-
2013
- 2013-10-16 CN CN201310484440.4A patent/CN103550989B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101053752A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method for removing mercury in flue gas |
| CN101455974A (en) * | 2008-12-29 | 2009-06-17 | 万山特区红晶汞业有限公司 | Tail-gas comprehensive utilization method in mercuric chloride catalyst |
| CN202555136U (en) * | 2012-05-05 | 2012-11-28 | 长葛市九州化工有限公司 | Tail gas purification device for mercuric chloride catalyst production |
| CN102942211A (en) * | 2012-11-19 | 2013-02-27 | 新疆天业（集团）有限公司 | Method for recycling mercury from mercury-containing solid wastes |
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Effective date of registration: 20190529 Address after: 554001 Mayintang, Dalong Economic Development Zone, Tongren City, Guizhou Province Patentee after: GUIZHOU ZHONGLI TECHNOLOGY ENVIRONMENT PROTECTION CO., LTD. Address before: 550000 17th Floor, Jingxie Building, Qiandao Street, Guiyang City, Guizhou Province Patentee before: GUIZHOU DALONG MERCURY SILVER STAR INDUSTRY CO., LTD. |
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Address after: 554300 mayintang, Dalong Economic Development Zone, Tongren City, Guizhou Province Patentee after: Guizhou gravity technology environmental protection Co.,Ltd. Address before: 554001 Mayintang, Dalong Economic Development Zone, Tongren City, Guizhou Province Patentee before: GUIZHOU GRAVITY TECHNOLOGY ENVIRONMENTAL PROTECTION CO.,LTD. |
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