CN104138706B - A kind of HCl recovery mercuric chloride produces the method for tail gas - Google Patents
A kind of HCl recovery mercuric chloride produces the method for tail gas Download PDFInfo
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- CN104138706B CN104138706B CN201310164587.5A CN201310164587A CN104138706B CN 104138706 B CN104138706 B CN 104138706B CN 201310164587 A CN201310164587 A CN 201310164587A CN 104138706 B CN104138706 B CN 104138706B
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- tail gas
- mercuric chloride
- hydrargyrum
- chlorine
- hydrochloric acid
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Abstract
The invention discloses a kind of method that HCl recovery mercuric chloride produces tail gas, chlorine and hydrargyrum react generation mercuric chloride, and the tail gas after settling at least one times and reclaiming mercuric chloride is through dilute hydrochloric acid jet cleaning, then discharges after alkali liquor absorption.The present invention is according to the feature of tail gas, the physicochemical properties of each component of ingenious utilization, use dilute hydrochloric acid jet cleaning tail gas, on the one hand by improving gas-to-liquid contact raising to the absorption of chlorine in tail gas, the hypochlorous acid making the chlorine in tail gas be dissolved in water generation can react with the hydrargyrum in tail gas, thus reclaim hydrargyrum, on the other hand hydrochloric acid can improve dissolution rate and the dissolution velocity of mercuric chloride, absorb the mercuric chloride in tail gas, hydrargyrum, chlorine etc., and absorbing liquid is used for catalyst immersion, the hydrochloric acid of excess can absorb partial impurities in activated carbon, improve catalyst quality, thus turn waste into wealth, reduce environmental pollution.
Description
Technical field
The present invention relates to a kind of mercury oxide production technology, particularly relate to a kind of method that HCl recovery mercuric chloride produces tail gas.
Background technology
The polrvinyl chloride that China's carbide produces accounts for the 63% of total amount.Generated by polyvinyl chloride by calcium carbide industry use mercury catalyst about 7000 tons,
About 770 tons of mercuric chloride, hydrargyrum about 570 tons, account for more than half of mercury in China consumption figure, be consumption hydrargyrum row Chinese or even the biggest in the world
Industry.By 2012, China's generated by polyvinyl chloride by calcium carbide yield about reached 10,000,000 tons, and mercury catalyst consumption is up to 1.2 ten thousand tons,
The consumption of hydrargyrum will be more than 1000 tons.Carbide produces the production of polrvinyl chloride and causes a large amount of mercury emissions.And along with China is to environment
Increasingly paying attention to and the restriction of international hydrargyrum pact of protection, in the urgent need to recovery and the recycle utilization of research and development hydrargyrum, to save hydrargyrum
Resource and protection environment.
In former mercuric chloride production technology, hydrargyrum and chlorine react in quartz rice steamer: Hg+Cl2=HgCl2, chlorination is reclaimed in the condensation of cooled tower
After hydrargyrum, tail gas about 10.0m3(mark state)/h, except the HgCl carried secretly containing non-total condensation and gas2Outside steam, dust, containing about
Hg10.00g/m3, Cl2 249.59g/m3.This waste gas discharges behind water stream injection pump, alkali liquor absorption pond.The main work of water stream injection pump
With being to provide negative pressure, the effect that hydrargyrum is reclaimed in its washing is undesirable, and the hydrargyrum of alkali liquor absorption is the most recyclable.The shortcoming of prior art is:
Mercuric chloride and hydrargyrum, chlorine in tail gas rely primarily on alkali liquor absorption, low to the absorbance of hydrargyrum, form hazardous waste after Alkali absorption,
Not only cause the waste of resource, increase refuse processing cost, and cause environmental pollution.
Summary of the invention
It is an object of the invention to provide a kind of method that HCl recovery mercuric chloride produces tail gas, reclaim the HgCl in tail gas2With Hg, Cl2,
Reduce mercuric chloride and produce the impact on environment, make mercuric chloride produce and realize qualified discharge.
The technical scheme of invention is: a kind of HCl recovery mercuric chloride produces the method for tail gas, and chlorine and hydrargyrum react generation mercuric chloride,
Tail gas after settling at least one times and reclaiming mercuric chloride is through dilute hydrochloric acid jet cleaning, then discharges after alkali liquor absorption.
The concentration of described dilute hydrochloric acid is 5%-10% mass concentration.
The described washing absorption liquid formed after dilute hydrochloric acid jet cleaning soaks for catalyst.Reach to reclaim mercuric chloride, improve catalyst
The purpose of quality.
Described chlorine first preheats before reacting with hydrargyrum.
Described chlorine is that the waste heat reacted by reclaiming chlorine and hydrargyrum preheats.
The amount of the described chlorine reacted with hydrargyrum that is that be passed through exceedes the amount needed for theory.
The amount of the described chlorine reacted with hydrargyrum that is that be passed through exceedes amount 5%-10% needed for theory.
Described chlorine waste heat reacted with hydrargyrum reclaims by being arranged on the coil of the outlet of the device that chlorine and hydrargyrum react.
Contacting of tail gas and dilute hydrochloric acid solution is increased by a device during described dilute hydrochloric acid jet cleaning.
Described device is screen cloth.
Beneficial effect: the present invention, according to the feature of tail gas, the physicochemical properties of each component of ingenious utilization, uses dilute hydrochloric acid injection
Washing tail gas, one side improves the absorption of chlorine in tail gas by improving gas-to-liquid contact, makes the chlorine in tail gas be dissolved in water and produces
Hypochlorous acid can react with the hydrargyrum in tail gas, thus reclaim hydrargyrum and chlorine, on the other hand hydrochloric acid can improve the dissolution rate of mercuric chloride
And dissolution velocity, absorb the mercuric chloride in tail gas, hydrargyrum, chlorine etc..
The washing absorption liquid of hydrochloric acid can be directly used for mercuric chloride and dissolves, and soaks Activated Carbon Production mercury catalyst, the hydrochloric acid solubilized of excess
The partial impurities of activated carbon, improves catalyst quality, thus fully achieves mercuric chloride, hydrargyrum, the recovery of chlorine in tail gas and combine
Close utilization rate.
By the present invention in that chlorine preheating suitable excess, to improve the conversion ratio of hydrargyrum, to reduce Elemental Mercury content in tail gas.
The mercuric chloride exhaust purifying method small investment of the present invention, simple to operate, it is possible not only to make expensive mercuric chloride and hydrargyrum return
Yield improves, and essentially eliminates the hydrargyrum pollution to environment in exhaust emissions, it is achieved qualified discharge.According to producing 400 tons of chlorine per year
Changing hydrargyrum, be about 99.5% through statistics mercuric chloride productivity, tail gas recycle rate calculates with 80%, every year from the recyclable mercuric chloride of tail gas about
1.6 tons, by 500,000 yuan/ton of calculating, produce a profit 800,000 yuan, reduce charges for disposing pollutants, hazardous waste processing cost simultaneously.
Accompanying drawing explanation
Fig. 1 is the method flow diagram of the HCl recovery mercuric chloride production tail gas of the embodiment of the present invention 1.
Detailed description of the invention
The present invention will be described in detail with embodiment below in conjunction with the accompanying drawings.
Embodiment 1
As it is shown in figure 1, the method that the HCl recovery mercuric chloride of the present invention produces tail gas, as follows:
Hydrargyrum and chlorine (excess 5%-10%) directly gas phase reaction are generated mercuric chloride.Reaction equation is as follows:
Hg+Cl2=HgCl2
First Gas-phase reactor (quartz rice steamer) is heated to about 360 DEG C with electric furnace, then by a small amount of for the chlorine dried with sulphuric acid
It is passed through in reactor, prevents superpressure and reaction from heating up too fast, when reaction temperature rises to 500 DEG C, add mercury metal, and control
Uniform temperature, after be passed through the chlorine being dried through sulphuric acid, chlorine and hydrargyrum kickback promote temperature to rise to 900～1000 DEG C, chlorine logical
Enter amount than theoretical amount excess 5%-10%, to prevent the generation of calomel.The chlorine coil being enclosed within reactor outlet reclaims
Waste heat preheats so that it is response speed is accelerated, to save the consumption of chlorine.The HgCl that reaction generates2Gas, Jing Guochen
HgCl can be formed after fall2Crystal reclaims, and sedimentation can be that once sedimentation can also repeatedly settle, as it is shown in figure 1, cold through pottery
But sedimentation tower forms crystal, is deposited at the bottom of tower, discharging opening release, metering packing.Tail gas after cooling-sedimentation tower can be again
After settler reclaims mercuric chloride further remaining tail gas enter ejector pump carry out dilute hydrochloric acid cyclic spray washing, dilute hydrochloric acid by
Water pump is input in ejector pump from circulating water pool.The chlorine of excess and uncooled mercuric chloride steam and mercuric chloride dust warp in tail gas
Dilute hydrochloric acid jet cleaning is cooled to 40 DEG C, during this, utilizes the chlorine in tail gas to be dissolved in the hypochlorous acid that water produces, residual with trace
Remaining hydrargyrum reaction, can improve the recovery of hydrargyrum.(chlorine and the hydrargyrum that enter alkali cleaning can not directly reclaim.) following equation:
Cl2+H2O=HClO+HCl
2Hg+2HClO=H2O+HgCl2·HgO
On the other hand, during this, hydrochloric acid can also improve dissolubility and the dissolution velocity of mercuric chloride, reclaims the effect of mercuric chloride
Fruit is preferably.The dilute hydrochloric acid solution of chloride containing hydrargyrum send catalyst production line mercuric chloride dissolving tank to recycle.Through dilute hydrochloric acid jet cleaning
After tail gas can carry out injection process through the venturi water stream injection pump shown in Fig. 1, after the alkali liquor absorption dechlorination removal of mercury is up to standard, by 15m
Aiutage discharges, and alkali liquor can be input in venturi water stream injection pump spray by pump by circulation alkali pond.After above-mentioned process
The gas Cl of discharge2Discharge reaches " discharge standard of air pollutants " (GB16297-1996) secondary standard, and mercury emissions reaches
To " industrial furnace atmosphere pollutants emission standards " (GB9078-1996) secondary standard.
The waste gas produced when package metro-measuring from cooling-sedimentation tower discharging opening mercuric chloride out is arranged after activated carbon adsorber again
Put.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, but is provided with a screen cloth (not shown) in circulating water pool, forms water
Film is for increasing the gas-to-liquid contact of tail gas and dilute hydrochloric acid solution, to improve dissolution rate and the dissolution velocity of mercuric chloride, and chlorine
Absorb.The intake pressure and the flow that optimize ejector pump improve the absorption of chlorine in tail gas to improve gas-to-liquid contact simultaneously.
Claims (3)
1. the method that HCl recovery mercuric chloride produces tail gas, chlorine and hydrargyrum react generation mercuric chloride, it is characterised in that through extremely
The most once the tail gas after sedimentation recovery mercuric chloride is through dilute hydrochloric acid jet cleaning, and when being cooled to 40 DEG C, then discharge after alkali liquor absorption；
Wherein, when temperature rises to 500 DEG C in Gas-phase reactor, add hydrargyrum, and control by the chlorine after preheating after uniform temperature,
To generate mercuric chloride；
The concentration of described dilute hydrochloric acid is 5%-10% mass concentration；
The amount of the described chlorine reacted with hydrargyrum being passed through exceedes amount 5%-10% needed for theory；
The described washing absorption liquid formed after dilute hydrochloric acid jet cleaning soaks for catalyst；
Contacting of tail gas and dilute hydrochloric acid solution is increased by a device during described dilute hydrochloric acid jet cleaning；
Described device is screen cloth.
HCl recovery mercuric chloride the most according to claim 1 produces the method for tail gas, it is characterised in that described chlorine is logical
Cross and reclaim the waste heat that chlorine and hydrargyrum reacts and preheat.
HCl recovery mercuric chloride the most according to claim 2 produces the method for tail gas, it is characterised in that described chlorine and hydrargyrum
Reacted waste heat reclaims by being arranged on the coil of the outlet of the device that chlorine and hydrargyrum react.
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Families Citing this family (3)
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| CN108034808B (en) * | 2017-12-13 | 2019-05-21 | 江西理工大学 | A method of the selective recovery mercury from melting waste slag |
| CN114345083A (en) * | 2021-11-30 | 2022-04-15 | 济南鲁洪环保材料有限公司 | Automatic tail gas collecting method for cuprous chloride process |
| CN114797414B (en) * | 2022-05-18 | 2023-06-06 | 中南大学 | Liquid-phase oxidation mercury removal method for activating peroxymonosulfate by using chloride ions |
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| US6638485B1 (en) * | 1997-02-19 | 2003-10-28 | Mitsubishi Heavy Industries, Ltd. | Process for treating exhaust gas and exhaust gas treating equipment |
| 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 |
| CN102115148A (en) * | 2010-12-28 | 2011-07-06 | 何侠 | Method for preparing silver chloride and coproducing mercuric oxide and aluminum nitrate by using mercury-containing dead catalyst |
| CN102516022A (en) * | 2011-12-06 | 2012-06-27 | 中南大学 | Comprehensive processing method of vinyl chloride synthetic gas |
| 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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2013
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| US6638485B1 (en) * | 1997-02-19 | 2003-10-28 | Mitsubishi Heavy Industries, Ltd. | Process for treating exhaust gas and exhaust gas treating equipment |
| 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 |
| CN102115148A (en) * | 2010-12-28 | 2011-07-06 | 何侠 | Method for preparing silver chloride and coproducing mercuric oxide and aluminum nitrate by using mercury-containing dead catalyst |
| CN102516022A (en) * | 2011-12-06 | 2012-06-27 | 中南大学 | Comprehensive processing method of vinyl chloride synthetic gas |
| 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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