CN106673055B - The recovery method of useless mercury catalyst in a kind of generated by polyvinyl chloride by calcium carbide production - Google Patents
The recovery method of useless mercury catalyst in a kind of generated by polyvinyl chloride by calcium carbide production Download PDFInfo
- Publication number
- CN106673055B CN106673055B CN201611149476.7A CN201611149476A CN106673055B CN 106673055 B CN106673055 B CN 106673055B CN 201611149476 A CN201611149476 A CN 201611149476A CN 106673055 B CN106673055 B CN 106673055B
- Authority
- CN
- China
- Prior art keywords
- mercury
- chloride
- recovery
- mercury catalyst
- generated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The recovery method of useless mercury catalyst, comprises the following steps in being produced the invention provides a kind of generated by polyvinyl chloride by calcium carbide：The useless mercury catalyst that mercury chloride, hydrogen chloride and vinyl chloride are adsorbed with activated carbon is crushed to certain fineness；Extraction with carbon disulfide is used again, is filtrated to get filter residue；Then filter residue is first heated under the conditions of lucifuge and condenses recovery mercury chloride afterwards；Remaining filter residue alkali process, the hydrogen chloride of absorption is neutralized, filtered, dried, recovered carbon；There is advantages below with the recovery method of the present invention：Heating-up temperature is low when reclaiming mercury chloride, it is only necessary to is carried out at 90 120 DEG C, and the rate of recovery is up to 95%, high purity 99.5%；Purity is high after treatment for the activated carbon of recovery, and the rate of recovery is up to 92%, recovers adsorption activity, and micro pore surface area returns to 1000 1200m2/ g, void content return to 0.3 0.6ml/g；Other this method is simple to operate, energy consumption reduces, green pollution-free, moreover it is possible to effectively removes organic substance and the hydrochloric acid materials such as vinyl chloride.
Description
Technical field
The present invention relates to catalyst recycling field, and in particular to give up mercury catalyst in a kind of generated by polyvinyl chloride by calcium carbide production
Recovery method.
Background technology
In generated by polyvinyl chloride by calcium carbide production process, acetylene and hydrogen chloride are used as raw material, and mercury chloride and activated carbon are to urge
Agent, carry out catalytic reaction and carry out synthesis vinyl chloride thereof monomer, then polymerization of vinyl choride monomer forms polyvinyl chloride.With catalytic reaction
Progress, the Hg chloride content easily to distil in activated carbon is reduced to less than 4%, while because having adsorbed excess in activated carbon hole
Raw material hydrogen chloride gas and product vinyl chloride, catalyst gradually inactivate.It is primary as requirement of the China to environmental protection is increasingly strict
State mercury resource is fewer and fewer, it is necessary to be reclaimed to useless mercury catalyst.Mercury catalyst recovery of giving up in the prior art is typically will be useless
The mercury catalyst first boiling together with limewash, mercury chloride is converted into mercury oxide, then mercury oxide is turned into single through 700-800 DEG C of high temperature
Matter mercury, this kind of method rate of recovery low only 57% or so, and energy consumption is big；Also have and poisonous chlorine time is passed through in heating process
Mercury and mercury chloride are received, mercury-containing waste water is caused again after the processing of last gas from dry distillation tail, pollutes environment；It is not right in the prior art in addition
The organic substance and hydrochloric acid material of charcoal absorption are effectively removed, and influence to reclaim the quality of material.
Therefore, how to solve these problems, it has also become those skilled in the art's technical barrier urgently to be resolved hurrily.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided mercury catalysis of being given up in a kind of generated by polyvinyl chloride by calcium carbide production
The recovery method of agent, solves above-mentioned technical problem.
To achieve these goals, the present invention provides following technical scheme：Give up mercury in a kind of generated by polyvinyl chloride by calcium carbide production
The recovery method of catalyst, comprises the following steps：
（1）Useless mercury catalyst is first crushed to certain fineness, the useless mercury catalysis system refer to be adsorbed with activated carbon mercury chloride,
The decaying catalyst of hydrogen chloride and vinyl chloride；
（2）Useless mercury catalyst after above-mentioned crushing is removed into vinyl chloride with extraction with carbon disulfide, is filtrated to get filter residue；
（3）Above-mentioned filter residue is heated under the conditions of lucifuge and obtains chlorination mercuryvapour, then condensation recovery mercury chloride solid；
（4）By remaining filter residue alkali process after above-mentioned recovery mercury chloride, the hydrogen chloride of absorption is neutralized, is filtered, is dried, is returned
Receive activated carbon.
As a further improvement on the present invention, step（1）Described in give up in mercury catalyst containing mass fraction be respectively 2-
The vinyl chloride of 3.8% mercury chloride, 0.5-1% hydrogen chloride and 0.1-0.4%.
As a further improvement on the present invention, step（1）Described in give up mercury catalyst crush after fineness be 40-80 mesh,
Other organic matters such as the contact area of useless mercury catalyst and extractant carbon disulfide, the vinyl chloride adsorbed in activated carbon can be increased
It is easier to be dissolved in carbon disulfide；More preferably 60 mesh, fineness block filter opening when easily causing filtering more than 80 mesh, and fineness is small
It is not high by extraction with carbon disulfide rate in 40 mesh, organic matter vinyl chloride.
As a further improvement on the present invention, step（2）Described in give up mercury catalyst be with carbon disulfide mass volume ratio
1：1.5-3 more preferably 1:2.2, make useless mercury catalyst be easier to be infiltrated by carbon disulfide, and extraction dosage is suitable, saves
Resource.
As a further improvement on the present invention, step（3）Described under the conditions of lucifuge heating-up temperature be 90-120 DEG C, add
The hot time is 30-120min, makes mercury chloride rapid sublimation, recovery is rapid, and lucifuge condition can avoid mercury chloride from being partially converted into
Calogreen, the rate of recovery are up to 95%, and recovery product purity is up to 99.5%.
As a further improvement on the present invention, step（3）Described in condensation temperature be 10-25 DEG C, condensation temperature is lower, more
Be advantageous to chlorination mercuryvapour and be changed into solid to separate out recovery, when temperature is higher than 25 DEG C, the mercury chloride rate of recovery is low, and it is at room temperature
Slowly distillation；When temperature is less than 10 DEG C, energy consumption increase.
As a further improvement on the present invention, step（4）Described in alkali be metal hydroxides, metal carbonate or metal
Bicarbonate, for the hydrogen chloride adsorbed in neutralization activity charcoal；The metal carbonate is preferably sodium carbonate, potassium carbonate, described
Alkali metal bicarbonate salt is preferably sodium acid carbonate, saleratus, and the metal hydroxides is preferably sodium hydroxide, potassium hydroxide,
More preferably mass fraction be 20-54% sodium hydrate aqueous solution, excessive concentration, when reaching hypersaturated state, part hydroxide
Sodium particle separates out the micro channel that can be blocked in activated carbon；Sodium hydrate aqueous solution volume is larger when concentration is too low, adds pair
The requirement of equipment volume or batch operation add processing time.
Compared with prior art, given up in generated by polyvinyl chloride by calcium carbide production of the invention mercury catalyst recovery method have with
Lower advantage：Heating-up temperature is low when reclaiming mercury chloride, it is only necessary to is carried out at 90-120 DEG C, and the rate of recovery is up to 95%, high purity
99.5%；Purity is high after treatment for the activated carbon of recovery, and the rate of recovery is up to 92%, recovers adsorption activity, and micro pore surface area is recovered
To 1000-1200m2/ g, void content return to 0.3-0.6ml/g；Other this method is simple to operate, energy consumption reduces, green ring
Protect pollution-free, moreover it is possible to effectively remove organic substance and the hydrochloric acid materials such as vinyl chloride.
Embodiment
With reference to specific embodiment, the present invention is expanded on further, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention；In addition, it is to be understood that after present disclosure has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values also fall within appended claims limited range.
Embodiment 1：
The recovery method of useless mercury catalyst, comprises the following steps in a kind of generated by polyvinyl chloride by calcium carbide production：
（1）It is 40 mesh that the useless mercury catalysts of first 100g, which are crushed to fineness, and the useless mercury catalysis system, which refers to, is adsorbed with 2% on activated carbon
The decaying catalyst of mercury chloride, 1% hydrogen chloride and 0.4% vinyl chloride；
（2）Useless mercury catalyst after above-mentioned crushing is removed into vinyl chloride with 150ml extraction with carbon disulfide, is filtrated to get filter
Slag；
（3）Above-mentioned filter residue is heated to 90 DEG C under the conditions of lucifuge, distillation 120min obtains chlorination mercuryvapour, then 18
Condensation recovery obtains the mercury chloride solid that 1.92g purity is 99.5%, the rate of recovery 96% at DEG C；
（4）At the sodium hydrate aqueous solution for being 20% with 120g mass fractions by remaining filter residue after above-mentioned recovery mercury chloride
Reason, filtering, dried at 80 DEG C, recovery obtains 88.9g activated carbons, the rate of recovery 92%, and its micro pore surface area returns to
1000m2/ g, void content return to 0.3ml/g.
Embodiment 2：
The recovery method of useless mercury catalyst, comprises the following steps in a kind of generated by polyvinyl chloride by calcium carbide production：
（1）It is 80 mesh that the useless mercury catalysts of first 100g, which are crushed to fineness, and the useless mercury catalysis system refers to be adsorbed with activated carbon
The decaying catalyst of 3.8% mercury chloride, 0.5% hydrogen chloride and 0.1% vinyl chloride；
（2）Useless mercury catalyst after above-mentioned crushing is removed into vinyl chloride with 300ml extraction with carbon disulfide, is filtrated to get filter
Slag；
（3）Above-mentioned filter residue is heated to 120 DEG C under the conditions of lucifuge, distillation 30min obtains chlorination mercuryvapour, then 10
Condensation recovery obtains the mercury chloride solid that 3.69g purity is 99.6%, the rate of recovery 97% at DEG C；
（4）At the sodium hydrate aqueous solution for being 54% with 80g mass fractions by remaining filter residue after above-mentioned recovery mercury chloride
Reason, filtering, dried at 80 DEG C, recovery obtains 88.9g activated carbons, the rate of recovery 93%, and its micro pore surface area returns to
1200m2/ g, void content return to 0.6ml/g.
Embodiment 3：
The recovery method of useless mercury catalyst, comprises the following steps in a kind of generated by polyvinyl chloride by calcium carbide production：
（1）It is 60 mesh that the useless mercury catalysts of first 100g, which are crushed to fineness, and the useless mercury catalysis system refers to be adsorbed with activated carbon
The decaying catalyst of 2.9% mercury chloride, 0.7% hydrogen chloride and 0.2% vinyl chloride；
（2）Useless mercury catalyst after above-mentioned crushing is removed into vinyl chloride with 220ml extraction with carbon disulfide, is filtrated to get filter
Slag；
（3）Above-mentioned filter residue is heated to 105 DEG C under the conditions of lucifuge, distillation 75min obtains chlorination mercuryvapour, then 25
Condensation recovery obtains the mercury chloride solid that 2.76g purity is 99.5%, the rate of recovery 95% at DEG C；
（4）At the sodium hydrate aqueous solution for being 35% with 105g mass fractions by remaining filter residue after above-mentioned recovery mercury chloride
Reason, filtering, dried at 80 DEG C, recovery obtains 88.5g activated carbons, the rate of recovery 92%, and its micro pore surface area returns to
1108m2/ g, void content return to 0.46ml/g.
Claims (8)
1. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production, it is characterised in that comprise the following steps：
（1）It is 40-80 mesh that useless mercury catalyst first is crushed into fineness, and the useless mercury catalyst, which refers to, is adsorbed with chlorination on activated carbon
The decaying catalyst of mercury, hydrogen chloride and vinyl chloride；
（2）Useless mercury catalyst after above-mentioned crushing is removed into vinyl chloride with extraction with carbon disulfide, is filtrated to get filter residue；
（3）Above-mentioned filter residue is heated under the conditions of lucifuge and obtains chlorination mercuryvapour, the heating-up temperature is 90-120 DEG C, during heating
Between be 30min-120min, then condensation recovery mercury chloride solid；
（4）By remaining filter residue alkali process after above-mentioned recovery mercury chloride, the hydrogen chloride of absorption is neutralized, is filtered, is dried, recovery is lived
Property charcoal.
2. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production according to claim 1, its feature
It is：Step（1）Described in give up in mercury catalyst containing mass fraction be respectively 2-3.8% mercury chloride, 0.5-1% hydrogen chloride
With 0.1-0.4% vinyl chloride.
3. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production according to claim 1, its feature
It is：Step（1）Described in give up mercury catalyst crush after fineness be 60 mesh.
4. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production according to claim 1, its feature
It is：Step（2）Described in give up mercury catalyst and carbon disulfide mass volume ratio be 1：1.5-3g/mL.
5. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production according to claim 4, its feature
It is：Step（2）Described in give up mercury catalyst and carbon disulfide mass volume ratio be 1：2.2 g/mL.
6. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production according to claim 1, its feature
It is：Step（3）Described in condensation temperature be 10-25 DEG C.
7. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production according to claim 1, its feature
It is：Step（4）Described in alkali be metal hydroxides, metal carbonate or alkali metal bicarbonate salt.
8. the recovery method for the mercury catalyst that given up in a kind of generated by polyvinyl chloride by calcium carbide production according to claim 7, its feature
It is：The metal hydroxides is the sodium hydrate aqueous solution that mass fraction is 20-54%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611149476.7A CN106673055B (en) | 2016-12-14 | 2016-12-14 | The recovery method of useless mercury catalyst in a kind of generated by polyvinyl chloride by calcium carbide production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611149476.7A CN106673055B (en) | 2016-12-14 | 2016-12-14 | The recovery method of useless mercury catalyst in a kind of generated by polyvinyl chloride by calcium carbide production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106673055A CN106673055A (en) | 2017-05-17 |
| CN106673055B true CN106673055B (en) | 2018-01-12 |
Family
ID=58868343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611149476.7A Active CN106673055B (en) | 2016-12-14 | 2016-12-14 | The recovery method of useless mercury catalyst in a kind of generated by polyvinyl chloride by calcium carbide production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106673055B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097583B (en) * | 2018-08-22 | 2020-11-17 | 昆明理工大学 | Method for cleanly and efficiently recovering waste low-mercury catalyst |
| CN114229843A (en) * | 2021-12-24 | 2022-03-25 | 贵州重力科技环保有限公司 | Method for activating and regenerating waste activated carbon after harmless treatment of waste mercury catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102814173A (en) * | 2012-08-03 | 2012-12-12 | 长葛市九州化工有限公司 | Waste active carbon mercury catalyst recovery process |
| CN102962033B (en) * | 2012-11-23 | 2014-12-10 | 那风换 | Method for synchronously recovering mercuric chloride, metal salt and active carbon in spent catalyst |
| CN104138767B (en) * | 2013-05-07 | 2016-10-05 | 贵州省万山银河化工有限责任公司 | Useless mercuric chloride catalyst activation recovery method |
| CN104451154A (en) * | 2014-11-14 | 2015-03-25 | 北京化工大学 | New technology for recovering mercury in mercury-containing catalyst by wet method |
-
2016
- 2016-12-14 CN CN201611149476.7A patent/CN106673055B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106673055A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2561625C2 (en) | Method of separating and purifying sodium sulphide | |
| CN105170108B (en) | A kind of rice husk cellulose adsorbent and its preparation method and application | |
| CA3072438C (en) | Non-destructive process for removing metals, metal ions and metal oxides from alumina-based materials | |
| CN103803638A (en) | Method for recycling waste mercury catalyst | |
| CN106340692A (en) | A kind of method that cleaning reclaims lithium in positive electrode | |
| CN104232900A (en) | Method for recovering palladium from waste palladium/alumina catalyst | |
| CN106673055B (en) | The recovery method of useless mercury catalyst in a kind of generated by polyvinyl chloride by calcium carbide production | |
| CN104878208B (en) | Recovery method for palladium and ruthenium in catalytic combustion catalyst Pd-Ru/alumina | |
| CN106565956A (en) | Method for comprehensive recycling of by-product slurry in polyphenylene sulfide productive process | |
| CN110590012B (en) | Resource utilization method of deep defluorination resin desorption solution | |
| CN103395925A (en) | Treatment method for recycling para-hydroxybenzoic acid wastewater | |
| CN108641023B (en) | Mercury-free polyvinyl chloride production process | |
| CN110668403A (en) | Continuous production method of insoluble sulfur | |
| CN105349790B (en) | The method of cobalt and manganese in the high manganese waste material of low cobalt is separated and recovered with ammonia ammonium hydrogen carbonate | |
| CN105296763B (en) | The method of cobalt and manganese in the high manganese waste material of low cobalt is separated and recovered with ammonia ammonium carbonate | |
| CN102078804A (en) | System technology for recycling oil-containing waste diatomite in aluminum industry | |
| CN108609661B (en) | Method for preparing iron oxide red, aluminum oxide and gallium by using iron-removing resin eluent | |
| CN111573641A (en) | Method for co-producing nitric acid and silver from electrode foil waste liquid | |
| CN110605106A (en) | Regeneration method of waste mercury catalyst activated carbon after harmless treatment | |
| CN105668597A (en) | Method of acid-alkali combined extraction of aluminum-based products and silicon-based products from fly ash | |
| CN110563016B (en) | Method for treating waste gas containing fluorine and chlorine by using white tungsten slag | |
| CN106565581A (en) | A method for comprehensive recovery and utilization of lithium containing mixed salts in a polyphenylene sulfide production process | |
| CN113666376A (en) | Recycling treatment method for silicon slag | |
| CN113800549A (en) | Method for extracting barium chloride from precipitated barium sulfate waste residue | |
| CN105349789B (en) | The method of cobalt and manganese in the high manganese waste material of low cobalt is separated and recovered with ammonia sodium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |