CN104438285A - Method for carrying out innocent treatment on waste mercury catalyst by mechanical ball milling via taking sulfur as additive - Google Patents
Method for carrying out innocent treatment on waste mercury catalyst by mechanical ball milling via taking sulfur as additive Download PDFInfo
- Publication number
- CN104438285A CN104438285A CN201410641749.4A CN201410641749A CN104438285A CN 104438285 A CN104438285 A CN 104438285A CN 201410641749 A CN201410641749 A CN 201410641749A CN 104438285 A CN104438285 A CN 104438285A
- Authority
- CN
- China
- Prior art keywords
- mercury
- mercury catalyst
- ball
- ball milling
- waste
- 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.)
- Granted
Links
Landscapes
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for carrying out innocent treatment on a waste mercury catalyst by mechanical ball milling via taking sulfur as an additive, belonging to the technical field of mercury-containing waste innocent treatment. The method concretely comprises the following steps: 1, evenly mixing the waste mercury catalyst and sublimed sulfur according to the mass ratio of 1 to 8, wherein the content of mercuric chloride (HgCl2) in the waste mercury catalyst is 4.0-7.0%; 2, feeding the waste mercury catalyst and the sublimed sulfur which are evenly mixed in the step 1 into a closed stainless steel ball milling tank of a ball mill, and carrying out a ball-milling reaction to enable the ball-to-powder weight ratio to be 40 to 1, wherein the ball-milling rotating speed is 550 revolutions per minute, and the reaction time is 2 hours. After the waste mercury catalyst is treated by the method, the toxicity leaching value of mercury is lower than the hazardous waste standard limited value (0.2mg/L) of the Ministry of Environmental Protection of the United States and the national hazardous waste identification standard limited value (0.1mg/L) of China, so that solidification and stabilization of the waste mercury catalyst can be realized. After the method is used, the problem of environmental pollution caused by a great deal of waste mercury catalysts produced in the process of producing polyvinyl chloride (PVC) by a calcium carbide method can be solved; the method has the characteristics of being rapid in treatment speed, simple in process, safe to operate, efficient and environment-friendly.
Description
Technical field
The invention belongs to mercurous refuse harmlessness disposing technical field, relate to mechanochemical reaction effective, harmless process carbide and produce in polyvinyl chloride (PVC) process the useless mercury catalyst produced, being specifically related to a kind of is that the harmless treatment of additive machinery ball milling is given up the method for mercury catalyst with sulphur.
Background technology
Mercuric chloride catalyst is the catalyst that carbide produces acetylene and hcl reaction in PVC industry.Its useless mercury catalyst produced has Leaching and corrosivity, and its mercury concentration leached exceedes fixing in " non-ferrous metals industry solid waste pollution standard ".China is calcium carbide process PVC producing country maximum in the world, and it is 1,512 ten thousand t that data is presented at calcium carbide process PVC production capacity in 2013, accounts for 82% of the total PVC production capacity in the whole nation.And the mercuric chloride catalyst that it is used be product that in industrial and commercial bank's industry, output is maximum is also consume the maximum product of mercury quantity.Calcium carbide process PVC is produced and is accounted for 60% of the total mercury use of China, accounts for 30% of world's mercury consumption.The useless mercury catalyst of annual generation is at about 1.1 ten thousand tons, and generation is with the speed increase of annual 10%-15%.In addition, useless mercury catalyst Recycling and reuse system imperfection in current calcium carbide process PVC industry, the yield of mercury is less than 1/3.
National Development and Reform Committee points out will encourage to adopt coal ethene, builds process for oxychlorination vinyl chloride process units, reduces the ratio of production of vinyl chloride by calcium carbide method gradually.Point out senior engineer's catalyst (mercury chloride mass fraction more than 6.5%) in " chlor-alkali industry dissolves the countermeasure and suggestion that production capacity surplus is accelerated restructuring " and use the calcium carbide process PVC process units of senior engineer's catalyst will be limited in 2015.Along with the development of olefin hydrocarbon making by coal, methanol-to-olefins, the source of ethene is more extensive, can impact calcium carbide process PVC manufacture.In addition, the research and development without mercury catalyst also progressively will substitute mercuric chloride catalyst.When the time comes, produce a large amount of useless mercury catalysts and cause huge environmental pressure, grave danger is formed to the health of people and ecological safety.
A large amount of stackings of the mercury catalyst after discarded can be crossed in environment in week and be discharged mercury contaminants in a large number, and these pollutants mainly exist with three kinds of forms: elemental mercury compounds, inorganic mercury compound and organomercurial compound.Mercury is one of several compounds that toxicity is the strongest, and its toxicity depends primarily on mercury existence form in the environment.Mercury metal has higher vapor pressure, is very easily inhaled into human body intravasation system and is distributed in inside of human body fast, is then oxidized to active very high bivalent mercury (Hg
2+).The inorganic mercury being exposed to high dose can damage the intestines and stomach of people, nervous system and renal system.Mercury contaminants also can form stable organomercurial compound with organic matter in certain circumstances.Relative to inorganic mercury, organic mercury mobility, bioaccumulation, toxicity are stronger.Especially the methyl mercury formed, can quickly through cell membrane, and the research of the people such as Clarkson and Lacerda shows, mercury and and compound can damage the neural growth of infant and the summary nervous system of adult.
Because mercury causes adverse effect to human health and environment, laws and regulations are formulated both at home and abroad to limit supply and the application of mercury.Therefore, a large amount of excessive mercury and mercurous refuse need safe disposal.National environmental protection portion of China also requires She Gong enterprise its discarded object of harmless treatment, avoids the air, the water and soil that pollute periphery.At present, mercurous refuse main methods comprises: amalgamation, heat treating process, glass solidification method, soil elution method, sulphur polymer stabilizing solidification method, formed mercuric sulphide method, phosphorus pottery chemical bonding processes and other seal technique up for safekeeping.At present, stable curing method is the method that the mercurous refuse of process is recommended, and has good disposal effect.These technology Problems existing costs are high, mercury in technical sophistication, mercurous refuse can not be completely fixed and may produce secondary pollution etc.
Ball-milling method is also known as mechanochemical reaction, the physicochemical properties of material and the transformation of structure thereof that are caused by mechanical force, by means such as shearing, friction, impact, extruding, the condensed state matter such as solid, liquid is made to produce active surface, promote mass transfer, and induced chemical reaction.Different from ordinary hot chemical reaction, the power of mechanico-chemical reaction is mechanical energy and non-thermal energy, and thus reaction need not the harsh conditions such as high temperature, high pressure can complete, simultaneously mechanochemical reaction simple to operate, flexible, the advantage such as degradation rate is fast in addition.The people such as Hispanic scientist F.A Lopez tentatively use mechanical attrition method mercury metal to be converted into mercuric sulphide, achieve the innoxious of mercury refuse.Literature survey shows, does not also have the report in mercury chloride and useless mercury catalyst innoxious process for treating at present.In view of China's mercury catalyst generation that gives up is huge, recovery and reusing and recycling rate is lower, and secondary pollution is serious, is badly in need of useless mercury catalyst solidification and stabilization harmlessness disposing technology and the technique of exploitation environment-friendly high-efficiency at present.
Summary of the invention
Based on the advantage of mechanochemical reaction, it is that the ball milling harmless treatment of additive machinery is given up the method for mercury catalyst with sulphur that the present invention creatively proposes a kind of, the toxicity leaching value having processed mercury in rear useless mercury catalyst, lower than the hazardous waste standard (0.2mg/L) in Environmental Protection in America portion and China national hazardous waste judging standard (0.1mg/L), has the features such as simple to operate, safe, flexible.
The technical scheme of employing of the present invention is:
The first step, mixes useless mercury catalyst and sublimed sulfur with mass ratio 1:8
Second step, the useless mercury catalyst first step mixed and sublimed sulfur join in the stainless steel closed ball milling tank of ball mill and carry out ball-milling reaction, and use ratio of grinding media to material is 40:1, and rotational speed of ball-mill is 550r/min, and the reaction time is 2 hours.
Described sublimed sulfur and mercury catalyst are with mass ratio 8:1, and ratio of grinding media to material is 40:1, and rotational speed of ball-mill is 550r/min, carries out under air atmosphere in airtight stainless steel jar mill under normal temperature and pressure conditions.
After described ball-milling reaction terminates, directly can open ball grinder in atmosphere, change a collection for the treatment of samples.
Tool of the present invention has the following advantages:
1) reaction time is short, and treatment effeciency is high, and the fixed rate of mercury reaches more than 99.9%;
2) useless mercury catalyst is after mechanical attrition method process, the toxicity leaching value of mercury is lower than the hazardous waste judging standard (0.2mg/L) in Environmental Protection in America portion and China national hazardous waste judging standard (0.1mg/L), and useless mercury catalyst can transfer household waste to by hazardous waste;
2) mercury of mercury catalyst transfers to for mercuric sulphide after the treatment, the form mercury that nature is the most stable
3) sublimed sulfur used is easy to get, and cost is low, wide material sources;
4) simple to operate, reaction condition is gentle, does not need high-temperature heating, reduces process energy consumption.
Accompanying drawing explanation
Fig. 1 be at different mercury catalysts with sublimed sulfur quality than in situation, the contrast of the toxicity leaching value of mercury after machinery ball milling, wherein Ball-milling Time is 12 hours, ordinate be toxicity leaching test after the leaching value of mercury, abscissa represents different mercury catalysts and sublimed sulfur mass ratio, sets forth in figure 1:1,1:2,1:4,1:8,1:20,1:40 etc. 6 different quality than the toxicity leaching value of situation mercury.Wherein: Ball-milling Time is 12 hours, ratio of grinding media to material is 40:1, and rotating speed is 550r/min, air atmosphere, and grinding jar Material quality of grinding balls is stainless steel.
Fig. 2 be in embodiment one with the mass ratio of mercury catalyst and sublimed sulfur for 1:8 time, the impact of the toxicity leaching value of different ball-milling reaction time mercury, wherein abscissa is Ball-milling Time, and unit is minute, and ordinate is the leaching value of mercury in milled sample after toxicity leaching test.Wherein: the mass ratio of mercury catalyst and sublimed sulfur is 1:8, and ratio of grinding media to material is 40:1, and rotating speed is 550r/min, air atmosphere, and grinding jar Material quality of grinding balls is stainless steel.
Fig. 3 be in embodiment one with the mass ratio of mercury catalyst and sublimed sulfur for 1:8 time, based on the mercury fixed efficiency that the toxicity leaching value of different ball-milling reaction time mercury goes out according to formulae discovery, wherein abscissa is Ball-milling Time, and unit is minute, and ordinate is the fixed rate of mercury.Wherein: the mass ratio of mercury catalyst and sublimed sulfur is 1:8, and ratio of grinding media to material is 40:1, and rotating speed is 550r/min, air atmosphere, and grinding jar Material quality of grinding balls is stainless steel.
S
rfor fixed efficiency; V
ufor not through the toxicity leaching value of the sample of ball-milling treatment; V
tthrough the toxicity leaching value of the sample of different Ball-milling Time process.
Fig. 4 be in embodiment one at different mercury catalysts with sublimed sulfur quality than in situation, the XRD diffraction analysis figure of ball milling mixed powder after 12 hours.When the mass ratio of mercury catalyst and sublimed sulfur is 1:2, mercuric sulphide is had to occur.In other milled sample, because sulphur is excessive, the mainly diffraction maximum of sulphur.The active structure of the back loading mercury chloride of ball milling is destroyed is converted into agraphitic carbon, so do not have corresponding peak to occur on XRD diffraction spectrogram.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further details.
Embodiment one
Mercury catalyst is mixed as ball-milling reaction thing by 1:1,1:2,1:4,1:8,1:20,1:40 with the mass ratio of sublimed sulfur respectively, 6g ball-milling reaction thing is added and 14 diameters are 15mm in each stainless steel jar mill, weight is the stainless steel bead of 15g and ball grinder dischargeable capacity is 250ml, seals between ball grinder and ball milling lid with elastomeric O-type circle.Setting drum's speed of rotation is 550r/min, Ball-milling Time 12h.
Be that 1:8 is mixed as ball-milling reaction thing by mercury catalyst and the mass ratio of sublimed sulfur, 6g ball-milling reaction thing is added and 14 diameters are 15mm in each stainless steel jar mill, weight is the stainless steel bead of 15g and ball grinder dischargeable capacity is 250ml, seals between ball grinder and ball milling lid with elastomeric O-type circle.Setting drum's speed of rotation is 550r/min, Ball-milling Time for being respectively 15min, 30min, 45min, 60min, 90min, 105min, 120min, 240min.
After different Ball-milling Times, take out ball milling powder, analyze according to the toxicity leaching characteristic step (TCLP) that EPA formulates.Take powder after 1.0g ball milling, add TCLP#1 extract, stir 18h at normal temperatures, filter and be settled to 100ml, then measure the mercury in extract with ICP-OES.After ball milling 2h.The leaching value of mercury is lower than 0.1mg/L, and the fixed rate of mercury is greater than 99%.
In sum, after using the present invention, the mercury in mercury catalyst is converted into mercuric sulphide, is that a kind of processing speed is fast, simple and safe operation process, the method for process environmental protection.
Claims (4)
1. be that the ball milling harmless treatment of additive machinery is given up the method for mercury catalyst with sulphur, comprise the following steps:
The first step, will give up mercury catalyst and sublimed sulfur take mass ratio as 1:8 Homogeneous phase mixing, and wherein in useless mercury catalyst, the content of mercury is 4.0% ~ 7.0%;
Second step, the useless mercury catalyst first step mixed and sublimed sulfur join in the stainless steel closed ball milling tank of ball mill and carry out mechanico-chemical reaction, and use ratio of grinding media to material is 40:1, and rotational speed of ball-mill is 550r/min, and the reaction time is 2 hours.
2. according to claim 1 a kind of be that the ball milling harmless treatment of additive machinery is given up the method for mercury catalyst with sulphur, it is characterized in that additive used in ball milling is sublimed sulfur.
3. according to claim 1 a kind of be that the ball milling harmless treatment of additive machinery is given up the method for mercury catalyst with sulphur, it is characterized in that the mass ratio of the useless mercury catalyst of required process and sublimed sulfur is not higher than 1:8.
4. according to claim 1 a kind of be that the ball milling harmless treatment of additive machinery is given up the method for mercury catalyst with sulphur, it is characterized in that described ball milling uses ratio of grinding media to material to be 40:1, rotational speed of ball-mill is 550r/min, carries out in air atmosphere in airtight stainless steel jar mill under normal temperature and pressure conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410641749.4A CN104438285B (en) | 2014-11-06 | 2014-11-06 | Method for innocent treatment of waste mercury catalyst by mechanical ball milling with sulfur as additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410641749.4A CN104438285B (en) | 2014-11-06 | 2014-11-06 | Method for innocent treatment of waste mercury catalyst by mechanical ball milling with sulfur as additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104438285A true CN104438285A (en) | 2015-03-25 |
| CN104438285B CN104438285B (en) | 2019-12-24 |
Family
ID=52885478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410641749.4A Expired - Fee Related CN104438285B (en) | 2014-11-06 | 2014-11-06 | Method for innocent treatment of waste mercury catalyst by mechanical ball milling with sulfur as additive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104438285B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526278A (en) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | A method of red mercuric sulfide is synthesized using mechanical attrition method low temperature |
| CN110526215A (en) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | A kind of method of synthesizing black mercuric sulphide |
| CN111228711A (en) * | 2020-01-15 | 2020-06-05 | 扬州杰嘉工业固废处置有限公司 | Method for stabilizing and curing mercury-containing waste salt slag by using petrochemical waste alkali slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010086A (en) * | 2010-12-01 | 2011-04-13 | 新疆天业（集团）有限公司 | Method for treating mercury-containing wastewater with three-section continuous process |
| US20120322918A1 (en) * | 2009-09-09 | 2012-12-20 | Felix Antonio Lopez Gomez | Method for stabilising liquid mercury using sulfur polymer cement, via mercury sulfide |
| 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 |
| CN104032139A (en) * | 2014-06-05 | 2014-09-10 | 东北大学 | Method for recovering mercury from mercury-contained tailings through complexing extraction and consolidating decomposition |
| CN104032138A (en) * | 2014-06-05 | 2014-09-10 | 东北大学 | Method for treating mercury-contained tailings by heap leaching-precipitate stabilization |
-
2014
- 2014-11-06 CN CN201410641749.4A patent/CN104438285B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120322918A1 (en) * | 2009-09-09 | 2012-12-20 | Felix Antonio Lopez Gomez | Method for stabilising liquid mercury using sulfur polymer cement, via mercury sulfide |
| CN102010086A (en) * | 2010-12-01 | 2011-04-13 | 新疆天业（集团）有限公司 | Method for treating mercury-containing wastewater with three-section continuous process |
| 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 |
| CN104032139A (en) * | 2014-06-05 | 2014-09-10 | 东北大学 | Method for recovering mercury from mercury-contained tailings through complexing extraction and consolidating decomposition |
| CN104032138A (en) * | 2014-06-05 | 2014-09-10 | 东北大学 | Method for treating mercury-contained tailings by heap leaching-precipitate stabilization |
Non-Patent Citations (1)
| Title |
|---|
| F.A. LÓPEZ等: "Formation of metacinnabar by milling of liquid mercury and elemental sulfur", 《SCIENCE OF THE TOTAL ENVIRONMENT》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526278A (en) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | A method of red mercuric sulfide is synthesized using mechanical attrition method low temperature |
| CN110526215A (en) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | A kind of method of synthesizing black mercuric sulphide |
| CN111228711A (en) * | 2020-01-15 | 2020-06-05 | 扬州杰嘉工业固废处置有限公司 | Method for stabilizing and curing mercury-containing waste salt slag by using petrochemical waste alkali slag |
| CN111228711B (en) * | 2020-01-15 | 2021-08-06 | 扬州杰嘉工业固废处置有限公司 | Method for stabilizing and curing mercury-containing waste salt slag by using petrochemical waste alkali slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104438285B (en) | 2019-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | Photocatalytic reduction of U (VI) in wastewater by mGO/g-C3N4 nanocomposite under visible LED light irradiation | |
| CN101113067A (en) | Resourceful treatment method for oily sludge | |
| CN106282585A (en) | The detoxification classification resource utilization method of one way of life incineration of refuse flyash | |
| CN107159684B (en) | Domestic waste incineration fly ash and waste SCR catalyst co-treatment method | |
| CN104784863A (en) | Persulfate enhanced ball-milling treatment method of chemical waste | |
| Rashed et al. | Heavy metals removal from wastewater by adsorption on modified physically activated sewage sludge | |
| CN106348484A (en) | Novel deep mercury removal process | |
| CN101514037A (en) | Method for removing low-concentration heavy metal in waste water by sludge absorption | |
| CN104438285A (en) | Method for carrying out innocent treatment on waste mercury catalyst by mechanical ball milling via taking sulfur as additive | |
| Zhang et al. | Removal of vanadium and chromium from vanadium wastewaters with amino-functionalized γ-AlOOH | |
| CN108341477A (en) | The method of Combined Treatment industrial emissions | |
| Li et al. | Preparation and application of red mud-based zero-valent iron heterogeneous Fenton catalyst: A new idea for red mud recycling | |
| CN102205340B (en) | Process for recycling incineration ash of hazardous wastes | |
| CN114405980A (en) | Method for comprehensively recycling municipal sludge incineration slag | |
| CN108555011B (en) | Carbonization remediation treatment system for volatile organic compound-heavy metal composite contaminated soil | |
| CN110252781A (en) | Rubbish three phase separation treatment process | |
| Hua et al. | Transforming industrial solid wastes into eco-friendly zeolite material for efficient heavy metal ion stabilization through host-guest combination | |
| Wang et al. | Behavior and mechanism of low-concentration rare earth ions precipitated by the microbial humic-like acids | |
| CN102688874B (en) | Mechanical dry sulfurization processing method for heavy metal waste residue | |
| CN215143308U (en) | Waste incineration fly ash resourceful treatment system | |
| Enslin et al. | Acid leaching of heavy metals from bentonite clay, used in the cleaning of acid mine drainage | |
| Huang et al. | Harnessing the power of nonthermal Plasma: A breakthrough in stabilizing Thallium contaminants in soil and unveiling the mechanism | |
| CN107381705B (en) | Method for separating and recovering multiple cationic heavy metals in water through phase change regulation | |
| Shu et al. | Migration and Transformation Behavior of Mn2+ and NH4+-N in Electrolytic Manganese Residue at Different Leaching pH Environments: Release Kinetic Model, Physical Phase Changes, and Formation of Manganese Oxide | |
| CN110642356A (en) | Method for treating heavy metal-containing wastewater by using modified expanded vermiculite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191224 Termination date: 20201106 |