CN104438285B - Method for innocent treatment of waste mercury catalyst by mechanical ball milling with sulfur as additive - Google Patents
Method for innocent treatment of waste mercury catalyst by mechanical ball milling with sulfur as additive Download PDFInfo
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- CN104438285B CN104438285B CN201410641749.4A CN201410641749A CN104438285B CN 104438285 B CN104438285 B CN 104438285B CN 201410641749 A CN201410641749 A CN 201410641749A CN 104438285 B CN104438285 B CN 104438285B
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Abstract
The invention relates to a method for mechanical ball-milling harmless treatment of waste mercury catalyst by taking sulfur as an additive, belonging to the technical field of harmless treatment of mercury-containing waste, and specifically comprising the following steps: firstly, uniformly mixing a waste mercury catalyst and sublimed sulfur according to a mass ratio of 1:8, wherein mercury chloride (HgCl) in the mercury catalyst2) The content of (A) is 4.0-7.0%; and secondly, adding the waste mercury catalyst and the sublimed sulfur which are uniformly mixed in the first step into a stainless steel closed ball milling tank of a ball mill for ball milling reaction, wherein the ball-material ratio is 40:1, the ball milling rotating speed is 550r/min, the reaction time is 2 hours, the toxicity leaching value of mercury is lower than the hazardous waste standard limit value (0.2mg/L) of the United states environmental protection department and the hazardous waste identification standard limit value (0.1mg/L) of China, and the solidification and stabilization of the waste mercury catalyst can be realized. The method can solve the problem of environmental pollution caused by a large amount of waste mercury catalysts generated in the production process of PVC by a calcium carbide method, and has the characteristics of high treatment speed, simple process, safe operation, high efficiency and environmental protection.
Description
Technical Field
The invention belongs to the field of mercury-containing hazardous waste management and safe disposal, relates to a waste mercury catalyst generated in the process of producing polyvinyl chloride (PVC) by a calcium carbide method through a mechanochemical method, and particularly relates to a method for performing mechanical ball milling harmless treatment on the waste mercury catalyst by taking sulfur as an additive.
Background
The mercuric chloride catalyst is a catalyst for the reaction of acetylene and hydrogen chloride in the industry of producing polyvinyl chloride by a calcium carbide method. The waste mercury catalyst produced by the method has leaching toxicity and corrosivity, and the concentration of leached mercury exceeds the fixation in the nonferrous metal industry solid waste pollution standard. China is the largest calcium carbide PVC producing country in the world, and the data show that the yield of calcium carbide PVC is 1512 ten thousand t in 2013, which accounts for about 82% of the total PVC yield in China. The mercury chloride catalyst used in the method is the product with the maximum production in the industry and the product with the maximum mercury consumption. The production of PVC by calcium carbide method accounts for 60% of the total mercury consumption in China and 30% of the mercury consumption in the world. The amount of waste mercury catalyst generated per year is about 1.1 ten thousand tons, and the generation amount is increased at a speed of 10% -15% per year. In addition, the waste mercury catalyst recycling system in the calcium carbide method PVC industry is imperfect at present, and the recovery amount of mercury is less than 1/3.
The countermeasure suggestion of accelerating the structure adjustment due to the excess of chemical decomposition and productivity in the chlor-alkali industry indicates that a high-industrial catalyst (the mass fraction of mercury chloride is more than 6.5%) and a calcium carbide method PVC production device using the high-industrial catalyst are limited in 2015. With the development of olefin preparation from coal and olefin preparation from methanol, the sources of ethylene are more extensive, and impact can be caused to the production industry of PVC by a calcium carbide method. In addition, the development of mercury-free catalysts will gradually replace mercury chloride catalysts. At that time, a large amount of waste mercury catalysts are generated to cause huge environmental pressure, and great threat is formed to the health and ecological safety of people.
The large inventory of spent mercury catalyst releases a large amount of mercury contaminants in the surrounding environment, which are mainly present in three forms: elemental mercury compounds, inorganic mercury compounds, and organic mercury compounds. Mercury is one of the most toxic compounds, and its toxicity depends mainly on the form in which it exists in the environment. The metal mercury has high vapor pressure, is easily absorbed into human body, enters the vascular system, is rapidly distributed in the human body, and is oxidized into divalent mercury (Hg) with high activity2+). Exposure to high doses of inorganic mercury can damage the human gastrointestinal tract, nervous system, and renal system. Mercury contaminants also form stable organomercury compounds with organics under certain circumstances. Compared with inorganic mercury, the organic mercury has stronger fluidity, biological accumulation and toxicity. In particular, methyl mercury is formed which rapidly passes through the cell membrane, and studies by Clarkson and Lacerda et al indicate that mercury and its compounds impair the development of the infant's nervous system and the adult's general nervous system.
Since mercury has adverse effects on human health and the environment, laws and regulations are made at home and abroad to limit the supply and application of mercury. Therefore, large excess amounts of mercury as well as mercury-containing waste require safe disposal. The national environmental protection ministry of China also requires mercury-related enterprises to treat the wastes harmlessly so as to avoid polluting surrounding atmosphere, water and soil. At present, the main treatment method of the mercury-containing waste comprises the following steps: amalgam, heat treatment, glass curing, soil elution, sulfur polymer stabilization curing, mercury sulfide formation, chemical bonding of phosphor ceramics, and other sequestration processes. At present, the stable solidification method is a recommended method for treating mercury-containing waste and has good treatment effect. These techniques have problems of high cost, complicated technique, incomplete fixation of mercury in the mercury-containing waste, and possibility of secondary pollution.
The ball milling method is also called mechanochemical method, and is characterized by that it utilizes the physical and chemical properties of material and its structure conversion caused by mechanical force, and utilizes the measures of shearing, friction, impact and extrusion to make the condensed material of solid and liquid produce active surface, promote mass transfer and induce chemical reaction. Different from common thermochemical reaction, the mechanochemical reaction has mechanical energy rather than heat energy, so that the reaction can be completed without harsh conditions of high temperature, high pressure and the like. Alopez et al, a spanish scientist, primarily used a mechanical ball milling process to convert metallic mercury into mercury sulfide, thereby achieving the harmless treatment of mercury waste. The literature research shows that no report on the harmless treatment technology of mercuric chloride and waste mercury catalyst exists at present. In view of the huge production amount, low recycling and regeneration utilization rate and serious secondary pollution of the waste mercury catalyst in China, the development of environment-friendly and efficient harmless treatment technology and process for curing and stabilizing the waste mercury catalyst is urgently needed.
Disclosure of Invention
Based on the advantages of a mechanochemical method, the invention creatively provides a method for harmless treatment of the waste mercury catalyst by mechanical ball milling by taking sulfur as an additive, the toxic leaching value of mercury in the treated waste mercury catalyst is lower than the hazardous waste standard (0.2mg/L) of the United states department of environmental protection and the national hazardous waste identification standard (0.1mg/L), and the method has the characteristics of simple, safe and flexible operation and the like.
The technical scheme adopted by the invention is as follows: :
firstly, uniformly mixing the waste mercury catalyst and the sublimed sulfur according to the mass ratio of 1:8
And secondly, adding the waste mercury catalyst and the sublimed sulfur which are uniformly mixed in the first step into a stainless steel closed ball-milling tank of a ball mill for ball-milling reaction, wherein the ball-material ratio is 40:1, the ball-milling rotating speed is 550r/min, and the reaction time is 2 hours.
The mass ratio of the sublimed sulfur to the mercury catalyst is 8:1, the ball-material ratio is 40:1, the ball milling rotating speed is 550r/min, and the sublimed sulfur and the mercury catalyst are carried out under the conditions of normal temperature and normal pressure in a sealed stainless steel ball milling tank under the air atmosphere.
After the ball milling reaction is finished, the ball milling tank can be directly opened in the air, and a batch of processing samples can be replaced.
The invention has the following advantages:
1) the reaction time is short, the treatment efficiency is high, and the mercury fixation rate reaches more than 99.9%;
2) after the waste mercury catalyst is treated by a mechanical ball milling method, the toxic leaching value of mercury is lower than the hazardous waste identification standard (0.2mg/L) of the United states department of environmental protection and the hazardous waste identification standard (0.1mg/L) of China, and the waste mercury catalyst can be converted into common waste from hazardous waste;
2) the mercury of the mercury catalyst is converted into mercury sulfide after treatment, and the mercury with the most stable form in the nature
3) The used sublimed sulfur is easy to obtain, the cost is low, and the source is wide;
4) the operation is simple, the reaction condition is mild, high-temperature heating is not needed, and the energy consumption for treatment is reduced.
Drawings
Fig. 1 is a comparison of the toxic leaching values of mercury after mechanical ball milling under different mass ratios of mercury catalyst to sublimed sulfur, wherein the ball milling time is 12 hours, the ordinate is the leaching value of mercury after the toxic leaching test, and the abscissa indicates the mass ratio of mercury catalyst to sublimed sulfur, and the toxic leaching values of mercury are given in 6 different mass ratios of mercury, such as 1:1, 1:2, 1:4, 1:8, 1:20, 1:40, respectively. Wherein: the ball milling time is 12 hours, the ball material ratio is 40:1, the rotating speed is 550r/min, the air atmosphere, and the material of the milling pot milling ball is stainless steel.
Fig. 2 is a graph showing the influence of the toxicity leaching values of mercury in different ball milling reaction times when the mass ratio of the mercury catalyst to the sublimed sulfur is 1:8 in the first example, wherein the abscissa is the ball milling time in minutes, and the ordinate is the leaching value of mercury in a ball-milled sample after the toxicity leaching test. Wherein: the mass ratio of the mercury catalyst to the sublimed sulfur is 1:8, the ball-material ratio is 40:1, the rotating speed is 550r/min, the material quality of the grinding pot grinding ball is stainless steel under air atmosphere.
Fig. 3 is mercury fixation efficiency calculated according to a formula based on the toxicity leaching values of mercury for different ball milling reaction times when the mass ratio of the mercury catalyst to the sublimed sulfur is 1:8 in the first example, wherein the abscissa is the ball milling time in minutes, and the ordinate is the fixation rate of mercury. Wherein: the mass ratio of the mercury catalyst to the sublimed sulfur is 1:8, the ball-material ratio is 40:1, the rotating speed is 550r/min, the material quality of the grinding pot grinding ball is stainless steel under air atmosphere.
SRTo fix the efficiency; vuThe toxicity leaching value of a sample which is not subjected to ball milling treatment is shown; vtToxicity leaching values for samples treated with different ball milling times.
FIG. 4 is an XRD diffraction analysis chart of the mixed powder after ball milling for 12 hours under different mass ratios of mercury catalyst and sublimed sulfur in the first example. When the mass ratio of the mercury catalyst to the sublimed sulfur is 1:2, mercury sulfide appears. In other ball-milled samples, the diffraction peak of sulfur was predominant due to excess sulfur. After ball milling, the mercury chloride-loaded active structure is destroyed and converted into amorphous carbon, so that no corresponding peak appears on an XRD diffraction pattern.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example one
Mixing a mercury catalyst and sublimed sulfur according to the mass ratio of 1:1, 1:2, 1:4, 1:8, 1:20 and 1:40 respectively to obtain ball milling reactants, adding 6g of the ball milling reactants and 14 stainless steel balls with the diameter of 15mm and the weight of 15g into each stainless steel ball milling tank, wherein the effective volume of each ball milling tank is 250ml, and the ball milling tanks and the ball milling covers are sealed by elastic O-rings. The rotating speed of the ball mill is set to be 550r/min, and the ball milling time is set to be 12 h.
Mixing the mercury catalyst and the sublimed sulfur according to the mass ratio of 1:8 to obtain ball-milling reactants, adding 6g of the ball-milling reactants and 14 stainless steel balls with the diameter of 15mm and the weight of 15g into each stainless steel ball-milling tank, wherein the effective volume of each ball-milling tank is 250ml, and the ball-milling tanks and the ball-milling covers are sealed by elastic O-rings. Setting the rotation speed of the ball mill to be 550r/min, and setting the ball milling time to be 15min, 30min, 45min, 60min, 90min, 105min, 120min and 240min respectively.
And taking out the ball-milled powder after different ball milling time, and analyzing according to the toxicity leaching characteristic step (TCLP) formulated by the U.S. environmental protection agency. Weighing 1.0g of powder after ball milling, adding TCLP #1 extracting solution, stirring for 18h at normal temperature, filtering to fix the volume to 100ml, and measuring mercury in the extracting solution by using ICP-OES. After ball milling for 2 h. The leaching value of mercury is lower than 0.1mg/L, and the fixation rate of mercury is more than 99%.
In conclusion, after the method is used, mercury in the mercury catalyst is converted into mercury sulfide, and the method is high in treatment speed, simple and safe in operation process and environment-friendly in process.
Claims (2)
1. A method for mechanical ball-milling harmless treatment of waste mercury catalyst by taking sulfur as an additive comprises the following steps:
step one, uniformly mixing a waste mercury catalyst and sublimed sulfur according to a mass ratio of not more than 1:8, wherein the content of mercury in the waste mercury catalyst is 4.0-7.0%;
and secondly, adding the uniformly mixed waste mercury catalyst and sublimed sulfur in the first step into a stainless steel closed ball-milling tank of a ball mill for mechanochemical reaction, wherein the ball-material ratio is 40:1, the ball-milling rotating speed is 550r/min, and the reaction time is 2 hours.
2. The method for harmless treatment of waste mercury catalyst by mechanical ball milling with sulfur as additive according to claim 1, wherein the method comprises the following steps: the ball milling is carried out under the conditions of normal temperature and normal pressure in a sealed stainless steel ball milling tank under the air atmosphere, wherein the ball-material ratio is 40:1, and the ball milling rotating speed is 550 r/min.
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| CN110526215A (en) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | A kind of method of synthesizing black mercuric sulphide |
| CN110526278B (en) * | 2019-08-26 | 2023-01-24 | 浙江工业大学 | Method for synthesizing red mercuric sulfide at low temperature by using mechanical ball milling method |
| 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 |
Citations (4)
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|---|---|---|---|---|
| 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 |
| CN104032138A (en) * | 2014-06-05 | 2014-09-10 | 东北大学 | Method for treating mercury-contained tailings by heap leaching-precipitate stabilization |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2355001B1 (en) * | 2009-09-09 | 2012-01-25 | Consejo Superior De Investigaciones Científicas (Csic) | LIQUID MERCURY STABILIZATION PROCEDURE THROUGH POLYMERIC CEMENT OF SULFUR, VIA SULFURO DE MERCURIO |
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Patent Citations (4)
| 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 |
| 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 |
| CN104032138A (en) * | 2014-06-05 | 2014-09-10 | 东北大学 | Method for treating mercury-contained tailings by heap leaching-precipitate stabilization |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Formation of metacinnabar by milling of liquid mercury and elemental sulfur;F.A. López等;《Science of the Total Environment》;20100731;第4341–4345页 * |
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