CN115463950A - High-pressure dehydration method for water-containing material - Google Patents
High-pressure dehydration method for water-containing material Download PDFInfo
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- CN115463950A CN115463950A CN202211132784.4A CN202211132784A CN115463950A CN 115463950 A CN115463950 A CN 115463950A CN 202211132784 A CN202211132784 A CN 202211132784A CN 115463950 A CN115463950 A CN 115463950A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000000463 material Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000018044 dehydration Effects 0.000 title claims abstract description 42
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 42
- 239000002893 slag Substances 0.000 claims abstract description 118
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000011669 selenium Substances 0.000 claims abstract description 46
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 27
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 24
- 239000011593 sulfur Substances 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229910052738 indium Inorganic materials 0.000 claims abstract description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 16
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004321 preservation Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 39
- 229940091258 selenium supplement Drugs 0.000 description 38
- 208000005156 Dehydration Diseases 0.000 description 36
- 239000012071 phase Substances 0.000 description 27
- -1 polypropylene Polymers 0.000 description 27
- 239000004810 polytetrafluoroethylene Substances 0.000 description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 24
- 239000011133 lead Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000005485 electric heating Methods 0.000 description 10
- 150000001621 bismuth Chemical class 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 150000003342 selenium Chemical class 0.000 description 9
- 150000003463 sulfur Chemical class 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 150000002471 indium Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229960001881 sodium selenate Drugs 0.000 description 2
- 239000011655 sodium selenate Substances 0.000 description 2
- 235000018716 sodium selenate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/55—Slag
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a high-pressure dehydration method for a water-containing material, belonging to the field of metallurgy and chemical industry. The method comprises the steps of placing a water-containing material in a closed reaction kettle, heating to a preset temperature, stirring the water-containing material under the conditions of low oxygen or no oxygen at the preset temperature and the preset pressure under the conditions of heat preservation and pressure maintaining to form a liquid-liquid two phase or a solid-liquid two phase, and carrying out liquid-liquid separation or liquid-solid separation to obtain a dehydrated mineral material, wherein the water-containing material is selenium slag, bismuth slag, sulfur slag, sponge indium, tin slag, lead slag or copper-cadmium slag. The method is operated in a high-pressure closed environment, has the advantages of small environmental pollution, simple equipment, obvious dehydration effect and high product direct yield.
Description
Technical Field
The invention relates to a high-pressure dehydration method for a water-containing material, belonging to the field of metallurgy and chemical industry.
Background
When mineral materials containing certain moisture enter a preset process flow or an experimental step, the preset parameters of the mineral materials are changed due to higher moisture content, such as granularity, viscosity, melting point, heat conduction performance, electric conduction performance, magnetic performance and the like of the mineral materials, so that the feasibility of subsequent operation is influenced, the production environment is deteriorated, the difficulty of the process is increased, the energy consumption is increased, and even the yield of products is reduced.
For example, selenium is present in the crust at 0.05X 10 -6 It is generally extremely difficult to form industrial enrichments. The main raw material (90%) for extracting selenium in modern industry is anode mud generated by copper electrolytic refining, and the rest is calcine generated by lead, cobalt and nickel refining, residual mud generated by sulfuric acid production and the like. Because the selenium in the copper electrolysis anode mud is symbiotic with the noble metal in the form of selenium compound, and the content of the selenium is about 5-25 percent (mass fraction), the process generally comprises the steps of firstly recovering the noble metal gold and silver and then recovering the selenium, and a method of firstly recovering the selenium from the anode mud and then producing the gold-silver alloy can be adopted. There are two main methods for industrial production of selenium: one is to oxidize and roast the anode mud and SeO 2 Distillation by passing gaseous SeO 2 The roasting gas is captured in a scrubbing tower with a solution and then in SO 2 Precipitating in acidic medium or with alkaline solutionPrecipitating selenium; and the other method is to add soda ash into the oxidizing atmosphere to sinter the anode mud so as to convert the selenium into a sodium selenide or sodium selenate water-soluble solution, oxidize the selenium and selenide into sodium selenite or sodium selenate which is easily soluble in water under the sintering condition, and then separate the selenium from the solution by purging. The two methods can be used for preparing selenium aiming at different selenium-containing raw materials and have higher yield. However, the two methods have the problems that the water content of the initial raw material or the intermediate raw material is too high, so that the energy consumption is increased in the sintering or roasting link in the process, a plurality of byproducts are generated, the yield is reduced, and the like.
The existing dehydration treatment mainly comprises filter pressing, leaching, natural drying, vacuum dehydration and the like, and one or more treatment processes can be selected according to the properties of different materials for reasonable and efficient treatment. However, the actual dehydration rate is not high in the filter pressing, leaching and natural drying processes, or most of free water and part of crystal water can be removed; and the treated object is usually a material with higher water content and coarser granularity, and for the material with low water content and large specific surface area, because the tap density of the fine particles is high, a discharge channel of liquid water is lacked, the water removal is hindered, meanwhile, a large amount of capillary effect is easily formed among the fine particles, the dehydration difficulty is enhanced, and the dehydration effect is not obvious. The vacuum dehydration treatment of a small amount of water-containing slag has a good effect, but the problems of material spraying, slow heat transfer, high energy consumption, scaling of dehydration equipment and the like exist in large-scale application, so that the dehydration effect of the product after actual treatment is lower than expected.
Disclosure of Invention
Aiming at the difficult problems of unobvious dehydration effect, high energy consumption and the like in the dehydration process of the traditional process, the invention provides the method for dehydrating the water-containing material under high pressure, namely, the dehydration treatment of the water-containing material is realized under the condition of higher than atmospheric pressure, the operation is carried out under the high-pressure closed environment, the environmental pollution is small, the used equipment is simple, the dehydration effect is obvious, and the direct yield of the product is high; the separated high-temperature and high-pressure water can be used for a steam power generation system, so that energy conservation and environmental protection are realized.
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
heating the water-containing material in a closed reaction kettle to a preset temperature, keeping the temperature and pressure of the water-containing material at the preset temperature and the preset pressure in a low-oxygen or anaerobic state, stirring to form a liquid-liquid two phase or a solid-liquid two phase, and performing liquid-liquid separation or liquid-solid separation to obtain a dehydrated mineral material, wherein the water-containing material is selenium slag, bismuth slag, sulfur slag, sponge indium, tin slag, lead slag or copper-cadmium slag.
In the device in the method for high-pressure dehydration of the water-containing material, a closed reaction kettle can be selected from a hydro-thermal synthesis reaction kettle, a stainless steel reaction kettle, a magnetic stirring reaction kettle, an electric heating reaction kettle, a steel-lined ETFE reaction kettle and a PCF series small-scale test high-pressure kettle; preferably, the closed reaction kettle is a hydrothermal synthesis reaction kettle, a stainless steel reaction kettle or a magnetic stirring reaction kettle.
The closed reaction kettle can be lined by steel lining, titanium alloy, polypropylene, polyethylene, polytetrafluoroethylene and PPL, and the lining is preferably polytetrafluoroethylene or PPL.
The heating mode is determined according to the selected closed reaction kettle and can be electric heating, hot water heating, heat conduction oil circulating heating, external (internal) coil heating and the like; the cooling mode can be jacket cooling and in-kettle coil cooling; the stirring forms can be an anchor type, a paddle type, a turbine type, a propelling type, a frame type and the like, and when the height-diameter ratio of the stirring device is larger, a plurality of layers of stirring blades can be used.
And stirring for 1-12 h, preferably 1-8 h, under the condition of heat preservation and pressure maintaining.
The selenium slag contains 65-70% of selenium, 25-30% of water and 0-10% of other impurities by mass; when the water-containing material is selenium slag, the preset temperature is 200-250 ℃, and the preset pressure is 2-6 Mpa.
The bismuth slag contains 20-55% of bismuth by mass, 10-55% of water by mass and 25-35% of other impurities by mass; when the water-containing material is bismuth slag, the preset temperature is 250-290 ℃, and the preset pressure is 3-8 Mpa.
The sulfur slag comprises, by mass, 70-75% of sulfur, 10-20% of water and 5-30% of other impurities; when the water-containing material is sulfur slag, the preset temperature is 90-140 ℃, and the preset pressure is 101-400 KPa.
The mass fraction of indium in the sponge indium is 90-98%, the mass fraction of water is 2-10%, and the mass fraction of other impurities is 1-6%; when the water-containing material is sponge indium, the preset temperature is 140-170 ℃, and the preset pressure is 400-900 KPa.
The mass fraction of tin in the tin slag is 30-50%, the mass fraction of water is 5-15%, and the mass fraction of other impurities is 15-35%; when the water-containing material is tin dross, the preset temperature is 210-270 ℃, and the preset pressure is 200-700 KPa.
The mass fraction of lead in the lead slag is 20-55%, the mass fraction of water is 10-30%, and the mass fraction of other impurities is 5-15%; when the water-containing material is lead slag, the preset temperature is 300-350 ℃, and the preset pressure is 8-18 MPa.
The copper-cadmium slag contains 1.5-17% of copper, 2.5-12% of cadmium, 8-30% of water and 30-45% of other impurities by mass; when the water-containing material is copper-cadmium slag, the preset temperature is 300-340 ℃, and the preset pressure is 8-16 MPa.
The preset pressure is controlled by introducing inert gas and/or reducing gas, the inert gas is He, ne or Ar, and the reducing gas is CO or SO 2 Or H 2 。
The liquid-liquid separation equipment can be selected from a liquid-liquid separation tank, a liquid-liquid separation filter element, a decanter and a liquid-liquid centrifuge, and the liquid-solid separation equipment can be selected from a sieve plate, a coalescence plate, hydrophobic stainless steel and a plate-and-frame filter press.
The principle of high-pressure dehydration of water-containing materials is as follows:
based on a gas-liquid phase equilibrium principle, the boiling point of liquid is related to external pressure, on one hand, when liquid water molecules are boiled, the saturated vapor pressure in bubbles formed inside the liquid water molecules is equal to the pressure applied from the outside, and at the moment, the bubbles grow and rise; on the other hand, the liquid water jumps to the air to become gaseous water, and is forced to be impacted by other water vapor, and the gaseous water tends to become liquid, namely, the water is more difficult to gasify as the aggregated state is changed into a dispersed state in the water phase change process and the absorbed energy pressure is larger, so that the higher the pressure is, the higher the boiling point is. By means of pressurization, water is still in liquid form at temperatures above 100 ℃, and the water-containing material may have two situations: one is to form two liquid-liquid phases, in which water is in a liquid state, the slag is melted to form a liquid phase after reaching a melting point, and the liquid-liquid separation of the water-containing material is realized by the density difference between the slag phase and the water phase, so that the dehydration of the material is realized. The other is to form a liquid-solid two phase, at the moment, water is still in a liquid state, slag cannot reach a molten state in the heating and pressurizing process, but the slag is sintered in a high-temperature water system, small particles among the slag are gathered and grown, fine particles are changed into solid large particles, most of surface attached water and pore water are removed finally, and the water content is greatly reduced. According to the reaction kinetics and the thermodynamic principle, the small particles have small particle size, large specific surface area and more adsorption sites, and can have more surface attached water; meanwhile, the pores of the small particles are small, the capillary phenomenon is serious, and capillary water in the particles can be increased. The driving force for crystal grain growth is to reduce the total energy of the interface, and aggregation of small grains with large specific surface area into large grains with small specific surface area is a dynamic process;
the mineral materials are dehydrated in a heating and pressurizing mode, heat can be transferred in a heat conduction mode, heat conduction can be realized through convection between liquid water molecules and slag, and a gas phase can form strong convection and heat radiation conditions under a high pressure condition, so that heat transfer among the mineral materials is further enhanced, and the heat utilization rate is improved; the method improves the limit of the problems of slag phase heat conductivity coefficient, fluidity and the like on heat transfer, solves the problems of uneven temperature distribution of the water-containing material and high dehydration energy consumption, improves the utilization of heat energy, and prevents the problems of material spraying, slow heat transfer, equipment scaling and the like.
The invention has the beneficial effects that:
(1) Based on the gas-liquid phase equilibrium, the metallurgy thermodynamics and the kinetics principle, the invention utilizes a pressurizing method to keep water in a liquid state at high temperature and improve the exchange and transfer of heat among slag phases, the boiling point of the water is raised by high pressure, the water can still keep the liquid state at the temperature higher than 100 ℃, and the mineral materials and the water can generate a liquid-liquid two phase or a liquid-solid two phase when the melting point of the mineral materials is reached; for example, the selenium slag forms a liquid-liquid phase because the selenium reaches a melting point and melts and is immiscible with liquid water, so that water and selenium are fully separated; the mineral materials form a liquid-solid two phase, namely aggregation growth possibly occurs among small crystal particles in the heating and pressurizing process, so that large particles with small specific surface area are generated, and the adsorption to water is reduced; in both cases, the problems that the actual dehydration rate is not high, or only most of free water and part of crystal water can be removed and the like are effectively solved; in addition, under high temperature and high pressure, the heat transfer process is enhanced, the problems of scaling of dehydration equipment with slow heat transfer, high energy consumption and high material spraying rate when a large amount of water-containing slag is treated are solved, and the dehydration effect of the actually treated product is lower than the expected dilemma;
(2) The method not only solves the problems that most of free water and part of crystal water can be removed, but also can effectively overcome the problems that the energy consumption is high, the dehydration effect of the product after actual treatment is lower than expected, and the like, realizes the dehydration treatment of the water-containing material under the condition higher than atmospheric pressure, operates in a high-pressure closed environment, has little environmental pollution, simple equipment, obvious dehydration effect and high product direct yield; the separated high-temperature and high-pressure water can be used for a steam power generation system, so that the energy conservation and environmental protection are realized, and the large-scale industrial popularization and application are facilitated.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the hydrous material of this example is selenium slag, the composition is shown in table 1,
TABLE 1 composition of selenium slag
| Composition (A) | Se | Water (W) | Impurities |
| Content (%) | 65 | 30 | 5 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of selenium slag, pouring the selenium slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a closed reaction kettle (stainless steel reaction kettle), electrically heating to 210 ℃ at a preset temperature, introducing an inert gas Ar to regulate the pressure to 3.5MPa, keeping the temperature and pressure of a water-containing material (selenium slag) at 210 ℃ at 3.5MPa at the preset temperature and under 3.5MPa for 6 hours under anaerobic condition, stirring for 6 hours to form a solid-liquid two phase, and separating by a solid-liquid separation device (sieve plate) to obtain dehydrated selenium slag;
in this example, the mass of the dehydrated selenium slag was 716g, the water content of the dehydrated selenium slag was 2.2%, and the direct yield of selenium was 91%.
Example 2: the aqueous material of this example was selenium slag with the composition shown in table 2,
TABLE 2 composition of selenium slag
| Composition (I) | Se | Water (W) | Impurities |
| Content (%) | 68 | 24 | 8 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of selenium slag, pouring the selenium slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a closed reaction kettle (stainless steel reaction kettle), electrically heating to the preset temperature of 215 ℃, introducing inert gas He to regulate the pressure to 3.8MPa, keeping the temperature and pressure of a water-containing material (selenium slag) at the preset temperature of 215 ℃ and the preset pressure of 3.8MPa, stirring for 6.5 hours under the conditions of oxygen-free state to form a solid-liquid two phase, and separating by a solid-liquid separation device (coalescence plate) to obtain a dehydrated selenium melt;
in this example, the mass of the dehydrated selenium melt was 775g, the moisture content of the dehydrated selenium melt was 1.9%, and the direct yield of selenium was 95%.
Example 3: the hydrous material of this example is selenium slag, the composition is shown in table 3,
TABLE 3 composition of selenium slag
| Composition (I) | Se | Water (W) | Impurities |
| Content (%) | 70 | 25 | 5 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of selenium slag, pouring the selenium slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a closed reaction kettle (stainless steel reaction kettle), electrically heating to the preset temperature of 220 ℃, introducing reducing gas CO to regulate the pressure to 4.0MPa, keeping the temperature and pressure of a water-containing material (selenium slag) at the preset temperature of 220 ℃ and the preset pressure of 4.0MPa, stirring for 6.3 hours under the conditions of oxygen-free state to form a liquid-liquid two phase, and separating by a liquid-liquid separation device (liquid-liquid separation tank) to obtain a dehydrated selenium melt;
in this example, the mass of the dehydrated selenium melt was 762g, the moisture content of the dehydrated selenium melt was 1.6%, and the direct yield of selenium was 93%. Example 4: the aqueous material of this example was sulphur slag, the composition of which is given in table 4,
TABLE 4 composition of Sulfur slag
| Composition (I) | S | Water (W) | Impurities in the product |
| Content (%) | 75 | 10 | 15 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of sulfur slag, pouring the sulfur slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a closed reaction kettle (hydrothermal synthesis reaction kettle) for electric heating to a preset temperature of 110 ℃, introducing inert gas Ar to regulate the pressure to 200KPa, keeping the temperature and pressure of a water-containing material (sulfur slag) at the preset temperature of 110 ℃ and the preset pressure of 200KPa, stirring for 6.6 hours to form a solid-liquid two phase, and separating by a solid-liquid separation device (sieve plate) to obtain dehydrated sulfur;
in this example, the mass of dehydrated sulfur was 812g, the water content of dehydrated sulfur was 1.5%, and the direct yield of sulfur was 94%.
Example 5: the aqueous material of this example was sulphur slag, the composition of which is given in table 5,
TABLE 5 composition of Sulfur residues
| Composition (I) | S | Water (W) | Impurities |
| Content (%) | 75 | 15 | 10 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of sulfur slag, pouring the sulfur slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a closed reaction kettle (hydrothermal synthesis reaction kettle) to be electrically heated to 120 ℃ of preset temperature, introducing inert gas He to regulate the pressure to 250KPa, keeping the temperature and pressure of a water-containing material (sulfur slag) at 120 ℃ of preset temperature and 250KPa of preset pressure for 6.2 hours under the condition of anaerobic state to form liquid-liquid two phases, and separating the two phases by a liquid-liquid separation device (liquid-liquid separation tank) to obtain a dehydrated sulfur melt;
the mass of the dehydrated sulfur melt in this example was 852g, the water content of the dehydrated sulfur melt was 0%, and the direct yield of sulfur was 98%. Example 6: the aqueous material of this example was sulphur slag, the composition of which is shown in Table 6,
TABLE 6 composition of Sulfur slag
| Composition (I) | S | Water (W) | Impurities in the product |
| Content (%) | 70 | 20 | 10 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of sulfur slag, pouring the sulfur slag into a PPL lining, placing the PPL lining in a closed reaction kettle (hydrothermal synthesis reaction kettle) for electric heating to the preset temperature of 140 ℃, introducing reducing gas CO to regulate the pressure to 300KPa, keeping the temperature and pressure of a water-containing material (sulfur slag) at the preset temperature of 140 ℃ and the preset pressure of 300KPa, stirring for 6.0 hours under the conditions of oxygen-free state to form a liquid-liquid two phase, and separating by a liquid-liquid separation device (liquid-liquid centrifuge) to obtain a dehydrated sulfur melt;
in this example, the mass of the dehydrated sulfur melt was 800g, the water content of the dehydrated sulfur melt was 0%, and the direct yield of sulfur was 97%. Example 7: the aqueous material of this example was bismuth slag, the composition of which is shown in Table 7,
TABLE 7 composition of bismuth slag
| Composition (A) | Bi | Water (I) | Impurities in the product |
| Content (%) | 25 | 40 | 35 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the particle size of 1000g of bismuth slag, pouring the bismuth slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a closed reaction kettle (magnetic stirring reaction kettle), electrically heating to a preset temperature of 260 ℃, introducing an inert gas Ar to regulate the pressure to 6MPa, keeping the temperature and pressure of a water-containing material (bismuth slag) at the preset temperature of 260 ℃ and the preset pressure of 6MPa and stirring for 6.0 hours under the anaerobic state to form a solid-liquid two phase, and separating by a solid-liquid separation device (sieve plate) to obtain dehydrated bismuth slag;
in this example, the mass of the dehydrated bismuth slag was 613g, the water content of the dehydrated bismuth slag was 2.1%, and the direct yield of bismuth was 95%.
Example 8: the aqueous material of this example was bismuth slag, the composition of which is shown in Table 8,
TABLE 8 composition of bismuth slag
| Composition (I) | Bi | Water (W) | Impurities in the product |
| Content (%) | 35 | 35 | 30 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the particle size of 1000g of bismuth slag, pouring the bismuth slag into a polytetrafluoroethylene inner lining, placing the polytetrafluoroethylene inner lining in a closed reaction kettle (magnetic stirring reaction kettle) for electric heating to a preset temperature of 275 ℃, introducing inert gas He to regulate the pressure to 7MPa, keeping the temperature and keeping the pressure of the water-containing material (bismuth slag) at the preset temperature of 275 ℃ and the preset pressure of 7MPa, stirring for 6.5 hours to form a solid-liquid two phase in an anaerobic state, and separating by a solid-liquid separation device (coalescence plate) to obtain dehydrated bismuth slag;
in this example, the mass of the dehydrated bismuth slag was 658g, the water content of the dehydrated bismuth slag was 1.2%, and the yield of bismuth was 96%.
Example 9: the aqueous material of this example was bismuth slag, the composition of which is shown in Table 9,
TABLE 9 composition of bismuth slag
| Composition (A) | Bi | Water (I) | Impurities |
| Content (%) | 55 | 20 | 25 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the particle size of 1000g of bismuth slag, pouring the bismuth slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a closed reaction kettle (magnetic stirring reaction kettle) for electric heating to a preset temperature of 290 ℃, introducing an inert gas Ar to regulate the pressure to 8MPa, stirring the water-containing material (bismuth slag) at the preset temperature of 290 ℃ and the preset pressure of 8MPa for 6.4 hours under the conditions of heat preservation and pressure maintaining at the anaerobic state to form a liquid-liquid two phase, and separating the liquid-liquid two phase to obtain a dehydrated bismuth melt through a liquid-liquid separation device (liquid-liquid centrifuge);
in this example, the mass of the dehydrated bismuth melt was 809g, the moisture content of the dehydrated bismuth melt was 1.1%, and the direct yield of bismuth was 94%. Example 10: the aqueous material of this example was sponge indium, the composition of which is shown in Table 10,
TABLE 10 composition of sponge indium
| Composition (I) | Indium (In) | Water (I) | Impurities in the product |
| Content (%) | 90 | 8 | 2 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the particle size of 1000g of sponge indium, pouring the sponge indium into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a closed reaction kettle (hydrothermal synthesis reaction kettle) for electric heating to the preset temperature of 140 ℃, introducing inert gas He to regulate the pressure to 400KPa, keeping the temperature and pressure of a water-containing material (sponge indium) at the preset temperature of 140 ℃ and the preset pressure of 400KPa, stirring for 6.0 hours under the conditions of oxygen-free state to form a solid-liquid two phase, and separating by a solid-liquid separation device (sieve plate) to obtain dehydrated indium;
in this example, the mass of dehydrated indium was 927g, the moisture content of dehydrated indium was 0.8%, and the direct yield of indium was 96%.
Example 11: the aqueous material of this example was tin dross, the composition of which is shown in Table 11,
TABLE 11 composition of tin dross
| Composition (A) | Tin (Sn) | Water (W) | Impurities |
| Content (%) | 50 | 15 | 35 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of tin slag, pouring the tin slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a closed reaction kettle (hydrothermal synthesis reaction kettle) for electric heating to a preset temperature of 230 ℃, introducing an inert gas Ar to regulate the pressure to 4MPa, keeping the temperature and pressure of a water-containing material (tin slag) at the preset temperature of 230 ℃ and the preset pressure of 4MPa, stirring for 6.0 hours under the conditions of heat preservation and pressure maintaining of the water-containing material (tin slag) in an anaerobic state to form a solid-liquid two phase, and separating by a solid-liquid separation device (sieve plate) to obtain dehydrated tin slag;
in this example, the mass of the dehydrated tin dross was 861g, the water content of the dehydrated tin dross was 1.3%, and the direct yield of tin was 94%.
Example 12: the water-containing material of this example was lead slag, the composition of which is shown in Table 12,
TABLE 12 composition of lead dross
| Composition (I) | Lead (II) | Water (W) | Impurities in the product |
| Content (%) | 55 | 30 | 15 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of lead slag, pouring the lead slag into a PPL lining, placing the PPL lining in a closed reaction kettle (magnetic stirring reaction kettle) for electric heating to a preset temperature of 340 ℃, introducing an inert gas Ar to regulate the pressure to 16MPa, keeping the temperature and pressure of a water-containing material (lead slag) at the preset temperature of 340 ℃ and the preset pressure of 16MPa and stirring for 6.0h under the anaerobic state to form a liquid-liquid two phase, and separating by a liquid-liquid separation device (liquid-liquid separation tank) to obtain a dehydrated lead melt;
in this example, the mass of the dehydrated lead melt was 706g, the moisture content of the dehydrated lead melt was 0.8%, and the direct yield of lead was 97%. Example 13: the water-containing material of this example is copper cadmium slag, the composition is shown in Table 13,
TABLE 13 composition of copper cadmium slag
| Composition (I) | Copper (Cu) | Cadmium (Cd) | Water (W) | Impurities |
| Content (%) | 9 | 16 | 30 | 45 |
A method for high-pressure dehydration of water-containing materials comprises the following specific steps:
adjusting the granularity of 1000g of copper-cadmium slag, pouring the copper-cadmium slag into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a closed reaction kettle (a magnetic stirring reaction kettle) for electric heating to a preset temperature of 340 ℃, introducing inert gas He to regulate the pressure to 16MPa, keeping the temperature and pressure of a water-containing material (copper-cadmium slag) at the preset temperature of 340 ℃ and the preset pressure of 16MPa, stirring for 6.0 hours under the conditions of oxygen-free state to form a liquid-liquid two phase, and separating by a liquid-liquid separation device (a liquid-liquid centrifuge) to obtain a dehydrated copper-cadmium melt;
in this example, the mass of the dehydrated copper-cadmium melt is 708g, the water content of the dehydrated copper-cadmium melt is 1.1%, the direct yield of copper is 91%, and the direct yield of cadmium is 93%.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (9)
1. A method for high-pressure dehydration of water-containing materials is characterized by comprising the following steps:
heating the water-containing material in a closed reaction kettle to a preset temperature, keeping the temperature and pressure of the water-containing material at the preset temperature and the preset pressure in a low-oxygen or anaerobic state, stirring to form a liquid-liquid two phase or a solid-liquid two phase, and performing liquid-liquid separation or liquid-solid separation to obtain a dehydrated mineral material, wherein the water-containing material is selenium slag, bismuth slag, sulfur slag, sponge indium, tin slag, lead slag or copper-cadmium slag.
2. The method for high-pressure dewatering of aqueous material according to claim 1, wherein: the selenium slag contains 65-70% of selenium, 25-30% of water and 0-10% of other impurities by mass; when the water-containing material is selenium slag, the preset temperature is 200-250 ℃, and the preset pressure is 2-6 Mpa.
3. The method for high-pressure dewatering of aqueous material according to claim 2, characterized in that: the bismuth slag contains 20-55% of bismuth by mass, 10-55% of water by mass and 25-35% of other impurities by mass; when the water-containing material is bismuth slag, the preset temperature is 250-290 ℃, and the preset pressure is 3-8 Mpa.
4. The method for high-pressure dewatering of aqueous material according to claim 1, characterized in that: the sulfur slag contains 70-75% of sulfur, 10-20% of water and 5-30% of other impurities by mass; when the water-containing material is sulfur slag, the preset temperature is 90-140 ℃, and the preset pressure is 101-400 KPa.
5. The method for high-pressure dewatering of aqueous material according to claim 1, characterized in that: the mass fraction of indium in the sponge indium is 90-98%, the mass fraction of water is 2-10%, and the mass fraction of other impurities is 1-6%; when the water-containing material is sponge indium, the preset temperature is 140-170 ℃, and the preset pressure is 400-900 KPa.
6. The method for high-pressure dewatering of aqueous material according to claim 1, characterized in that: the mass fraction of tin in the tin slag is 30-50%, the mass fraction of water is 5-15%, and the mass fraction of other impurities is 15-35%; when the water-containing material is tin dross, the preset temperature is 210-270 ℃, and the preset pressure is 200-700 KPa.
7. The method for high-pressure dewatering of aqueous material according to claim 1, characterized in that: the mass fraction of lead in the lead slag is 20-55%, the mass fraction of water is 10-30%, and the mass fraction of other impurities is 5-15%; when the water-containing material is lead slag, the preset temperature is 300-350 ℃, and the preset pressure is 8-18 MPa.
8. The method for high-pressure dewatering of aqueous material according to claim 1, wherein: the mass fraction of copper in the copper-cadmium slag is 1.5-17%, the mass fraction of cadmium is 2.5-12%, the mass fraction of water is 8-30%, and the mass fraction of other impurities is 30-45%; when the water-containing material is copper-cadmium slag, the preset temperature is 300-340 ℃, and the preset pressure is 8-16 MPa.
9. The method for high-pressure dewatering of aqueous material according to claim 1, characterized in that: the preset pressure is controlled by introducing inert gas and/or reducing gas, wherein the reducing gas is CO or SO 2 Or H 2 。
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| CN101524698A (en) * | 2009-04-03 | 2009-09-09 | 天津大学 | Caustic sludge dehydration method |
| CN102876354A (en) * | 2012-10-12 | 2013-01-16 | 西南石油大学 | Device and method for dehydrating crude oil |
| CN108580513A (en) * | 2018-04-18 | 2018-09-28 | 中南大学 | A kind of arsenic sulfide slag hot pressed sintering curing |
| CN111348815A (en) * | 2020-04-10 | 2020-06-30 | 中国科学院城市环境研究所 | Sludge dewatering and drying device and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524698A (en) * | 2009-04-03 | 2009-09-09 | 天津大学 | Caustic sludge dehydration method |
| CN102876354A (en) * | 2012-10-12 | 2013-01-16 | 西南石油大学 | Device and method for dehydrating crude oil |
| CN108580513A (en) * | 2018-04-18 | 2018-09-28 | 中南大学 | A kind of arsenic sulfide slag hot pressed sintering curing |
| CN111348815A (en) * | 2020-04-10 | 2020-06-30 | 中国科学院城市环境研究所 | Sludge dewatering and drying device and method |
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