Extraction of metals from flow enriched in hydrocarbons and carbon residues
SUBSTANCE: invention relates to extraction of metals from flow rich in hydrocarbons and carbon residues with the help of treatment section. Proposed method comprises feeding of said flow to extraction by its mixing with appropriate hydrophilising agent to kill hydrophobic properties of said flow. Mix of said flow and said agent are fed so separation of liquid phase containing major portion of hydrophilising agent and hydrocarbons precipitated from solid phase. Separated solid phase is dried at 350°C to remove medium-light hydrocarbon components. Separated solid phase, preferably dried, is fed for leaching by alkaline solution in the presence of air and/or oxygen, possibly, in the presence of emulsifier or its precursor. Then, leached mix is fed for separation to remove solid residue from leach liquor.
EFFECT: higher yield of valuable metals and hydrocarbons.
13 cl, 3 dwg, 1 tbl, 8 ex
The present invention relates to a method for extracting metals from a stream enriched in hydrocarbons and carbon residues, where the metals can be dispersed in the form of aggregates having a size essentially less than one millimeter, for example, as in purge streams from processes hydrobromide in the suspension phase.
Different methods of conversion of heavy feedstocks such as crude oil, heavy and superheavy, and remains after the distillation of crude oil, by hydrobromide in the suspension phase is known in patent literature.
Some ways include sharing three processing units; hydrobromide heavy raw materials with the use of catalysts in slurry phase, distillation or flash evaporation of the product emerging from the installation of hydrobromide, deasphalting in the presence of solvents distillation residue or liquid coming out of the installation, flash evaporation, containing the catalyst in dispersed phase, enriched in metal sulfides formed in the demetallization of raw materials and possibly of coking (IT MA; IT MA; IT MI2004A2446).
In the methods described above, as a rule, it is necessary to purge to prevent excessive accumulation in the reactor hydrobromide of compounds such as sulfides metal is, present in the feedstock, which, according to the method can be carried out on the asphaltene stream coming from the deasphalting section, or the residue after distillation or liquid coming out of the install flash evaporation.
To significantly reduce the amount of catalyst and is capable of providing recycling at least part of the catalyst is still active in the reactor hydrobromide, in patent application IT-MI2003A000693 the proposed introduction of section secondary treatment blowdown stream.
In this patent application the purge stream is sent to the processing section with a suitable solvent to separate the product into a solid fraction and a liquid fraction from which the specified solvent may subsequently be removed.
The processing section facing the purge stream, preferably in an amount of from 0.5 to 10 vol.%, in terms of fresh raw materials, consists of stage obezbalivaniya solvent (toluene or gas oil, or other threads, enriched with aromatic compounds) and separating the solid fraction from the liquid fraction.
The solid fraction can be recycled, as it is, or, more preferably, may be focused on treatment for selective removal of the transition metal or metals contained in the catalyst based on plumage is of one metal (e.g. Mo), relative to the other metals present in the obtained residue (for example, Ni and V)in order to make possible the flow of the recycle stream enriched transition metal (Mo), in the reactor hydrobromide.
Stage obezbalivaniya is in the processing of the purge stream, which represents the minimum fraction of asphaltene stream coming from the deasphalting section (SDA) in the setting of primary hydrobromide heavy raw materials, the solvent, which is capable of transferring the maximum amount of organic compounds in the liquid phase, leaving the sulphides of metals, coke and worse machinable carbon residues (insoluble in toluene or similar products) in the solid phase.
After receiving mixed phase solvent and the purge stream, the output stream with stirring refer to the section separation of the liquid phase from the solid phase, for example by desantirovaniya, centrifugation or filtration.
The liquid phase can then be directed to the stage distillation or separation of solvent, which return to the first stage of processing (de-oiling) purge flow, or it can be returned to the reactor hydrobromide.
In other recent patent applications (IT MA, IT MA) hydroconversion heavy oil described methods, including the direction t is geloy oil phase of hydrobromide, carried out in a suitable reactor, accumulating solids, using a hydrogenation catalyst in a slurry phase, in which the injected hydrogen, obtaining the conversion products in the vapor phase, and from which the solids supplied and generated heavy oil, which is subjected to conversion, is removed by purging.
In another recent patent application (IT MA) hydroconversion heavy oil described method, including the direction of the heavy oil in the section of hydroconversion, which is carried in one or more fluidized bed reactors, in which the injected hydrogen in the presence of a suitable heterogeneous deposited catalyst hydroconversion and a suitable hydrogenation catalyst, nanodispersions in heavy oil, and the direction extending from hydroconversion flow section of the division from which the separated liquid fraction containing nanodispersions catalyst return in fluidized bed reactors, except for the purge.
In these recent applications also always necessary purging to prevent excessive accumulation of the above compounds in the reactor hydrobromide.
In all the ways mentioned above, the amount of purge flow, though very limited relative to other technologies hydrobromide, in any case the e pose significant problems, associated with their use or disposal.
Now discovered that the purge flow methods hydrobromide in the suspension phase, some of which are described above, can be processed by a method including at least one extraction gidrofiliziruyuschim agent and subsequent leaching with alkaline solution and obtaining in this way the final product essentially consisting of soluble inorganic substances suitable for the selective extraction of metal components.
The claimed method also provides processing of raw materials containing significant amounts of metals, which avoids problems such as the formation of volatile compounds such as molybdenum oxide(VI), which can be formed in the process of oxidation when heated.
Strategic advantage is to extract and reuse the active component of the catalyst of this method.
Also remove large amounts of precious metals, such as Nickel and vanadium, which are used in the steel industry.
Finally, when processing a large number of hydrocarbons, again available for use in the methods that might otherwise be directed to waste, and this significantly reduces the amount of bitumen intended for having utilizacii, and at the same time increases the overall yield of the process hydrobromide.
The object of the present invention, a method for extracting metals from a stream enriched in hydrocarbons and carbon residues, through a section of the processing differs in that it comprises the following stages:
- the direction of the specified stream to the extraction by mixing the specified stream with a suitable gidrofiliziruyuschim agent, i.e. the agent is able to eliminate the hydrophobic property of the specified flow;
- the direction of the mixture consisting of the specified stream and specified hydrophilizing agent, separation with separation of the liquid phase, containing most of hydrophilizing agent and hydrocarbons dissolved from the solid phase;
- preferably drying the separated solid "phase, which is carried out at a maximum temperature of 350°C to remove medium-light hydrocarbon components from the solid phase;
- direction separated by a "solid" phase, preferably dried, leaching alkaline solution in the presence of air and/or oxygen and possibly in the presence of an emulsifying agent or its precursor;
- the direction of the leached mixture separation with separation of solids from the liquor.
The solid residue can be either removed or treated with extraction not present in nevydelujeme metals.
Liquor may be treated with the extraction of metals. In the presence of molybdenum and vanadium in the liquor, for example, you can use the method claimed in the patent application IT ME.
Streams, intended for processing, such as the purge flow can usually be a bituminous mixture consisting, for example, of:
- solid substances (i.e. components insoluble in tetrahydrofuran);
- metal compounds (mainly sulfides of Ni, V, Fe, Mo, CR);
- carbon residues;
- liquids (i.e. components that are soluble in tetrahydrofuran);
- hydrocarbons (essentially with a boiling point above 170°C);
- sulfur-containing organic compounds;
is a nitrogen - containing organic compounds.
The stream enriched in hydrocarbons and carbon residues before it is sent to the stage of extraction, may possibly be directed at the primary processing carried out in one or more stages, in which the specified stream is treated in the presence of a thinning agent in a suitable apparatus at a temperature of from 80 to 180°C., preferably from 100 to 160°C., and subjected to separation of the liquid/solid with obtaining a clarified product essentially consisting of liquids, and phase enriched solids (cake or tile), direction is appropriated for the specified stage of extraction.
Thinning agent, the function of which is to
- reducing the asphaltenes content associated with the KEK-phase by simple mixing,
- the decrease of the viscosity of the flow directed to the enrichment of the "solids" in the KEK-phase
preferably selected from the threads available at the facility, which have a pour point of below 180°C, such as VGO (vacuum gas oil) and LCO (light cycle oil).
The primary processing stage, which is carried with purpose
- weight reduction "liquids"associated with "solids"at least 2 times,
- save at least 80% solids in the cake-phase, can be carried out in one stage or in several stages, preferably from 2 to 5.
The advantage of multi-stage processing is more marked decrease in the content of asphaltenes and hydrocarbons with a boiling point above 300°C at KEK-phase and easier transportiruetes cake.
In the case of one-stage thinning agent preferably served in a co-current relative to the flow, that is processed.
In the case of multiple stages of thinning agent preferably served in counter-current relative to the flow of that process, because at each stage, the solid is separated by separation, refer to the next stage of processing liquid is th separated by separation, return as a thinning agent in the previous stage of processing.
This primary treatment is carried out in apparatuses that provide separation by physical processing, based on different density/different sizes of liquid-solid substances, such as, in particular, filter presses, centrifuges, desantiruemye centrifuges and hydrocyclones. Delantera centrifuge is the preferred device.
In the case of more than one stage, the devices may be different, but it is preferable to use decantorului centrifuges at the first stage.
Possible stage of drying is to remove the hydrocarbon fraction from the solid phase, which minimizes the real possibility of thermal cracking.
It is preferably carried out by heating to the specified target "solid" phase in an inert atmosphere at temperatures up to 350°C, more preferably up to 280°C and the pressure is preferably 100 kPa (1 bar) or vacuum up to 5 kPa (0.05 bar), and with the possible dilution with an inert gas (for example nitrogen).
One of the advantages of the drying operation is the formation of the final product, which can be easily transported and stored.
Hydrophilicity agent may be preferably selected from tetrahydrofuran is a, furfural, n-methyl-2-pyrrolidone, Isobutanol, piperidine, pyrrolidine, pyridine, methyltetrahydrofuran, diglyme, LCO, and VGO, more preferably from tetrahydrofuran and methyl-2-pyrrolidone.
Preferably, hydrophilicity agent at least partially soluble in the aqueous phase.
Preferably, the liquid phase containing the major part hydrophilizing agent and dissolved hydrocarbons, may be subject to separation from the Department hydrophilizing agent who returns to the stage extraction, and hydrocarbons.
Preferably, the stage leaching can be carried out at the operating temperature from 50 to 250°C and a pressure of from atmospheric pressure up to 10,000 kPa (100 bar).
Alkali metal in solution can be preferably selected from sodium and potassium concentration is preferably from 0.3 to 2 g/g of solid substance.
This stage leaching can be carried out in the presence of a dispersing agent or its predecessor.
Couples that go from the stage of drying, can be condensed and returned to the stage extraction, or they can be directed to the torch.
Some embodiments of the present invention is further described using the supplied graphic materials, which, however, should not be construed as limiting the scope of the invention.
Figure 1 is schematics and presents the method according to the present invention.
Bituminous mixture (BM) is preferably subjected to primary treatment (RT) in the presence of a thinning agent (F), separating thus essentially liquid flow (clarified product) (FB), cutback asphalt (which return for the installation of hydrobromide) and phase enriched solids (R).
Phase enriched solids (P), direct to the stage extraction (EX), which is carried out by mixing the specified phase, enriched in solids, with gidrofiliziruyuschim agent (IA), resulting in a portion of the hydrocarbons present in this phase, dissolved in hydrophilizing agent.
The mixture (C)obtained in this way are sent to phase separation (SEP1) to obtain the liquid phase (LIQ), containing most of hydrophilizing agent and dissolved hydrocarbons, and the "solid" phase (SOL).
The liquid phase (LIQ) subject to division (SEP2), separating the hydrocarbons (HC) from hydrophilizing agent (IA), which return to the stage extraction (EX).
Separated "solid" phase (SOL) is preferably subjected to a stage of drying (E) to remove from the "solid" phase components having boiling points below the temperature from 300 to 350°C.
Hydrocarbons with a boiling point below 300-350°C (VAP) is separated by drying, and after condensation in the condenser (CD) they can be returned to the stage and extraction (EX), and/or can be used as a thinning agent (F), and/or can be used for other purposes in cleaning, and/or may be directed to the torch.
Separated "solid" phase (ES), possibly dried, subjected to leaching (LC) alkaline solution (AS) in the presence of air and/or oxygen and possibly in the presence of a dispersing agent (DIS).
Leached mixture (LM) is directed to the additional phase separation (SEP3) separating the solid residue (RES), which is disposed or treated (SM), liquor (LQ), which is subjected to processing (MS).
Figure 2 schematically presents the primary processing is carried out in one stage.
Bituminous mixture (BM) after mixing in a suitable mixer (D) thinning agent (F), fed in parallel with bituminous mixture is subjected to primary processing (RT) in a suitable equipment (such as decantorului the centrifuge (S), dividing it in the separator (S) liquid (L), clarified the product, which may be a small amount of solids, and phase enriched solids (R).
Figure 3 schematically represents the primary processing carried out in several stages (stage 2).
Bituminous mixture (BM) is subjected to the first processing (PT1) in a suitable apparatus (for example in decantorului CE is trifuge (S1)) - thinning agent (F1), sharing in the separator (S1) to the liquid (L1), the final clarified product, and the intermediate phase, enriched solids (P1), which is sent to the second stage of primary processing (RT), implemented in other suitable device (such as decantorului centrifuge (S2)), fresh-thinning agent (F2), dividing it into liquid (L2), intermediate clarified product that is returned to the cycle and use, possibly after adding an additional quantity of fresh-thinning agent, such as a thinning agent (F1) of the first stage and a phase enriched solids (P2).
As shown in Figure 3, when the multistage processing of relative flows thinning agent and bituminous mixtures are mainly in counter-current.
For better illustration of the present invention shows some examples of the method on the material obtained from the pilot installation of hydrobromide in the suspension phase, with the content of organic substances above 80 wt.%.
These examples should not be construed as limiting the scope of the invention.
10 g blowing from the installation of hydrobromide in the suspension phase is subjected to processing to solubilize metals in alkaline solution, which is carried out under the following conditions:
the concentration of the sample is in an alkaline solution: 50 g/l;
- NaOH: 0.6 g/g sample;
- temperature: 80°C;
the presence of oxygen;
- the mixer rotation speed: 600 rpm At the end of processing the achieved outputs metals after leaching was negligible (<5%).
Example 2 was performed under the same conditions as in example 1, adding to the variance of naphthenic acid to improve the wettability of solids.
As indicated in table 1, the yields are much higher.
A sample of the same material is dispersed in a light recycle the oil (LCO) at a mass ratio of 1:2 (sample:L), and the resulting dispersion is filtered at 0.5-micron balloon filter under nitrogen pressure.
The resulting album, not washed and still containing hydrocarbons, is subjected to drying at 170°C for 8 hours in an inert atmosphere to remove light organic components.
The final product is subjected to the same washing treatment, which is described in example 1 demonstrates the increase in the degree of extraction of the metals, as shown in table 1.
The cake obtained as described in example 3, not dried, dispersed a second time using LCO mass ratio of 1:5.
The dispersion is again filtered by the same procedure as in example 3.
The resulting plate is dried at 280°C in an inert atmosphere and subjected to the same washing about what abode, as described in example 1.
The outputs of the leachate are listed in table 1.
KEK, as in example 3, not dried, treated with tetrahydrofuran (THF) at a ratio of 1:10, filtered and then dried at 100°C in an inert atmosphere.
The final dried product is subjected to leaching, as described in example 1; the results are listed in table 1.
KEK, as in example 3, not dried, treated with toluene in a ratio of 1:10, filtered and then dried at 100°C.
The final dried product is treated as described in example 1; the results are listed in table 1.
10 g of the same starting material as in Example 1, treated with THF in a ratio of 1:40. The dispersion was filtered as in example 3, and the plate is dried at 100°C and then subjected to leaching under the same conditions as in example 1. The outputs are listed in table 1.
10 g of the same starting material is treated with N-methyl-2-pyrrolidone in a ratio of 1:10.
The suspension is filtered, dried at 170°C in an inert atmosphere and then subjected to leaching in the same way as in example 1. The results are listed in table 1.
|Example||Exit after leaching|
1. The method of extraction of metals from enriched in hydrocarbons and carbon residue stream by processing, characterized in that it comprises the following stages:
- the direction of the specified stream to the extraction by mixing the specified stream with gidrofiliziruyuschim agent, is able to eliminate the hydrophobic property of the specified flow;
- the direction of the mixture consisting of the specified stream and specified hydrophilizing agent, separation with separation of the liquid phase, containing most frequent is hydrophilizing agent and hydrocarbons, dissolved from the solid phase;
- preferably drying the separated solid phase, which is carried out at a maximum temperature of 350°C to remove medium and light hydrocarbon components from the solid phase;
- the direction of the separated solid phase, preferably dried, leaching alkaline solution in the presence of air and/or oxygen and possibly in the presence of an emulsifying agent or its precursor;
- the direction of the leached mixture separation with separation of solids from the liquor.
2. The method according to claim 1, in which at the stage of extraction of the specified stream is directed to the primary processing carried out in one or more stages, in which the specified stream is treated in the presence of a thinning agent in the apparatus at a temperature of from 80 to 180°C, and subjected to separation of the liquid/solid with obtaining a clarified product essentially consisting of liquids, and phase enriched solids sent to the specified phase extraction.
3. The method according to claim 2, in which the primary treatment is carried out at a temperature of from 100 to 160°C.
4. The method according to claim 2, in which the stage of primary processing is carried out in one stage, on which the thinning agent is co-current with respect to the processed stream.
5. The method according to claim 2, in which the primary treatments is ku is carried out in two or more stages, moreover, the thinning agent is countercurrent with respect to the processed stream at each stage, and the solid is separated by separation, send the next stage of processing, and the liquid separated in the repeated cycle of separation, as a thinning agent sent to the previous stage of processing.
6. The method according to claim 1, in which the drying of the solid phase is carried out by heating the specified solid phase in an inert atmosphere at temperatures up to 350°C and a pressure of 100 kPa (1 bar) or vacuum up to 5 kPa (0.05 bar).
7. The method according to claim 1, in which the drying is also carried out by an inert gas purge.
8. The method according to claim 1, in which the liquid phase, containing most of hydrophilizing agent and dissolved hydrocarbons, is subjected to separation with separation from hydrocarbons hydrophilizing agent who returns to the stage extraction.
9. The method according to claim 1, in which stage leaching is performed at a temperature of from 50 to 250°C and at a pressure of from atmospheric pressure up to 10,000 kPa (100 bar).
10. The method according to claim 1 in which the alkali metal in the solution is selected from sodium and potassium concentration from 0.3 to 2 g/g of sample.
11. The method according to claim 1, in which stage leaching is performed in the presence of a dispersing agent or its predecessor.
12. The method according to claim 1, in which the ary, emerging from the stage of drying, condense and return to the stage extraction.
13. The method according to claim 1, in which hydrophilicity agent at least partially soluble in the aqueous phase.
SUBSTANCE: method includes oxidising roasting, percolation leaching of the roasted product with aqueous solution of an oxidising agent or mixtures of oxidising agents to obtain a rhenium-containing solution and an insoluble residue, sorption of rhenium from the rhenium-containing solution in a separate apparatus, drying the insoluble residue, mixing with fluxing agents and fusion on a metal collector. Percolation leaching is carried out at redox potential values of 900-1100 mV and temperature of 50-90°C, with simultaneous sorption of rhenium, followed by desorption and separation of rhenium compounds or rhenium metal from the strippant. The fluxing agents used to fuse the insoluble residue are fluorspar, sodium carbonate and sodium nitrate. Fusion is carried out at temperature of 1200-1800°C on a metal collector in several steps, while discharging the formed slag after each step and fusing the next portion of the mixture on the collector from the previous fusion with separation of the alloy of platinum metals with the collector.
EFFECT: high degree of extraction of rhenium, low reactant consumption, labour input, faster processing of the material, considerable reduction of the volume of solutions which require recycling.
8 cl, 1 dwg, 1 ex
SUBSTANCE: device contains successively installed a feed hopper, an open hearth furnace, an afterburning chamber, a recuperator of combustion air heating, a heat recovery unit, a smoke exhauster and a smokestack, means for fuel supply. The furnace is provided with a bag filter for purification of flue gases from dust and a catalytic apparatus for purification of flue gases from carbon oxides and nitrogen oxides. The catalytic apparatus consists of a vertical case with a conic bottom, inside which from top to bottom placed are: a vertical heat-exchanger, a liquid distributer, an absorption section, a desorption-cooling section, an aspiration hood with a fan and a Venturi tube. A method includes preparation of a charge in the form of a mixture of wastes with flux, loading of the charge and its melting in a bath of the open hearth furnace at a temperature of 1450-1500°C. Performed are: discharge of released combustible components into the afterburning chamber with heat recovery of flue gases, purification of flue gases from dust in the bag filter, purification of smoke gases from carbon oxides and nitrogen oxides is performed in the catalytic apparatus.
EFFECT: method improvement.
2 cl, 2 dwg
SUBSTANCE: group of inventions relates to utilisation of solid mercury-containing wastes, in particular fluorescent lamps. A method of utilisation of solid mercury-containing wastes includes an oxidation stage with further stand, processing a wastes mixture with a demercurised solution of an alkali metal polysulfide with further stand of the reaction mixture. Wastes are divided into two parts. One part, which contains crushed wastes, is processed with an oxidant, and then with a demercurised iodine-alcohol solution or a sodium sulfide solution. The second part of wastes in the form of aeromixture is passed through a nanoporous carbon sorbent NCMS-J. A device for utilisation of mercury-containing wastes contains a unit of loading and crushing, a purification unit and an aeromixture unit. The purification unit is made in the form of a truncated cone, connected by means of a flange to a cylindrical reservoir with a perforated screw, provided with a valve for the solution discharge, and an upper part of the perforated screw is provided with an unloading flange for discharge into a storage hopper. The aeromixture unit is made in the form of a column type adsorber with the nanoporous carbon sorbent NCMS-J.
EFFECT: ensuring reduction of mercury vapour concentration in air and water extract to TLV level, neutralisation of solid wastes of compact fluorescent lamps to IV class of hazard.
7 cl, 1 dwg, 4 ex
SUBSTANCE: furnace includes a housing formed with refractory external side, front and rear end walls, two baths restricted with bottoms, an arch and walls, two drain tap holes, a gas duct and a pedestal, on which all parts are arranged. In the furnace there is external heat insulation of walls, which consists of asbestos tailings and a double layer of asbestos boards. The furnace pedestal has two layers made of light-weight brick with the double layer of asbestos boards between them, a quartz sand layer from below and from above, which is mixed with asbestos tailings, and three layers of asbestos boards on the top, on which bottom block are laid. A casting shoe includes a housing formed with refractory external side, front and rear end walls, a bath, restricted with a bottom, an arch and walls, and drain tap holes. The casting shoe pedestal has two layers made of light-weight brick and separated with an asbestos board layer, and a lower asbestos board layer. The casting shoe has two tap holes made in quick-changeable tap-hole bricks in a box. The furnace has two turning chutes with a turning bowl, which are installed on brackets welded to the casting shoe box, which are turned during liquid metal pouring process for subsequent pouring of molten metal in the furnace to pouring equipment located in a maintenance sector with an angle of 143°. Five injection burners are installed in the furnace and the casting shoe. The furnace operates at natural and artificial draft with a dust and gas cleaning system.
EFFECT: improving efficiency and decreasing heat losses.
5 cl, 12 dwg
SUBSTANCE: electronic waste is crushed on a hammer crusher; crushed copper is added, and then, it is fused in presence of flux during 45-60 minutes at the temperature of 1320-1350°C with air blowdown at its flow rate of 3-4.5 l/h and the obtained slag containing at least 2.6 wt % of precious metals is separated from slag.
EFFECT: effective electronic waste processing with increase of content of precious metals in an alloy.
SUBSTANCE: mixture, consisting of sulphur powder, granules of floatation sulphur pyrite of grade KSF-4 in mixture with broken stone with fraction 20-70 mm or brick crumbs, which are simultaneously agent binding mercury in ionised and neutral forms, taken in ratio 1:9 by weight, and water. After that, mixture is homogenised at rotation rate 20 rev/min, argon is supplied at rate 5.5-6.5 m3/h and then mercury-containing wastes are charged in amount which is at least 50 times less than weight of sulphur powder. Grinding of wastes is carried out to complete binding of metal mercury into water-insoluble compound HgS.
EFFECT: simplification of technology, increase of ecological safety of the process.
SUBSTANCE: method includes combined grinding of wastes with sulphur powder and crushing medium in rotary reactor for binding metal mercury into water-insoluble compound. As crushing medium used is sulphur pyrate with fraction 50-150 mm, which is simultaneously agent, binding mercury in ionised and neutral forms. Before combined grinding mixture of sulphur powder, sulphur pyrate and water is preliminarily homogenised, and reactor is filled with nitrogen, supplied at rate 7.5-8.5 m3/h, in amount which is at least 50 times less than weight of sulphur powder. After that mercury-containing wastes are charged and grinding is carried out to complete binding of metal mercury into water-insoluble compound HgS.
EFFECT: simplification of technology and increase of processing process safety.
SUBSTANCE: oxidised zinc-containing materials with coke dross as a hard carbon reducer are supplied into a rotary tubular furnace and exposed to Waelz process with supply of blow in the form of a steam and air mixture into zone of temperatures 1050-1150°C with content of steam in the mixture 14-25%.
EFFECT: reduced consumption of a reducer and content of zinc and lead in a clinker, eliminates softening of material in a furnace.
2 tbl, 2 ex
FIELD: process engineering.
SUBSTANCE: invention relates to extraction of precious metals. Continuous extraction of precious metal composition from raw stock comprises heating of said stock in plasma kiln to produce slag top layer and fused metal bottom layer. Then, slag layer and fused metal layer are removed. Fused metal removed layer is solidified and fragmented for extraction of precious metals from produced fragments. Note here that said raw stock comprises material containing precious metal and collector metal. The latter is either metal or alloy able to form solid solution, alloy or intermetallide compound with one or several precious metals. Proposed device comprises plasma kiln, teeming table for continuous teeming of fused metal pool to form solidified sheet, fragmentation device and separation unit for extraction of precious metals from sheet fragment alloys.
EFFECT: higher yield.
20 cl, 11 dwg, 2 ex
SUBSTANCE: method of demercurisation of waste luminescent lamps comprises destruction of lamps and vibratory cleaning of lamp breakage from luminophore. At that the destruction of lamps is carried out to the glass particle size of no more than 8 mm. After the destruction of luminescent lamps the lamps bases are separated from the glass on the vibrating grate and removed to the collector which is sent to demercurisation- annealing electric furnace. The heat treatment of bases is carried out at a temperature up to 100°C and the holding time of at least 30 minutes. Division of luminophore from the glass is carried out by blowing it in the counterflow-moving system "broken glass-air" under the conditions of vibration.
EFFECT: increased efficiency and energy saving of recycling luminescent lamps, cost reduction and simplification of disposal technology.
SUBSTANCE: invention relates to extraction of pure vanadium pentoxide from slag obtained during production thereof. The method involves taking ground vanadium-containing slag, fusion thereof with sodium hydroxide to obtain sodium metavanadate. The sodium metavanadate is then leached with water and the solution is separated from the solid phase. The obtained solution is then mixed with an inorganic acid to achieve pH≤4 and a sorbent is added, the sorbent used being powdered coal which is modified with cation-active nitrogen-containing surfactants. After the sorption process, the spent sorbet is separated from the liquid phase, dried and calcined at temperature of 600-640°C to obtain pure vanadium pentoxide. The cation-active nitrogen-containing surfactants used are, for example, lauryl dimethylbenzyl ammonium chloride, cetylpyridinium chloride and polyhexamethylene guanidine hydrochloride.
EFFECT: wider raw material base for producing vanadium pentoxide, providing high output and high degree of purity of vanadium pentoxide.
4 cl, 1 tbl, 3 ex
SUBSTANCE: method involves decomposition of vanadium oxytrichloride with alkali solution so that sodium metavanadate is obtained; loading of solid ammonium-containing non-organic compound so that pulp of ammonium metavanadate is obtained; then, ammonium metavanadate deposition, its flushing, drying and roasting till vanadium pentoxide is obtained. Sodium carbonate mixed with sodium hydroxide at the weight ratio of (0.05-0.1):1 is used as alkali solution; for that purpose, first, solid sodium carbonate and then, solution of sodium hydroxide at mass concentration of 100-150 g/l is loaded subsequently to water solution in the form of mother solutions from flushing of pulp of sodium metavanadate and flushing of pulp of ammonium metavanadate. Solution of vanadium oxytrichloride is loaded to the obtained alkali solution till content of pH of the medium, which is equal to 7-8 so that pulp is obtained. After filtration of the pulp the mother solution of sodium metavanadate is treated with solid salt of ammonium-containing non-organic compound so that ammonium metavanadate pulp is obtained.
EFFECT: increasing degree of vanadium extraction to finished product.
9 cl, 1 ex
SUBSTANCE: method includes sorption of rich components from production solutions by ion-exchange material counterflow under controlled pH of environment and oxidation-reduction potential Eh. Sorption is performed by ion-exchange materials in stages from production solutions containing uranium, molybdenum, vanadium and rare earth elements. At the first stage uranium and molybdenum are extracted by anion-exchange material sorption. At the second stage vanadium is extracted by anion-exchange material sorption with hydrogen dioxide available at Eh of 750-800 mV, pH of 1.8-2.0 and temperature of 60°C, at that vanadium sorption is performed till complete destruction of hydrogen dioxide and till Eh is below 400 mV. Then barren solutions are transferred to cationite at pH of 2.0-2.5 and Eh of 300-350 mV for extraction of rare earth elements.
EFFECT: sorption concentration and selective separation of uranium and molybdenum from vanadium, and vanadium from rare earth elements, and rare earth elements from iron and aluminium, intensification of sorption process, reduction of flow diagram and possibility of environmentally sound oxidants use.
1 dwg, 4 tbl, 1 ex
SUBSTANCE: processing method of black-shale ores includes crushing, counterflow two-stage leaching by sulfuric acid solution upon heating, separation of pulps formed after leaching at both stages by filtration. Then valuable soluble materials are washed from deposit at the second stage with strengthened and washing solutions being produced, marketable filtrate is clarified at the first stage for its further processing. Ore is crushed till the size of 0.2 mm, leaching at the first stage is performed by cycling acid solution with vanadium under atmospheric pressure, temperature of 65-95°C during 2-3 hours, till residual content of free sulphuric acid is equal to 5-15 g/l. Leaching at the second stage is performed at sulphuric acid rate of 9-12% from the quantity of initial hard material under pressure of 10-15 atm and temperature of 140-160°C during 2-3 hours. Cake filtered after the first stage is unpulped by part of strengthened solution which content is specified within 35-45% of total quantity.
EFFECT: high-efficiency extraction of rich components, possibility of pulps separation by filtration after leaching with high properties thus reducing costs for separation processes.
3 cl, 1 dwg, 1 tbl
SUBSTANCE: processing method of black-shale ores with rare metals extracting includes leaching of ore by sulphuric acid solution with dilution of rare metals. Leaching is performed in autoclave by sulphuric acid solution consisting of free and combined sulphuric acid with ratio of H2SO4(free):H2SO4(comb)=2:1, and containing 25-45 g/l of iron sulphate, 70-90 g/l of aluminium sulphate and 0.5 g/l of nitric acid. At that the process is performed under pressure in autoclave equal to 10-15 atm with mixing at temperature of 140-160°C in concentration range of general H2SO4(gen) equal to 350-450 g/l under pulp density S: L=1:0.7-0.9, preferably 1:0.8, under constant oxidation-reduction potential Eh in the system equal to 350-450 mV during 2-3 hours till residual concentration of free H2SO4(free) is within 45-75 g/l.
EFFECT: increasing break-down of ore and extraction of rare metals: vanadium, uranium, molybdenum and rare-earth elements, reducing consumption of acid and improving efficiency of autoclave volume usage.
1 tbl, 1 ex
SUBSTANCE: proposed method comprises vanadium extraction by treatment with extracting agent composed of secondary aliphatic alcohol at increased temperature to obtain vanadium-containing extract. Vanadium is then re-extracted by ammonium solution to obtain vanadium-containing solution and vanadium-free extracting agent to be directed to extraction stage. Said extracting agent represents said secondary aliphatic alcohol with the number of atoms of 8-12. Extraction is carried out in a-3 steps at organic phase-to-water phase ratio of 0.5:5.1, temperature of 40-60°C and solution pH of 1.5-3.0. Before re-extraction of vanadium the extract is flushed by weak-acid solution to be added after flushing to initial acid solution.
EFFECT: higher yield of high-purity vanadium.
6 cl, 7 ex
SUBSTANCE: invention refers to complex processing method of carbon-silicic black-shale ores, which contain vanadium, uranium, molybdenum and rare-earth elements. The above method involves ore crushing to the particle size of not more than 0.2 mm and two leaching stages. Oxidation sulphuric-acid leaching is performed at atmospheric pressure. Autoclave oxidation sulphuric-acid leaching is performed at the temperature of 130-150°C in presence of oxygen-containing gas and addition of a substance forming nitrogen oxide, as a catalyst of oxygen oxidation. Ion-exchange sorption of uranium, molybdenum, vanadium and rare-earth elements is performed from the obtained product solution.
EFFECT: increasing extraction degree of vanadium, uranium, molybdenum; improving the complexity of ore use owing to associated extraction of rare-earth elements.
18 cl, 1 dwg
SUBSTANCE: method involves the following steps at which: initial material is processed into the ash containing the metals subject to regeneration, which have been chosen from the metals including vanadium, metals of group 8-10 and metals of group 6; the above ash is leached by leaching solution so that the first solid substance is obtained, which contains metals of group 8-10, solid carbonaceous material and supernatant fluid containing vanadium and metal of group 6; supernatant fluid is mixed with solution of ammonia sulphate and the deposit containing vanadium and additional fluid containing metal of group 6 is obtained; additional supernatant fluid is mixed with leaching solution, solution of ammonia sulphate and solution of sulphuric acid and the deposit containing metal of group 6 is obtained.
EFFECT: methods are effective for regeneration of metals without formation of other undesirable by-products.
10 cl, 9 dwg, 12 tbl, 3 ex
SUBSTANCE: invention relates to vanadium oxide extraction. The method of producing vanadium oxide involves preparation of starting vanadium-containing material for burning, burning with lime treatment, leaching with sulphuric acid, separating the solid substance and liquid, precipitation of ammonium polyvanadate with an ammonium salt and removing ammonia by calcination or reduction to obtain vanadium oxide. The solid starting material used at said steps has total amount of alkali metal of not more than 0.3 wt % and total amount of Cl- and NO3 - ions of not more than 0.1 wt %, and the liquid starting material has total amount of alkali metal of not more than 0.1 g/l and total amount of of Cl- and NO3 - ions of not more than 0.1 g/l.
EFFECT: invention increases the degree of extraction of vanadium and enables to recycle waste water formed during the vanadium extraction process.
10 cl, 1 dwg, 12 tbl, 3 ex
SUBSTANCE: method involves disintegration, heat treatment, leaching and precipitation of vanadium compounds. The slag is ground to a particle size from - 0.2 to - 0.3 mm, vanadium and other metals are transferred from the slag into a solution of sulphates of metals using the heat of exothermic chemical reactions, "vanadium slag - sulfuric acid aqueous solution," which is conducted at temperatures ranging from 75 to 85 °C, achieved by changing the acid concentration from 20 to 30% in proportion to the size of the leaching slag particles. Vanadium and other metals are precipitated as hydroxides by treating a sulphate solution with magnesium oxide at a ratio of MgO:H2SO4 from 1:2.6 to 1:2.7 and pH 10.0÷10.4 for reactions such as: MeSO4 + MgO + H2O → Me(OH)2 ↓ +MgSO4, (1) with a turnover of magnesium reagents in the interaction of MgSO4 with NaOH: MgSO4 + 2NaOH → Mg(OH)2 ↓ +Na2SO, (2) with a possibility of exchange of MgO in (1) Mg(OH)2 by (3): MeSO4 + Mg(OH)2 → Me(OH)2 ↓ +MgSO4, (3) using the reaction: Na2SO4+Ca(OH)2 ("lime milk")→2Na(OH)+CaSO4·2H2O (gypsum)↓, for turnover of the reagents of sodium and utilisation of gypsum obtained in the form of gypsum concrete, alabaster.
EFFECT: decrease in power consumption.
1 tbl, 1 ex
SUBSTANCE: invention can be implemented at withdrawing purified gas G from reservoir, where a) gas flow of hydrogen from at least converted fraction G1 of said gas G used in installation (I) for processing hydrocarbons and usually another fraction G2 of said gas G are used as fuel in said installation (I) for hydrocarbon processing; b) natural liquid transportable crude oil P1 is withdrawn at temperature of solidifying 0°C or less including vacuum residue with contents of sulphur over 1% of weight and is transported via not-heated pipeline or not-heated oil tanker; c) said oil P1 is processed on said installation for hydrocarbon processing (I), also said processing is performed essentially without carbon unloading, and said processing includes: at least one stage of de-sulphurisation by means of hydro-purification (HDT, RHDT) or hydro-conversion (HDC, RHDC), or hydro-cracking (HDK) of at least one fraction of oil P1; also said fraction mainly includes compositions with boiling temperature exceeding 343°C; further said stage consumes at least part of flow H2, at least one stage, which can be common with said stage of de-sulphurisation or separate from it to decrease amount of vacuum residue included into oil P1 with separation of part or total vacuum residue, not necessary with conversion of part of said vacuum residue, where complete separation of at least part of pyrobitumens of said vacuum residue is carried out with the purpose of obtaining at least one preliminary purified oil product PA including compounds produced from stage of de-sulphurisation; also said preliminary purified oil product PA in essence does not contain pyrobitumens and contains reduced amount of sulphur at least at 50%, while contents of vacuum residue with sulphur contents is over 1 wt %, which is accepted as zero or reduced at least at 15% relative to oil P1, and at least separate fraction including at least basic part of pyrobitumens, not necessary cracked and/or replenished with other fractions from P1 in form of heavy liquid fuel and/or residual oil product PB, which is liquid at temperature of environment d), said preliminary purified oil product PA is pumped to oil port as source raw material for refinery designed to be purified at refinery, which differs and is distanced from installation (I).
EFFECT: reduction of excess of sulphur containing residues of oil refinery, reduction of power and ecological costs caused by transporting of said excessive residues and by liquation and transporting of natural gas.
26 cl, 5 dwg