Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0006—Controlling or regulating processes
  • B01J19/0013—Controlling the temperature of the process
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
  • B01J6/008—Pyrolysis reactions
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/02—Silicon
  • C01B33/021—Preparation
  • C01B33/023—Preparation by reduction of silica or free silica-containing material
  • C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00004—Scale aspects
  • B01J2219/00006—Large-scale industrial plants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
  • B01J2219/00117—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
  • C01B2203/0272—Processes for making hydrogen or synthesis gas containing a decomposition step containing a non-catalytic decomposition step
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
  • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

• the invention relates to a plant for the production of silicon, preferably high-purity silicon, in particular solar silicon, and a method for producing silicon, preferably high-purity silicon, in particular solar silicon, each with particularly effective resource utilization and reduced emission of pollutants.
• the plant according to the invention can achieve considerable process intensification in the production of silicon, in particular solar silicon, which leads to a significant reduction of climate-damaging carbon dioxide and / or carbon monoxide and to a significantly reduced demand for electrical energy.
• formed by recycling of silica which in the reduction of
• Silica is formed to silicon in the electric arc furnace, in the carbon black reactor and the return of the resulting in the production of carbon black in the reduction reactor, a silicon oxide cycle by the silicon oxide waste largely ideal, even completely avoided. Furthermore, the material balance of the silicon used in the overall process is significantly increased by the new plant, whereby a total of less silica as starting material must be introduced into the process.
• the waste heat ie the thermal energy that accumulates in the production of soot (carbon black)
• the waste heat of the carbon black process is usually currently used for preheating or preheating of the educts, such as natural gas and oil, the same process.
• the waste heat of the production of silicon especially in the form of hot process gases, only quenched with air and directed to the separation of silica by hot gas filters.
• the flames strike against water-cooled rolls, which stops the combustion reaction. A part of the soot formed inside the flame is deposited on the rollers and is scraped off by them. The soot remaining in the exhaust gas stream is separated in filters. Further, the Channelruss method (Carbon Black, Prof. Donnet, 1993 by MARCEL DECCER, INC., New York, page 57ff) is known in which a plurality of natural gas-fed small flames burn against water-cooled iron channels. The soot deposited on the iron channels is scraped off and collected in a funnel.
• waste heat in particular in the form of hot residual gases (tail gas) and hot steam. So far, the waste heat is partially removed from the gases, for example via capacitors, then the gases are purified and blown into the environment. The extracted waste heat is not used meaningfully so far.
• silicon oxide in particular of silicon dioxide, such as precipitated silica or silica, which has been purified by means of ion exchangers, a supply of particularly high energy, for example, to dry the wet silicon oxides needed.
• the object of the present invention was therefore to develop an efficient plant for the production of silicon-in particular solar silicon-by reducing silicon dioxide and thereby to reduce the use of raw materials. Another task was to develop an overall system that can be operated with the lowest possible demand for resources, especially raw materials as well as thermal and electrical energy.
• the subject of the present invention is an overall plant 1 according to FIG. 1 with at least one reactor 4.1 for the thermal conversion of carbon-containing compounds and at least one reactor 6.1 for the reduction of metallic compounds, wherein the carbon produced in the reactor 4.1, preferably in the form of carbon black or carbon or the pyrolysis product of at least one carbohydrate, fed via the Stoffström 4.2 and the reactor 4.1 as a by-product silicon dioxide over the Stoffström 4.3 the reactor 6.1 and also obtained in the reactor 6.1 as a by-product mixture of carbon monoxide and silicon monoxide over the Stoffström 6.3 back into the Reactor 4.1 are performed.
• Appendix (Ia) is over the Stoffström 7.2, preferably continuously, silica, preferably high purity silica, and about 4.4 a carbon-containing compound, preferably natural gas, oil or carbohydrates such.
• a carbon-containing compound preferably natural gas, oil or carbohydrates such.
• the systems according to the invention are characterized by a special silicon circuit, which ensures that the silicon introduced in the form of an oxide is approximately quantitative, ie. at least 80%, preferably 90 to 100%, more preferably 95 to 99.5%, most preferably 97 to 99% in, preferably highly pure, silicon is converted and almost no silicon in the form of one of its oxides is lost as a waste product.
• the subject of the present invention is an overall installation 2 which, in addition to the components of the entire installation 1, comprises a device or machine or installation 8.1 for further processing of the silicon dioxide stream 4.3 and the carbon stream 4.2 so that the streams 4.2 and 4.3 Appendix 8.1 and the product of this further processing via a stream 8.2 are fed to the reactor 4.1.
• the SiO / SiO 2 cycle between the reactors 4.1 and 6.1 is thus retained, it is merely added with 8.1 another system component.
• the entire system 2 comprises at least one reactor 4.1 for the thermal conversion of carbon-containing compounds, at least one reactor 6.1 for the reduction of metallic compounds and at least one device or machine or system 8.1 for further processing of the silicon dioxide stream 4.3 and the carbon stream 4.2.
• the reactor for the thermal conversion of carbon-containing compounds 4.1 carbon, preferably in the form of carbon black or coal or the pyrolysis of at least one carbohydrate, produced and fed via 4.2 of the further processing device 8.1.
• the im Reactor for the thermal conversion of carbon-containing compounds 4.1 by-produced silicon dioxide, preferably in powder form, is also fed to the further processing via 4.3.
• the further processing device / machine / plant 8.1 preferably comprises a mixing unit in which carbon and silicon dioxide are mixed as homogeneously as possible and / or a unit for the production of moldings made of carbon and silicon dioxide.
• the production of the shaped bodies can be carried out, for example, by granulation, tableting, pelleting, briquetting or other suitable measures which are well known to the person skilled in the art.
• the products thus obtained are then fed via 8.2 the reduction furnace 6.1.
• the reduction furnace 6.1 the mixture of carbon and silicon dioxide is converted to high-purity elemental silicon, which is stripped off (not shown in the figures).
• By-products of this reaction include silicon monoxide, carbon monoxide and carbon dioxide.
• the silicon and the carbon monoxide are valuable raw materials in the process according to the invention and are therefore recycled via 6.3 into the reactor 4.1.
• the streams 4.2 and 4.3 can be designed as separate pipe systems, but it is also possible to transfer both the carbon from 4.2 and the silicon dioxide from 4.3 to the reactor 4.1 in a line for further processing 8.1.
• the plant according to the invention comprises in this case a grinding device. Grinding, mixing and
• Production of the shaped bodies can be carried out in 8.1 each as separate steps in separate machines but also partially or completely simultaneously in one machine.
• the feed of the raw materials in the material cycle via 7.2 and 4.4 preferably continuously, wherein more than 7.2 silicon dioxide, preferably high-purity silicon dioxide, and 4.4 a carbon source is supplied.
• high-purity silicon is withdrawn (stream in the figures not shown).
• the special silicon cycle of the system according to the invention ensures that the silicon introduced in the form of an oxide is obtained almost quantitatively as high-purity silicon and virtually no silicon in the form of one of its oxides is lost as a waste product.
• the embodiments according to FIGS. 1 and Ia the embodiments according to FIGS.
• the reactor 4.1 for the thermal conversion of carbon-containing compounds 4.1 are all reactors for the production of carbon black, graphite, carbon or generally a compound containing a carbon matrix, for example, silicon carbide-containing carbons as well as other skilled in the art corresponding compounds.
• the reactor 4.1 for the thermal conversion of carbon-containing compounds is a reactor or furnace for the production of carbon black or for the combustion and / or pyrolysis of carbohydrates, for example the pyrolysis of sugar optionally in the presence of silicon dioxide, for the production of carbon containing matrices, for example in the presence of high purity silica.
• Usual reactors for the thermal conversion of carbon-containing compounds 4.1 are all reactors for the production of carbon black, graphite, carbon or generally a compound containing a carbon matrix, for example, silicon carbide-containing carbons as well as other skilled in the art corresponding compounds.
• the reactor 4.1 for the thermal conversion of carbon-containing compounds is a reactor or furnace for the production of carbon black or for the combustion and / or pyro
• Production of carbon black are operated at process temperatures of 1200 to over 2200 ° C. in the combustion chamber.
• the best known methods for the production of carbon black are the Lamp Black process, the Furnace Black process, the Gas Black process, the Flußruss- Acetylenruss- or Thermalruss vide.
• the reactor 4.1 is preferably designed for carrying out the said processes.
• the system according to the invention is preferably known from the prior art Reactor used to produce carbon black or for the thermal conversion of carbon-containing compounds.
• Such reactors are well known to those skilled in the art.
• Preferred according to the invention as reactor 4.1 is the furnace black reactor, which is fed with clean, ie, for example, by distillation, prepurified oil fractions.
• the decisive factor is the content of impurities that determines the choice of raw materials.
• Common reactor types generally include all furnaces suitable for carbon black production. These in turn can be equipped with different burner technologies.
• An example of this is the Hüls' arc furnace (arc).
• arc Hüls' arc furnace
• the reactors may include the following burners: gas burners with integrated combustion air blowers, gas burners for twisted air flow, gas-injected combination gas burners via peripheral lances, high-speed burners, Schoppe impulse burners, parallel diffusion burners, combined oil-gas burners, overhead burners, evaporative oil burners, burners with air or steam atomization, flat flame burners, gas-heated radiant tubes, as well as all burners and reactors which are suitable for the production of carbon black or for the pyrolysis of carbohydrates, for example sugar, if appropriate in the presence of silicon dioxide.
• the reactor comprises the reaction chamber, a combustion zone, a mixing zone, reaction zone and / or quench zone.
• recuperators are used in the quench zone, such as radiation recuperator with a ring of steel pipes.
• the reactor 6.1 for the reduction of metallic compounds - reduction reactor - is particularly preferably an electric arc furnace, an electric melting furnace, a thermal reactor, an induction furnace, a melt reactor or a blast furnace.
• the reactor is 6.1 and / or the reactor 4.1, preferably both, so tightly designed that the penetration of oxygen is avoided.
• the line 6.3 in the systems according to the invention is particularly preferably designed as a hot gas line so that it largely prevents condensation of the gaseous silicon oxide of the hot process gases, which arise in the production of silicon in the reduction reactor 6.1.
• the hot process gases usually include carbon monoxide, silica and / or carbon dioxide.
• the condensation of silica carries a significant risk of sudden disintegration. Therefore, the hot gas line is preferably provided on its inner surface with a so-called Beschle réelle, which reduces this condensation on the inner surface of the hot gas line, preferably prevented.
• the Beschlemaschine can, for example, on the generation of
• the hot gas line 6.3 can be equipped with a tracing heater and / or have an air gas addition to the temperature control over the surface, in particular for a reactive temperature increase, preferably in the wall area. It goes without saying that the hot gas line 6.3 should be made as short as possible, i. that the exit of the exhaust gas flow 6.3 from the reduction reactor and the entry into the reactor for the thermal conversion of carbon compounds 4.1 should be arranged spatially as close to each other as possible. A corresponding system design can be carried out by a person skilled in the art on the basis of his general knowledge.
• the yield of silicon by up to 20 Mol .-% compared to methods of the prior art can be increased because the silicon oxide formed always remains in the process and only the desired end product silicon is withdrawn from the reactor 6.1.
• the overall process can lead to an increase in yield of silicon in relation to the silicon oxide used by the inventive plant with special streams and special plant design. Due to the introduced heat of reaction of the hot gases reduced z. B. at the same time also the amount of natural gas in Russ production.
• the plant according to the invention for producing high-purity silicon can be operated even more efficiently if special energy flows are used in addition to the special material flows.
• special energy flows are used in addition to the special material flows.
• these energy flows are explained in detail. These energy flows supplement the already discussed material flows, which are used in preferred variants of the present invention together with the energy flows described below.
• Figures 3 to 3i and 4 to 4h the streams are shown with solid lines and the energy flows with dashed lines.
• the subject of the present invention is an overall system 3 or 4 comprising a reactor 4.1 for the thermal conversion of Carbon-containing compounds, wherein the reactor is connected to a combined heat and power system 5.1, via which part of the waste heat 5.3 coupled out of the thermal conversion and another part of the waste heat is converted into electrical energy 5.2.
• the plants also comprise a reduction reactor 6.1 and in Appendix 4 a
• Device / machine / system 8.1 for further processing of material flows 4.2 and 4.3.
• the systems 3 and 4 comprise the streams 4.2, 4.3, 4.4, 6.3, 7.2 and 8.2 which are configured as described above.
• the waste heat is used directly or indirectly for heating or temperature control of the precipitation vessel for the formation of precipitated silicas or silica gels and / or for drying of silica, in particular silica, such as precipitated silica or silica gels, which has been purified by ion exchangers, used in the device 7.1.
• a direct drying of SiO 2 in 7.1 with superheated steam 5.3 can take place. With low-temperature steam 5.3 contact dryers can be operated.
• the recovered electrical energy from the combined heat and power 5.2 can be used to power a reactor 6.1 for the reduction of metallic compounds (see Annexes 3a, 3b, 4a and 4b), for the production of silicon dioxide (see Annexes 3c, 3d, 4c and 4d) , are particularly preferably used in the production of precipitated silica, fumed silica or silica gels and / or are preferably used for drying and / or for temperature control during the precipitation, in the device 7.1. Similarly, the use of electrical energy for the operation of a furnace in the production of fumed silica in 7.1 is possible.
• the whole complex allowed to provide the silicon dioxide and soot production at one site and, if appropriate, to provide the reactor 6.1 for the reduction of metallic compounds via a power grid at another location. Furthermore, it may be advantageous to supply at least a portion of the electrical energy obtained in the power-heat coupling 5.1 via an energy flow 5.4 (not explicitly shown in the figures) to the further processing 8.1.
• the person skilled in the well-known devices 5.1 or 5.1 systems can be used.
• the combined heat and power has a much better efficiency than the pure power generation of thermal thermal power plants.
• the degree of utilization of combined heat and power can be up to 90 percent in particularly preferred cases.
• the combined heat and power not only flow and heat-controlled according to the invention, but also exclusively flow or heat operated operated.
• a combined heat and power plant usually works with hot water steam, which drives steam turbines, over which then takes place the power generation. The extraction of water vapor and supply in one
• Heat exchangers preferably in processes for the production of silicon dioxide, such as for temperature control or for drying of silicon oxide, in a device 7.1, usually takes place before the last turbine stage.
• the decoupling can be carried out expediently also after the last turbine stage.
• Waste heat for drying possible can waste heat from the soot production, such as preferably from the quench zone or other hot reactor parts, for example via heat exchangers or direct use of the process vapors and / or from the combustion of
• Tailgases which in turn can serve for the production of water vapor refer.
• the cogeneration is operated with steam.
• the tail gases contain among other things Water vapor, hydrogen, nitrogen, Cx, carbon monoxide, argon H2S and carbon dioxide.
• the cogeneration operates in the back pressure, whereby no thermal losses occur in the steam cycle. As a result, there is usually no need for fresh cooling water.
• the steam from the quench zone and / or the waste heat from the combustion of the tail gases in 5.1 can be used as waste heat 5.3.
• superheated steam 5.3 from 4.1 or above 5.1 can also be used directly in a process for the production of silicon dioxide, in particular for the direct drying of silicon dioxide, such as silica gel or precipitated silica.
• a contact dryer (device 7.1), for example plate dryer or preferably a rotary tube dryer can be operated with low-temperature steam.
• a contact dryer for example plate dryer or preferably a rotary tube dryer
• With the current obtained from 5.1 preferably primary dryers, in particular nozzle tower dryers or spinflash dryers for drying silicon dioxide can also be operated.
• soot production and the production of silicon oxide in particular the precipitated silica or of the silica gel
• silicon oxide in particular the precipitated silica or of the silica gel
• the educts supplied by the material streams 4.4 and 7.2 must be present in a highly pure form and must not exceed the following limit values for impurities:
• ⁇ boron up to 10 ppm, preferably at most 1 ppm, particularly preferably at most 0.1 ppm, very particularly preferably 0.001 ppm to 0.099 ppm, especially preferably 0.001 ppm to 0.09 ppm, and very especially preferably 0.01 ppm to
• ⁇ calcium maximum of 10 ppm preferably at most 1 ppm, particularly preferably less than or equal to 0.3 ppm, especially preferably 0.001 ppm to 0.3 ppm, very particularly preferably from 0.01 ppm to 0.3 ppm, and particularly preferably 0.05 to
• ⁇ iron maximum of 10 ppm preferably at most 1 ppm, particularly preferably less than or equal to 0.6 ppm, especially preferably 0.001 ppm to 0.6 ppm, very particularly preferably from 0.05 ppm to 0.5 ppm, and particularly preferably 0.01 to 0 , 4 ppm
• Nickel at most 10 ppm, preferably at most 1 ppm, more preferably less than or equal to 0.5 ppm, especially preferably from 0.001 ppm to 0.5 ppm, very particularly preferably 0.01 ppm to 0.5 ppm, and more preferably 0.05 ppm to 0.4 ppm
• ⁇ phosphorus maximum of 10 ppm preferably at most 1 ppm, particularly preferably less than 0.1 ppm, very particularly preferably 0.001 ppm to 0.099 ppm, especially preferably
• Titanium up to 10 ppm, preferably at most 1 ppm, particularly preferably less than 1 ppm, most preferably 0.001 ppm to 0.8 ppm, especially preferably 0.01 ppm to
• Zinc up to 10 ppm, preferably at most 1 ppm, particularly preferably less than or equal to 0.3 ppm, very particularly preferably 0.001 ppm to 0.3 ppm, especially preferably 0.01 ppm to 0.2 ppm and very especially preferably 0.05 ppm to
• the Si ⁇ 2 fed through the material stream 7.2 may be amorphous or crystalline SiO 2, preferably amorphous SiO 2, particular preference being given to precipitated silicas, silica gels, eg. As aerogels or xerogels, fumed silicas, mixed forms or mixtures of precipitated silicas, silica gels and fumed silicas. More preferably, it may be prepared by a process comprising the following steps
• step c Add the silicate solution from step b. into the template from step a. such that the pH of the resulting precipitation suspension is always at a value less than 2, preferably less than 1.5, more preferably less than 1 and most preferably less than 0.5 remains
• the washing medium has a pH of less than 2, preferably less than 1.5, more preferably less than 1 and most preferably less than 0.5
• a template of an acidifier or an acidifier and water is preferably prepared in step a) in the precipitation container.
• the water is preferably distilled or demineralized water.
• the acidulant may be the acidulant which is also used in step d to wash the filter cake.
• the acidulant may be hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, chlorosulphonic acid, sulphuryl chloride or perchloric acid in concentrated or diluted form or mixtures of the abovementioned acids.
• hydrochloric acid preferably 2 to 14 N, more preferably 2 to 12 N, most preferably 2 to 10 N, especially preferably 2 to 7 N and most preferably 3 to 6 N
• phosphoric acid preferably 2 to 59 N, particularly preferred 2 to 50 N, very particularly preferably 3 to 40 N, especially preferably 3 to 30 N and very particularly preferably 4 to 20 N
• nitric acid preferably 1 to 24 N, particularly preferably 1 to 20 N, very particularly preferably 1 to 15 N , especially preferably 2 to 10 N,
• Sulfuric acid preferably 1 to 37 N, more preferably 1 to 30 N, most preferably 2 to 20 N, especially preferably 2 to 10 N are used. Most preferably, concentrated sulfuric acid is used.
• a peroxide is added to the original in step a, which causes a yellow / brown coloration with titanium (IV) ions under acidic conditions.
• This is particularly preferably hydrogen peroxide or potassium peroxodisulfate. Due to the yellow / brown color of the reaction solution, the degree of purification during the washing step d) can be very good be traced. In fact, it has been found that titanium in particular is a very stubborn contaminant, which readily accumulates at the silicon dioxide even at pH values above 2. The disappearance of the yellow coloration in step d) usually means that the desired purity of the
• a silicate solution having a viscosity of 0.1 to 2 poise, preferably 0.2 to 1.9 poise, especially 0.3 to 1.8 poise and especially preferably 0.4, is used in step b) to 1.6 poise, and most preferably 0.5 to 1.5 poise.
• the silicate solution used may be an alkali metal or alkaline earth metal silicate solution, preferably an alkali metal silicate solution, particularly preferably sodium silicate (water glass) and / or potassium silicate solution. Mixtures of several silicate solutions can also be used. Alkali silicate solutions have the advantage that the alkali metal ions can be easily separated by washing. The in step b.
• the silicate solution used preferably has a modulus, ie weight ratio of metal oxide to silicon dioxide, of from 1.5 to 4.5, preferably from 1.7 to 4.2, particularly preferably from 2 to 4.0.
• the viscosity can, for. B. by concentration of commercially available silicate solutions or by dissolving the silicates in water.
• An example of a highly concentrated high viscosity waterglass is water glass 58/60 having a density of 1.690-1.710, an SiO 2 content of 36-37 wt%, an Na 2 O content of 17.8-18.4 % By weight and a Viskosi decisiv at 20 0 C of about 600 poise as in Ullmanns
• PQ Corporation offers water glasses with viscosities of, for example, 15 and 21 pois. The person skilled in the art is aware that he can produce highly concentrated silicate solutions by concentrating less viscous silicate solutions or by dissolving solid silicates in water.
• Silicate solution can be an alkali and / or alkaline earth silicate solution are used, preferably we use an alkali metal silicate solution, particularly preferably sodium silicate (water glass) and / or potassium silicate solution. Mixtures of several silicate solutions can also be used. Alkali silicate solutions have the advantage that the alkali metal ions can be easily separated by washing.
• the silicate solution used in step b) preferably has a modulus, ie weight ratio of metal oxide to silicon dioxide, of from 1.5 to 4.5, preferably from 1.7 to 4.2, particularly preferably from 2 to 4.0.
• the viscosity can, for. B. by concentration of commercially available silicate solutions or by dissolution of the silicates are adjusted in water.
• step c) of this method the silicate solution is added to the template and thus the silicon dioxide is precipitated. It is important to ensure that the acidifier is always present in excess.
• the addition of the silicate solution therefore takes place in such a way that the pH of the reaction solution is always less than 2, preferably less than 1.5, more preferably less than 1, very preferably less than 0.5, and especially preferably from 0.01 to 0.5. If necessary, further acidulant may be added.
• the temperature of the reaction solution is kept at 20 to 95 0 C, preferably 30 to 90 0 C, more preferably 40 to 80 0 C during the addition of the silicate solution by heating or cooling the precipitation vessel.
• Particularly well filterable precipitates are obtained when the silicate solution enters the template and / or precipitation suspension in drop form.
• care is therefore taken to ensure that the silicate solution enters the original and / or precipitation suspension in droplet form. This can be achieved, for example, by introducing the silicate solution into the original by means of drops. This may be a dosing unit mounted outside the template / precipitation suspension and / or dipping in the template / precipitation suspension.
• the original / precipitation suspension is stirred so that the flow rate measured in a region of the surface of the reaction solution to 10 cm below the reaction surface ranges from 0.001 to 10 m / s, preferably 0.005 to 8 m / s, more preferably 0.01 to 5 m / s, more preferably 0.01 to 4 m / s, especially preferably 0.01 to 2 m / s and most preferably 0.01 to 1 m / s.
• the silicate solution is dropped into a receiver / precipitation suspension at a flow rate measured in a range of the surface of the reaction solution to 10 cm below the surface
• Reaction surface ranges from 0.001 to 10 m / s, preferably 0.005 to 8 m / s, more preferably 0.01 to 5 m / s, very particularly 0.01 to 4 m / s, especially preferably 0.01 to 2 m / s and very especially preferably 0.01 to 1 m / s s introduced.
• silica particles which can be filtered very well.
• very fine particles are formed in processes in which there is a high flow velocity in the receiver / precipitation suspension, and these particles are very difficult to filter.
• step d) The silicon dioxide obtained after step c) is in this process in step d) of the remaining constituents of
• Precipitated suspension separated. Depending on the filterability of the precipitate, this can be done by conventional filtration techniques known to those skilled in the art, e.g. As filter presses or rotary filter, done. In difficult to filter precipitates, the separation can also by centrifugation and / or by
• the precipitate is washed in this process, it being ensured by means of a suitable washing medium that the pH of the washing medium during the wash and thus also that of the silicon dioxide is less than 2, preferably less than 1.5, particularly preferably less than 1 , very particularly preferably 0.5 and especially preferably 0.001 to 0.5.
• a suitable washing medium that the pH of the washing medium during the wash and thus also that of the silicon dioxide is less than 2, preferably less than 1.5, particularly preferably less than 1 , very particularly preferably 0.5 and especially preferably 0.001 to 0.5.
• the washing medium is preferably used in step a) and c) acidifier or
• a chelating reagent to the washing medium or to precipitate the silica in a washing medium having a corresponding pH of less than 2, preferably less than 1.5, more preferably less than 1, most preferably 0.5, and especially preferably From 0.001 to 0.5 containing a chelating reagent.
• the washing with the acidic washing medium takes place immediately after the separation of the silicon dioxide precipitate, without further steps being carried out. Washing is continued until the wash suspension consisting of silicon dioxide after step c) and the washing medium no longer shows any yellowing.
• the thus-washed silica is preferably used in an intermediate step d1), i. between step d) and e) further washed with distilled water or demineralized water until the pH of the silica obtained is 4 to 7.5 and / or the conductivity of the washing suspension is less than or equal to 9 ⁇ S / cm, preferably less than or equal to 5 ⁇ S / cm. This ensures that any acid residues adhering to the silica have been sufficiently removed.
• the entire washing steps can preferably be carried out at temperatures of 15 to 100 ° C.
• the milling is carried out in fluidized bed counter-jet mills to minimize or avoid contamination of the high-purity silicon dioxide with metal abrasion of the mill walls.
• the grinding parameters are selected so that the obtained particles have a mean particle size d 5 o of 1 to 100 microns, preferably 3 to 30 .mu.m, particularly preferably from 5 to 15 microns.
• the method described above for the production of silicon dioxide can be carried out in the device 7.1, ie in this case the device 7.1 comprises all the necessary parts of the plant for carrying out the method described above, but it is also possible that the device 7.1 itself only a part of a plant , such as B. a precipitation vessel for precipitation or gelation and / or a dryer, is, in which the previously described Si ⁇ 2 ⁇ production method is performed. It should be emphasized at this point that the present invention is not limited to the method described above, but the SiO 2 can also be prepared by other methods, in particular, when the SiO 2 is pyrogenic silicic acids or silica gels.
• Another object of the invention is an overall system, such as 3e, 3f, 4e and 4f, in which a reactor 4.1 is connected to the thermal conversion of carbon-containing compounds with a combined heat and power 5.1, on the part of the waste heat 5.3, from the thermal conversion in 4.1, decoupled and another part of the waste heat can be converted into electrical energy 5.2, wherein the decoupled waste heat 5.3, in particular in processes for the production of silicon dioxide, is used in a device 7.1.
• the device 7.1 can be part of a plant for the production of silicon dioxide.
• the waste heat 5.3 or the waste heat stream 5.3 for temperature control of a precipitation vessel and / or for drying of silica, in particular of silica, such as precipitated silica, silica gel or silica, which has been purified by ion exchangers, are used in the device 7.1.
• the decoupled waste heat in particular directly (see Figure 3e or 4e) or by means of heat exchanger 8, as shown in Figures 3f and 4f of the device 7.1.
• the electrical energy 5.2 is used to supply energy to a reactor 6.1 for the reduction of metallic compounds or in processes for producing silicon dioxide, in particular for the device 7.1.
• Figures 3e and 3f is the
• the waste heat 6.2 from the reactor 6.1 for the reduction of metallic compounds in a process for the production of silicon dioxide for example, used to control the temperature or drying of silica in the device 7.1 .
• Waste heat streams from the reactors 4.1 and 6.1 used together for the operation of 7.1.
• the waste heat 6.2 of the reactor for the reduction of metallic compounds in the device 7.1 is used, in particular the waste heat is 6.2 via heat exchanger 8 (in Figures 3e, 3f, 4e, 4f not shown) or the previously described modifications thereof from the reactor 6.1 transferred to the device 7.1.
• This can be done by the waste heat, in particular a waste heat stream 6.2, the reactor 6.1 is connected to the device 7.1.
• part of the hot process gases from the reactor 6.1 preferably the part which can not be further utilized in 4.1, i. the part without CO and SiO, to lead via a hot gas line 6.3 in the cogeneration 5.1 or in the thermal power plant 5.1.
• a hot gas line 6.3 connects the reactor 6.1 for the reduction of metallic compounds with the combined heat and power 5.1 or a thermal power plant 5.1, in particular for transferring the hot process gases from the reactor 6.1 in 5.1 for steam generation.
• an alternative object of the invention is a system according to the invention with a reactor 4.1 for the thermal conversion of carbon-containing compounds, wherein the reactor is connected to a combined heat and power 5.1 via the part of the waste heat 5.3 coupled out of the thermal conversion and / or another part of the waste heat is converted into mechanical or electrical energy 5.2, or, wherein the reactor 4.1 is connected to a thermal power plant 5.1, via which the waste heat is converted into mechanical or electrical energy 5.2.
• the electrical energy obtained can be fed into the public grid, internally to the power supply or according to the invention for the operation of the reduction reactor 6.1 in the production of silicon or for the production of silica, preferably of precipitated silica or fumed silica or silica gels in precipitated silicas and silica gels particularly preferred for drying or Heating the precipitation tank to be used.
• the decoupled waste heat can be fed into a district heating network, it being preferred that the waste heat via heat exchangers in the process for the production of silicon dioxide, such as for temperature control or drying of silica, in particular of silica for further use in the production of silicon.
• a further alternative embodiment provides a combination in which the plant according to the invention, for. B. plants 3a, 3b, 3g, 4a or 4b, - as a unit - a reactor 4.1 for the thermal conversion of carbon-containing compounds, wherein the reactor may be connected to a combined heat and power 5.1 on the part of the waste heat 5.3 decoupled from the thermal conversion and / or another part of the waste heat can be converted into mechanical or electrical energy 5.2, or, wherein the reactor 4.1 is connected to a thermal power plant 5.1, via which the waste heat is converted into mechanical or electrical energy 5.2 and the electrical energy 5.2 for supplying energy to a reactor 6.1 for the reduction of metallic compounds, in particular an electric arc furnace 6.1 electric melting furnace, thermal reactor, induction furnace, melt reactor or blast furnace, preferably for the production of silicon, or also for supplying energy to a device 7.1 in the production of silicon dioxide, such as for temperature control one
• Feller for the drying of silica, such as SiO 2, or for the operation of a furnace for the production of fumed silica is used.
• 5.1 can also be operated in such a way that only the waste heat 5.3 or electrical energy 5.2 or any mixed forms are used.
• the decoupled waste heat 5.3 is guided to the device 7.1, in particular the waste heat is transferred via a heat exchanger 5.3 5.3 or used directly as superheated steam, preferably the device 7.1 part of a plant for the production of silica.
• the device 7.1 may be a precipitation vessel for precipitation or gelation of SiO 2 and / or a dryer, a tunnel kiln, rotary kiln, rotary kiln, fluidized bed, rotary kiln, circulating fluidized bed apparatus, continuous furnace and / or an oven for pyrolysis in all plants.
• directly superheated steam 5.3 which is obtained directly or indirectly in 4.1, for example by quenching with water, preferably demineralized or distilled water, from the waste heat of 4.1 or via the combustion of tail gases from 4.1, can be used for drying silicon dioxide become.
• contact dryers 7.1 for example, plate dryers or particularly preferably rotary kiln dryers offers.
• the current obtained via 5.1 5.2 can be used directly for the operation of primary driers.
• These are preferably nozzle tower dryers or spinflash dryers. It is clear to the person skilled in the art that the abovementioned enumeration is to be understood only as an example and that other conventional dryers can also be used.
• the reactors 4.1 or 6.1 applies that all or parts of the waste heat produced there, such as the reaction zone, the hot reactor parts, steam by quenching with water, preferably deionized or distilled water, in 4.1 or the waste heat of the reaction products, such as Gases or other streams, as used waste heat to be detected according to the invention.
• the waste heat generated is used in the plant according to the invention.
• the system operates continuously 24 hours a day, 7 days a week, so that the use of waste heat, directly or via the heat exchanger 8, in a continuous cycle, in particular via primary and / or secondary circuits occurs.
• the energy savings that can be achieved per kilogram of dried silicon dioxide from 7.1 can be between 1 to 10 kWh, preferably 2 to 6 kWh, particularly preferably around 2 kWh. It is clear to the person skilled in the art that the respectively achieved energy balance directly depends on the residual moisture and the used drying device as well as on other
• Process parameters depends, so that the values are to be understood as indicative only.
• the obtained electrical energy of about 1 to 10 kWh, preferably by 5 kWh per kilogram of soot for reduction of one kilogram of silicon dioxide to molten silicon in 6.1
• the energy savings can increase to 5 kWh to 20 kWh, in particular, it may, considering the overall process, comprising the production of silicon dioxide and carbon black and their conversion to silicon, in the range of 17 kWh.
• the waste heat 6.2 together with the waste heat 5.3 can be used in a process for the production of silicon dioxide for the device 7.1, preferably for the temperature control or for the drying of silicon dioxide. in particular of precipitated silica or silica gel or precipitated silica or silica gel which has been purified by means of an ion exchanger.
• the use of the waste heat 6.2 and / or 5.3 for drying the silica preferably takes place via one or more heat exchangers 8 (not shown in FIGS. 3e, 3f, 4e, 4f).
• the device 7.1 can be part of a plant for the production of silicon dioxide in all plants.
• Heat exchangers 8 are preferably used to prevent contamination of the silicon dioxide, in particular of high-purity silicon dioxide.
• the waste heat from the reactor 6.1 is used by means of a secondary circuit in a process for the production of silicon dioxide, such as for drying of silicon dioxide or temperature control of a precipitation tank.
• a medium water a conventional coolant or other media well-known to those skilled.
• An expedient system 3h, 3i, 4g or 4h also provides for the sole use of the waste heat 6.2 from the reactor 6.1 for the reduction of metallic compounds in the process for the production of silicon dioxide in the device 7.1, in particular for the temperature control of a precipitation container 7.1 or dryer 7.1 for drying of silicon oxide, in particular, the system 3i or 4h can be carried out in such a way that the waste heat 6.2 is conducted from the reactor 6.1 via the heat exchanger 8 into the device 7.1 by means of the heat exchanger 8.
• the device 7.1 which may in particular be a reactor, precipitation vessel and / or dryer, is only part of a partial or total plant for the production of silicon oxide and is connected upstream and / or downstream with other plants or devices or is connectable, for example, to produce high purity silica from contaminated silicates.
• the supply line 7.2 in all systems is to be regarded as a direct or indirect supply line into the reactor or as a material flow into the reactor 6.1.
• the silica dried in 7.1 in 8.1 may preferably be subjected to further processing steps before it is fed to the reactor 6.1. These are in particular grinding, formulating, briquetting. Also in these steps the electrical energy flow according to 5.2 can be used.
• the waste heat of the reactor 4.1 is used for the thermal conversion of carbon-containing compounds for the production of electrical energy, in particular by means of a combined heat and power or thermal thermal power plant. As waste heat, the waste heat of the
• Tailgases and the waste heat which is produced by combustion of the tail gas. It is particularly preferred if the waste heat is used in whole or in part, in particular directly or indirectly, in processes for the production of silicon dioxide, such as for temperature control or for drying.
• superheated steam from 4.1 and / or 5.1 in 7.1 can be used for drying or tempering.
• the electrical energy obtained can preferably be used to operate a reactor 6.1 for the reduction of metallic compounds or for the operation of devices 7.1, in processes for the production of silicon dioxide, preferably for the operation of dryers, such as primary dryers, furnaces for the production of fumed silica for the production of silicon or for the temperature control of precipitation tanks or for the operation of other process steps, which work with electric current.
• dryers such as primary dryers, furnaces for the production of fumed silica for the production of silicon or for the temperature control of precipitation tanks or for the operation of other process steps, which work with electric current.
• the energy balance of the silicon dioxide process may be preferred in the particularly energy intensive steps, such as For example, the heating of the precipitation container or in drying steps of the silicon dioxide and further process steps, which must be supplied with energy considerably improved.
• the consistent use of waste heat, combustible residual gases and / or the return of the hot gas from 6.1 all material cycles can be driven in the system with an improved energy balance over known methods of the prior art.
• the recirculation of the hot gases, the carbon monoxide and silica, in particular gaseous SiO include in the reactor 4.1 to a process intensification, in particular, the formation of carbon monoxide can be reduced during the process for the production of soot in the overall balance.
• the overall process in the overall plant according to the invention or in the subsystems leads to a significant reduction of the carbon dioxide and / or carbon monoxide formed over the entire process in the production of silicon, in particular compounds containing silicon dioxide and carbon, such as carbon black or pyrolyzed high-purity carbohydrate.
• the plants mentioned can also have a multiplicity of reactors, which in particular can permit the continuous and uninterrupted execution of the overall process.
• the reactors can be operated continuously or discontinuously.
• the inventive system for further purification of the elemental silicon obtained from 6.1 additional purification units such. B. investments or
• the contaminant is elemental sulfur, it evaporates above 444.6 ° C. and is expelled from the reactor 6.1 with the furnace gas CO / SiO. When the furnace gas is burned, 4.1 SO2 is produced in the reactor. Hydrogen excess in the reactor 4.1 produces H2S, which must be disposed of.
• impurities are sulfates, eg. B. from the SiO 2 -HerStellung.
• CaSO 4 + C CaO + SO 2 + CO Above 801 0 C the equilibrium is shifted to the right.
• the sulfate sulfur is driven with the furnace gas from the reactor 6.1 and excreted from the cycle process as described above as H 2 S.
• the CaO remains in the reactor 6.1 and forms with the silica a calcium silicate which is then reduced and the silicon is contaminated.
• sulfides are FeS 2 , MnS, MgS and CaS. No roasting reaction can take place around the Si arc furnace since there is no free oxygen.
• SiS evaporates from the reactor 6.1, Fe is dissolved in the Si. Additional purification may be by directional solidification.
• MnS + Si SiS + Mn equilibrium at 2000 ° C SiS evaporates, Mn dissolves in Si. Additional purification can only be done by directional solidification.
• SiS evaporates. Mg dissolves in Si. Additional purification can only be done by directional solidification.
• reactor for the production of silicon from silicon dioxide and carbon for example electric melting furnace, induction furnace, electric arc furnace (other alternatives are mentioned in the description);
• Silica for example in a drying stage, preferably a dryer, for example, fluidized bed reactor or other reactor for drying substrates, a reactor (furnace for the production of fumed silica) or a precipitation vessel; 8.1: Device / machine / plant for further processing of the streams 4.2 and 4.3 comprising, for example, a mixing unit in the carbon and the silica mixed as homogeneously as possible and / or a unit for the production of moldings of SiO 2 and C by
• heat exchangers preferably they have a secondary circuit and allow the dissipation of waste heat (thermal energy) of processes, in 4.1 and / or 6.1, and the supply of thermal energy in endothermic processes, in particular in 7.1 for drying;
• Material streams 4.2 stream of carbon produced in the reactor 4.1, preferably in the form of carbon black or coal or the pyrolysis product of a carbohydrate
• thermal energy flow or energy flow such as superheated steam or low-temperature steam, which is used for example by pipes, optionally with connected heat exchangers 8, to use the waste heat from 4.1, which is decoupled over 5.1, for drying or tempering in 7.1;
• thermal energy flow for example, line (s), in particular with connected heat exchangers 8, to use the waste heat from 6.1 in 7.1, preferably as a secondary circuit;
• FIGS. 1, Ia are identical to FIGS. 1, Ia:
• FIGS. 2, 2a are identical to FIGS. 2, 2a:
• FIGS. 3 a to 3 i show combinations according to the invention of installations in which the waste heat or exhaust gas streams of the reactors 4.1 and 6.1, for example, are heated. B. in the tempering or in the drying step in the production of silicon dioxide, partially via a combined heat and power (5.1, 5.3 and 5.2) or via heat exchanger 8 can be used. In the alternatives 3a and 3b also obtained by means of combined heat and power from the waste heat and the exhaust gases of the reactor 4.1 energy flows for the operation of the reduction reactor 6.1 are used.
• FIGS. 4a to 3h show combinations according to the invention of installations in which the waste heat or waste gas streams of the reactors 4.1 and 6.1, for. B.
• the systems according to FIGS. 4a to 4h additionally comprise a further processing device 8.1 which ensures that the raw materials SiO 2 and C are supplied to the reduction reactor 6.1 in optimized form and optimum weight ratio.
• Figures 3 and 4 represent a system 3 with a reactor 4.1 for the thermal conversion of carbon-containing compounds, wherein the reactor is connected to a combined heat and power 5.1, decoupled over the part of the waste heat 5.3 thermal conversion and another part is converted into mechanical or electrical energy 5.2. Via the line 5.3, the decoupled heat is dissipated.
• the entire waste heat or a portion of the waste heat for temperature control of the device 7.1 see Figures 3a to i and 4 a to h) or used for energy.
• a precipitation tank can be tempered or dryer 7.1 can be operated. About 5.2, the generated electrical energy can be forwarded.
• the electrical energy can be fed into the public power grid, used in the process for the production of silicon dioxide or directly in an overall process for producing silicon in an electric furnace, for example an electric arc furnace 6.1 (see FIGS. 3a, 3b, 3g, 4a to 4g) , According to Annexes 3 c - f and 4 c - d, 5.1 can be used to generate electricity, whereby the electricity can also be used to operate 7.1 or other parts of the system.
• a special system according to the invention as shown schematically in FIG. 4e, with its energy and material flows will be explained in more detail below.
• This plant comprises a plant for the production of silicon dioxide 7.1 with a precipitation tank, facilities for
• the waste heat of the reduction reactor 6.1 can be used via the heat flow 6.2 in addition to the drying of the silicon dioxide.
• the total energy requirement of 14.33 kwh of energy per kg of 7.1 can be obtained by the energy flows
• Streams are quenched into the carbon black reactor 4.1 via 4.4 1.28 kg of oil per kg of carbon produced and 3,843 kg of water per kg of carbon produced. This gives an output of 1,281 kg of carbon in the form of soot, which is fed to the sparger 8.1 via the material flow 4.2. Furthermore, 0.656 kg of powdery SiO 2 is obtained, to which it is fed via the stream 4.3. Finally, a tail gas is obtained with a calorific value of 5 kwh / kg C and 3,847 kg of water vapor which are fed via the combined heat and power plant 5.1 and the energy stream 5.3 of the precipitation 7.1.
• the drawn in Figure 4e energy stream 5.2 is not used in this example, instead the energy obtained from the combined heat and power is used over 5.3 for drying the SiO 2.
• the silicon dioxide production 7.1 and the carbon production in 4.1 must first be carried out once.
• the SiO / SiO 2 cycle described above forms between the electric arc furnace 6.1, the carbon black reactor 4.1. From this cycle finished silicon is withdrawn and introduced new SiO 2 from the precipitate 7.1 via 7.2 in the circuit.
• the SiO and CO formed during the reduction reaction in the electric arc furnace are utilized in the carbon black reactor.
• the main waste product from the cycle is thus mainly CO2, which must be disposed of. Other waste products in small to very small amounts may be due to contamination of the reactants arise, such. B. H 2 S, when sulfur impurities are included.

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