CN109279609B - Modification method of petroleum coke, modified petroleum coke obtained by modification method, carbonaceous reducing agent and smelting method of industrial silicon - Google Patents
Modification method of petroleum coke, modified petroleum coke obtained by modification method, carbonaceous reducing agent and smelting method of industrial silicon Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to the technical field of industrial silicon smelting and new energy, and discloses a petroleum coke modification method, a modified petroleum coke obtained by the petroleum coke modification method, a carbonaceous reducing agent and an industrial silicon smelting method, wherein the modification method comprises the following steps: mixing a modifier with petroleum coke, drying and forming the mixture, wherein the modifier is asphalt and/or heavy oil. The modified petroleum coke obtained by the modification method of the invention replaces charcoal to be used as the carbonaceous reducing agent component of the industrial silicon, can overcome the defects of low reaction activity, low volatile component and the like when the petroleum coke is used as the carbonaceous reducing agent component for the industrial silicon smelting, and improves the adaptability of the petroleum coke.
Description
Technical Field
The invention relates to the technical field of industrial silicon smelting and new energy, in particular to a petroleum coke modification method, modified petroleum coke obtained by the petroleum coke modification method, a carbonaceous reducing agent and an industrial silicon smelting method.
Background
Charcoal and coal washing are commonly used carbonaceous reducing agents in the industrial silicon industry at present, and the charcoal process and the coal tar coke washing process are mainstream processes in the industrial silicon production at present. Because the dependence of the charcoal on forest resources seriously damages the ecological environment, along with the enhancement of the protection consciousness of the forest resources, the supply of the charcoal is increasingly tense, and the reduction of the consumption of the charcoal becomes a trend. Therefore, a new carbonaceous reducing agent suitable for industrial silicon smelting must be found to ensure the production requirement and reduce the production cost. In foreign countries, some countries with advanced industrial silicon smelting technology, such as Norway and the like, use coal or coal-based carbon as a reducing agent for industrial silicon smelting, can reduce the production cost and improve the economic benefit of enterprises. However, coal or coal-based carbon has the problem of high ash content, so that the content of trace elements in industrial silicon products is caused, and the quality and the grade of the products are influenced.
The petroleum coke is used as one of carbonaceous reducing agents, has the characteristics of small ash content, high fixed carbon content, certain mechanical strength and the like, and can be used as a reducing agent according to the requirements of furnace conditions and product quality. The annual output of the petroleum coke in China is about 2500 million tons, and the petroleum coke is used as an industrial silicon smelting reducing agent instead of charcoal, so that the application field of the petroleum coke can be widened, and the additional value of the petroleum coke can be improved. However, in order to improve economic benefits, the delayed coking unit in China at present adopts relatively harsh process operation conditions to obtain higher liquid product yield, so that the volatile components of petroleum coke have strict assessment indexes, and the volatile components of the petroleum coke (green coke) are required to be not more than 12 percent and are generally about 10 percent on average. The low volatile content is not suitable for the requirement of the industrial silicon smelting on the carbonaceous reducing agent. Meanwhile, the petroleum coke also has the problems of poor reaction performance and low reducibility utilization efficiency.
CN103626183A discloses a reducing agent for industrial silicon production, which comprises 0-100% of petroleum coke particles and 0-100% of modified petroleum coke particles by mass percentage, wherein the particle sizes of the petroleum coke particles and the modified petroleum coke particles are both in the range of 5-60 mm. The dry-base fixed carbon of the reducing agent is more than or equal to 76 percent, the residual ash content is less than or equal to 1 percent, the volatile matter is 10 to 16 percent, the water content is less than or equal to 8 percent, and the furnace life can be prolonged by about one time. However, the reactivity of petroleum coke in the reducing agent is to be improved.
CN105329897A discloses a preparation method of a composite reducing agent applied to industrial silicon smelting production, wherein the grain size ratio of petroleum coke materials is as follows: 60-75 wt% of petroleum coke with the particle size of less than 0.1mm and 25-40 wt% of petroleum coke with the particle size of more than 0.1 mm; the particle size ratio of the anthracite/bituminous coal material is as follows: 55-75% of the particles with the particle size of 0.15-0.3 mm, and 25-45% of the particles with the particle size of less than 0.15 mm; mixing charcoal powder and biomass charcoal/semicoke according to any proportion to obtain a charcoal powder mixture, wherein the grain size ratio of the charcoal powder mixture is as follows: the particle size ratio of the particles with the particle size of less than 0.075mm accounts for 75-90%, and the particle size ratio of the particles with the particle size of more than 0.075mm accounts for 10-25%; uniformly mixing the prepared petroleum coke material, anthracite/bituminous coal material and carbon powder mixed material to obtain a mixture, adding an organic binder, an additive and water into the mixture, uniformly stirring, preparing pellets, and drying to obtain the composite reducing agent.
The above patent application mainly designs the formula of the reducing agent, and considers the grain size distribution and the proportion of various materials in the formula.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a petroleum coke modification method, modified petroleum coke obtained by the petroleum coke modification method, a carbonaceous reducing agent and an industrial silicon smelting method.
In order to achieve the above object, in a first aspect, the present invention provides a method for modifying petroleum coke, the method comprising: mixing a modifier with petroleum coke, drying and forming the mixture, wherein the modifier is asphalt and/or heavy oil.
In a second aspect, the invention provides modified petroleum coke prepared by the method of the invention.
In a third aspect, the present invention provides a carbonaceous reducing agent, wherein the carbonaceous reducing agent comprises bituminous coal and/or anthracite and petroleum coke, the bituminous coal and/or anthracite is 10 to 90 wt% and the petroleum coke is 10 to 90 wt% based on the weight of the carbonaceous reducing agent, and the petroleum coke is the modified petroleum coke of the present invention.
In a fourth aspect, the present invention provides a method for smelting industrial silicon, comprising: under smelting conditions, a silicon source is contacted with the carbonaceous reducing agent.
The modified petroleum coke obtained by the modification method of the invention replaces charcoal to be used as the carbonaceous reducing agent component of the industrial silicon, can overcome the defects of low reaction activity, low volatile component and the like when the petroleum coke is used as the carbonaceous reducing agent component for the industrial silicon smelting, and improves the adaptability of the petroleum coke.
The carbonaceous reducing agent does not need to contain charcoal, the production requirement can be ensured, the production cost can be greatly reduced, and the obtained silicon has high grade and high yield, namely, petroleum coke is used for replacing the charcoal as the component of the carbonaceous reducing agent of the industrial silicon, and the carbonaceous reducing agent is a solution for protecting forest resources and ecological environment.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for modifying petroleum coke, the process comprising: mixing a modifier with petroleum coke, drying and forming the mixture, wherein the modifier is asphalt and/or heavy oil.
In the invention, the modifier is liquid and/or solid at normal temperature, preferably, the asphalt is petroleum asphalt and/or coal asphalt, and the heavy oil is at least one of ethylene tar, coal tar, atmospheric residue, vacuum residue, heavy oil and catalytic cracking slurry oil. Among them, it will be understood by those skilled in the art that when the modifier is two or more species, the amount used may be any ratio between the species, and the ash content of each of the foregoing modifiers is less than 0.3% by weight.
Preferably, the petroleum coke to be modified is petroleum coke produced by a conventional delayed coking unit, and the volatile content is 5 to 12 wt%, more preferably 6 to 10 wt%.
Preferably, the ash content of the petroleum coke to be modified is less than 0.3 wt.%, more preferably 0-0.2 wt.%.
Preferably, the weight ratio of the modifier to the petroleum coke is 1: 0.1 to 20, more preferably 1: 0.1-10.
Preferably, the method of mixing the modifier with the petroleum coke comprises: heating a mixture of a modifier and petroleum coke to a modification temperature of 50-200 ℃, and at which the modifier is liquid. It is understood by those skilled in the art that, in the modifier, the ethylene tar and the coal tar are liquid at normal temperature, and when the modifier is the ethylene tar and/or the coal tar, the modification temperature can be 50-80 ℃; among the above-mentioned modifiers, petroleum asphalt, coal asphalt, atmospheric residue, vacuum residue, heavy oil and catalytic cracking slurry oil are solid at normal temperature, and when the modifier contains at least one of the above-mentioned substances which are solid at normal temperature, the modification temperature may be 20 to 50 ℃ higher than the softening point of the modifier. The specific modification temperature can be selected between 50 ℃ and 200 ℃ according to different types of the modifying agent, and the modifying agent has good fluidity at the modification temperature, so that the petroleum coke and the modifying agent can be uniformly mixed.
Preferably, the mixing is performed under stirring for the purpose of uniform mixing, wherein the stirring speed may be 80-200 rpm.
Preferably, the drying conditions include: the temperature is 100-200 ℃ and the time is 1-5 h. The drying treatment can not only improve the volatile component of the petroleum coke, but also improve the reaction performance of the petroleum coke as a carbonaceous reducing agent.
The molding method is not particularly limited, and various molding methods commonly used in the art may be used, which are well known to those skilled in the art and will not be described herein again.
In a second aspect, the invention provides modified petroleum coke prepared by the method of the invention.
Preferably, the volatile content of the modified petroleum coke is 12 to 20 wt%, and more preferably 14 to 18 wt%.
In a third aspect, the present invention provides a carbonaceous reducing agent, wherein the carbonaceous reducing agent comprises bituminous coal and/or anthracite and petroleum coke, the bituminous coal and/or anthracite is 10 to 90 wt% and the petroleum coke is 10 to 90 wt% based on the weight of the carbonaceous reducing agent, and the petroleum coke is the modified petroleum coke of the present invention.
Preferably, the bituminous coal and/or anthracite coal is present in an amount of 25 to 50 wt% and the petroleum coke is present in an amount of 50 to 75 wt% based on the weight of the carbonaceous reductant.
Among the carbonaceous reducing agents of the present invention, bituminous coal and/or anthracite coal may be various bituminous coals and anthracite coals, respectively, which are commonly used in the art for carbonaceous reducing agents. Among them, it is understood by those skilled in the art that charcoal is not included in the carbonaceous reducing agent of the present invention.
In a fourth aspect, the present invention provides a method for smelting industrial silicon, comprising: under smelting conditions, a silicon source is contacted with the carbonaceous reducing agent.
In the method of the present invention, the silicon source is any silicon source commonly used in the art, such as silica.
In the method of the present invention, the smelting conditions may be various smelting conditions commonly used in the art, for example, the smelting conditions may include: the temperature is 2350-3000 deg.C, preferably 2600-2800 deg.C.
In the method of the present invention, the weight ratio of the silicon source to the carbonaceous reducing agent is preferably 1: 0.8 to 2, more preferably 1: 1-1.4.
Examples
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, each material used was commercially available, and each method used was a method conventional in the art.
Wherein, the bituminous coal is from Ningxia, the volatile content is 25 wt%, and the ash content is 7.5 wt%.
The method for measuring the volatile content in the petroleum coke comprises the following steps: SH/T0026-1990 Petroleum coke volatiles assay.
The method for measuring the content of the volatile components in the bituminous coal comprises the following steps: GB-T212-2008 coal industrial analysis method.
The method for measuring the ash content in the petroleum coke comprises the following steps: SH/T0029-1990 Petroleum coke ash assay.
The method for measuring the ash content in the modifier comprises the following steps: GB508 petroleum products ash assay.
The method for measuring the ash content in the bituminous coal comprises the following steps: GB-T212-2008 coal industrial analysis method.
The method for measuring the reactivity of petroleum coke air comprises the following steps: YS/T587.1-587.14 carbon anode is detected by using calcined petroleum coke.
The classification method of the silicon grade comprises the following steps: the silicon is classified according to the contents of iron, aluminum and calcium in the silicon, and the purity of the silicon is represented as follows: such as 553 rating, 442 rating, 441 rating, 421 rating, etc.; taking a 553 rating as an example, the first number represents the highest iron content, i.e. no more than 0.5 wt.%, the second number represents the highest aluminum content, i.e. no more than 0.5 wt.%, and the third number represents the highest calcium content, i.e. no more than 0.3 wt.%.
Example 1
Heating petroleum coke with volatile content of 8.9 wt% and ash content of 0.29 wt% and petroleum asphalt with ash content of 0.06 wt% at 105 ℃, and stirring at 100rpm to mix them uniformly, wherein the weight ratio of petroleum coke to petroleum asphalt is 4: 1, drying the mixture at 150 ℃ for 2h, and forming to obtain the modified petroleum coke A with the volatile content of 14.2 wt% and the ash content of 0.25 wt%.
The reactivity of the petroleum coke before modification and the modified petroleum coke A obtained are respectively measured, and the results are respectively 60% and 78%. Namely, the petroleum coke is modified by the method of the embodiment, so that the volatile content of the modified petroleum coke is increased by 5.3 wt%, the reaction activity is increased by 18%, and the requirement of the industrial silicon-carbon reducing agent can be better met.
Example 2
Heating petroleum coke with the volatile content of 8.9 wt% and the ash content of 0.29 wt% and catalytic cracking slurry oil with the ash content of 0.24 wt% at 80 ℃, and stirring at 100rpm to uniformly mix the petroleum coke and the catalytic cracking slurry oil, wherein the weight ratio of the petroleum coke to the catalytic cracking slurry oil is 1: 1, drying the mixture at 100 ℃ for 4h, and forming to obtain the modified petroleum coke B with the volatile content of 14.8 wt% and the ash content of 0.27 wt%.
The reactivity of the petroleum coke before modification and the modified petroleum coke B obtained are respectively measured, and the results are respectively 60% and 82%. Namely, the petroleum coke is modified by the method of the embodiment, the volatile content of the modified petroleum coke is increased by 5.9 wt%, the reaction activity is increased by 22%, and the requirement of the industrial silicon-carbon reducing agent can be better met.
Example 3
Heating petroleum coke with the volatile content of 9.1 wt% and the ash content of 0.21 wt% and a modifier with the ash content of 0.12 wt% at 95 ℃, and stirring at 100rpm to uniformly mix, wherein the modifier is a mixture of petroleum asphalt and ethylene tar, and the weight ratio of the petroleum asphalt to the ethylene tar is 3: 1, the weight ratio of the petroleum coke to the modifier is 10: 1, drying the mixture at 180 ℃ for 1h, and forming to obtain the modified petroleum coke C with the volatile content of 14.5 wt% and the ash content of 0.20 wt%.
The reactivity of the petroleum coke before modification and the modified petroleum coke C obtained is respectively determined, and the result is respectively 62% and 84%. Namely, the petroleum coke is modified by the method of the embodiment, the volatile content of the modified petroleum coke is increased by 5.4 wt%, the reaction activity is increased by 22%, and the requirement of the industrial silicon-carbon reducing agent can be better met.
Example 4
Heating petroleum coke with the volatile content of 9.1 wt% and the ash content of 0.21 wt% and a modifier with the ash content of 0.17 wt% at 105 ℃, and stirring at 100rpm to uniformly mix, wherein the modifier is a mixture of catalytic cracking slurry oil and vacuum residue, and the weight ratio of the catalytic cracking slurry oil to the vacuum residue is 1: 1, the weight ratio of the petroleum coke to the modifier is 1.5: 1, drying the mixture at 140 ℃ for 1.5h, and forming to obtain the modified petroleum coke D with the volatile content of 14.9 wt% and the ash content of 0.19 wt%.
The reactivity of the petroleum coke before modification and the modified petroleum coke D obtained were measured respectively and the results were 62% and 86%, respectively. Namely, the petroleum coke is modified by the method of the embodiment, so that the volatile content of the modified petroleum coke is increased by 5.8 wt%, the reaction activity is increased by 24%, and the requirement of the industrial silicon-carbon reducing agent can be better met.
Example 5
Heating petroleum coke with the volatile content of 9.1 wt% and the ash content of 0.21 wt% and coal tar with the ash content of 0.005 wt% at 50 ℃, and stirring at 100rpm to uniformly mix the petroleum coke and the coal tar, wherein the weight ratio of the petroleum coke to the coal tar is 9: 1, drying the mixture at 160 ℃ for 1.5h, and forming to obtain the modified petroleum coke E with the volatile content of 14.8 wt% and the ash content of 0.19 wt%.
The reactivity of the petroleum coke before modification and the modified petroleum coke E obtained are respectively determined, and the result is respectively 62% and 88%. Namely, the petroleum coke is modified by the method of the embodiment, the volatile content of the modified petroleum coke is increased by 5.7 wt%, the reaction activity is increased by 26%, and the requirement of the industrial silicon-carbon reducing agent can be better met.
Example 6
The process of example 1 was followed except that the weight ratio of petroleum coke to petroleum pitch was 0.1: 1, obtaining the modified petroleum coke F with the volatile content of 15.2 weight percent and the ash content of 0.08 weight percent.
The reactivity of the petroleum coke before modification and the modified petroleum coke F is respectively determined, and the result is respectively 60% and 85%.
Example 7
The process of example 1 was followed except that the weight ratio of petroleum coke to petroleum pitch was 20: 1, obtaining the modified petroleum coke G with the volatile content of 9.8 weight percent and the ash content of 0.29 weight percent.
The reactivity of the petroleum coke before modification and the obtained modified petroleum coke is respectively determined, and the result is respectively 60% and 67%.
Example 8
Uniformly mixing silica and a carbonaceous reducing agent, wherein the carbonaceous reducing agent comprises bituminous coal and modified petroleum coke A, the bituminous coal content is 40 wt%, the modified petroleum coke A content is 60 wt%, and the weight ratio of the silica to the carbonaceous reducing agent is 1: 1.2, putting the mixture into a submerged arc furnace for smelting heat treatment.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 29.8 percent, and the grade of the silicon product is 442 grade.
Example 9
Uniformly mixing silica and a carbonaceous reducing agent, wherein the carbonaceous reducing agent comprises bituminous coal and modified petroleum coke B, the bituminous coal content is 25 wt%, the modified petroleum coke B content is 75 wt%, and the weight ratio of the silica to the carbonaceous reducing agent is 1: and 1.4, putting the mixture into a submerged arc furnace for smelting heat treatment.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 30.2 percent, and the grade of the silicon product is 442 grade.
Example 10
Uniformly mixing silica and a carbonaceous reducing agent, wherein the carbonaceous reducing agent comprises bituminous coal and modified petroleum coke C, the bituminous coal content is 50 wt%, the modified petroleum coke C content is 50 wt%, and the weight ratio of the silica to the carbonaceous reducing agent is 1: 1.3, putting the mixture into a submerged arc furnace for smelting heat treatment.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 30.5 percent, and the grade of the silicon product is 441 grade.
Example 11
Uniformly mixing silica and a carbonaceous reducing agent, wherein the carbonaceous reducing agent comprises bituminous coal and modified petroleum coke D, the bituminous coal content is 30 wt%, the modified petroleum coke D content is 70 wt%, and the weight ratio of the silica to the carbonaceous reducing agent is 1: and 1.5, putting the mixture into a submerged arc furnace for smelting heat treatment.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 30.6 percent, and the grade of the silicon product is 421 grade.
Example 12
Uniformly mixing silica and a carbonaceous reducing agent, wherein the carbonaceous reducing agent comprises bituminous coal and modified petroleum coke E, the bituminous coal content is 40 wt%, the modified petroleum coke E content is 60 wt%, and the weight ratio of the silica to the carbonaceous reducing agent is 1: 1.3, putting the mixture into a submerged arc furnace for smelting heat treatment.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 30.2 percent, and the grade of the silicon product is 421 grade.
Example 13
The procedure of example 8 was followed except that modified petroleum coke F was used instead of modified petroleum coke a.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 29.7 percent, and the grade of the silicon product is 421 grade.
Example 14
The procedure of example 8 was followed except that modified petroleum coke G was used instead of modified petroleum coke a.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 28.9 percent, and the grade of the silicon product is 553 grade.
Example 15
The process of example 8 was followed except that the bituminous coal was present in an amount of 10 wt% and the modified petroleum coke a was present in an amount of 90 wt% based on the weight of the carbonaceous reducing agent.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 29.5 percent, and the grade of the silicon product is 442 grade.
Example 16
The process of example 8 was followed except that the bituminous coal was 90 wt% and the modified petroleum coke a was 10 wt% based on the weight of carbonaceous reducing agent.
The phenomena of furnace bottom rising, fire stabbing, material surface death and the like are not seen in the smelting process. The furnace condition in the smelting process is good: it can be observed that the electrode is deeply and stably buried in the furnace charge, the sinking speed of the charge level is high, the gas is uniformly emitted from the upper part of the hearth, the current load is stable, the silicon is smoothly discharged, the silicon yield reaches 29.8 percent, and the grade of the silicon product is 553 grade.
Comparative example 1
The procedure of example 8 was followed except that unmodified petroleum coke was used in place of modified petroleum coke a.
In the smelting process, the charge level is too loose, the material is easy to catch fire, the arc sound is large, and the furnace bottom is easy to rise, so that the normal smelting production cannot be realized.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A method for modifying petroleum coke, the method comprising: mixing a modifier with petroleum coke, drying and forming the mixture, wherein the modifier is asphalt and/or heavy oil;
the method for mixing the modifier with the petroleum coke comprises the following steps: heating a mixture of a modifier and petroleum coke to a modification temperature of 50-200 ℃ and at which the modifier is liquid;
the drying conditions include: the temperature is 100-200 ℃ and the time is 1-5 h.
2. The method of claim 1, wherein the bitumen is petroleum pitch and/or coal pitch, and the heavy oil is at least one of ethylene tar, coal tar, atmospheric residue, vacuum residue, heavy oil, and catalytic cracking slurry oil.
3. The process according to claim 1, wherein the petroleum coke has a volatiles content of 5-12 wt%, and/or
The ash content of the petroleum coke is less than 0.3 wt%.
4. The process of any of claims 1-3, wherein the weight ratio of modifier to petroleum coke is 1: 0.1-20.
5. The process of claim 4, wherein the weight ratio of modifier to petroleum coke is 1: 0.1-10.
6. The method of claim 1, wherein the mixing is performed under agitation.
7. Modified petroleum coke prepared by the process of any one of claims 1 to 6.
8. The modified petroleum coke as claimed in claim 7, wherein the volatile content of the modified petroleum coke is 12-20 wt%.
9. The modified petroleum coke as claimed in claim 8, wherein the volatile content of the modified petroleum coke is 14-18 wt%.
10. A carbonaceous reducing agent, characterized in that the carbonaceous reducing agent comprises bituminous coal and/or anthracite and petroleum coke, the content of bituminous coal and/or anthracite is 10-90 wt% and the content of petroleum coke is 10-90 wt% based on the weight of the carbonaceous reducing agent, wherein the petroleum coke is the modified petroleum coke according to any one of claims 7-9.
11. The carbonaceous reductant according to claim 10, wherein the bituminous coal and/or anthracite coal is present in an amount of 25-50 wt% and the petroleum coke is present in an amount of 50-75 wt%, based on the weight of the carbonaceous reductant.
12. A method for smelting industrial silicon, which is characterized by comprising the following steps: contacting a silicon source with the carbonaceous reducing agent of claim 10 or 11 under metallurgical conditions.
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| CN101112986B (en) * | 2007-06-29 | 2010-07-28 | 商南中剑实业有限责任公司 | Method for producing industrial silicon by using petroleum coke as reducing agent |
| CN101434392A (en) * | 2007-11-13 | 2009-05-20 | 李岱 | Reducer synthetic carbon for smelting metallic silicon and producing method thereof |
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