CN109279609A - The smelting process of the method for modifying of petroleum coke and thus obtained modified petroleum coke and carbonaceous reducing agent and industrial silicon - Google Patents
The smelting process of the method for modifying of petroleum coke and thus obtained modified petroleum coke and carbonaceous reducing agent and industrial silicon Download PDFInfo
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- CN109279609A CN109279609A CN201710595989.9A CN201710595989A CN109279609A CN 109279609 A CN109279609 A CN 109279609A CN 201710595989 A CN201710595989 A CN 201710595989A CN 109279609 A CN109279609 A CN 109279609A
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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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention relates to smelting industrial silicons and field of new energy technologies, it discloses a kind of method of modifying of petroleum coke and thus obtained modified petroleum is burnt and the smelting process of carbonaceous reducing agent and industrial silicon, the method of modifying includes: to mix modifying agent with petroleum coke, then by mixture drying, molding, wherein, the modifying agent is pitch and/or heavy oil.The modified petroleum coke substitution charcoal obtained using method of modifying of the present invention is as the carbonaceous reducing agent component of industrial silicon, petroleum coke is able to solve as the deficiencies of reactivity is relatively low, volatile matter is relatively low existing for smelting industrial silicon carbonaceous reducing agent group timesharing, improves its adaptability.
Description
Technical field
The present invention relates to smelting industrial silicons and field of new energy technologies, and in particular to a kind of method of modifying of petroleum coke and by
This obtained modified petroleum coke and a kind of carbonaceous reducing agent and a kind of smelting process of industrial silicon.
Background technique
Charcoal, coal washing are common carbonaceous reducing agents in current industrial silicon industry, and charcoal technique and coal washing oil coke technique are
The prevailing technology of industrial silicon production at present.Dependence due to charcoal to the forest reserves, seriously destroys ecological environment, as forest provides
The protective awareness in source is reinforced, and charcoal supply is becoming tight day, reduces charcoal usage amount and has become trend.Therefore, it is necessary to find
It is suitble to the novel carbonaceous reducing agent of smelting industrial silicon, to guarantee the needs of production and reduce production cost.At abroad, some works
The advanced country of industry silicon smelting technique, such as Norway can reduce production using coal or coal-based carbon as the reducing agent of industrial silicon smelting
Cost improves the economic benefit of enterprise.But coal or coal-based carbon have that content of ashes is high, so as to cause in industrial silicon product
Micronutrient levels influences product quality and its grade.
Petroleum coke has that content of ashes is small, fixed carbon content is high as one of carbonaceous reducing agent, has certain machinery strong
The features such as spending can require to use as reducing agent according to the working of a furnace and product quality.China Petroleum coke annual output is 25,000,000 tons of left sides
On the one hand the right side can widen the application field of petroleum coke as smelting industrial silicon reducing agent using petroleum coke substitution charcoal, while can
Improve the added value of petroleum coke.But country's delayed coking unit is at present in order to increase economic efficiency, the work of all taking comparison harsh
Skill operating condition has stringent performance assessment criteria to the volatile matter of petroleum coke to obtain higher liquid product yield, it is desirable that
The volatile matter of petroleum coke (green coke) cannot be greater than 12%, and average is 10% or so.Low volatile matter is not suitable for industrial silicon smelting
Refine the requirement to carbonaceous reducing agent.Meanwhile petroleum coke there is also reactivity worth poor, the low problem of reproducibility utilization efficiency.
CN103626183A discloses a kind of industrial silicon production reducing agent, the reducing agent by mass percentage by 0~
100% petroleum coke particles and 0~100% modified petroleum coke particle composition, the petroleum coke particles and modified petroleum burnt
The granularity of grain is within the scope of 5~60mm.Butt fixed carbon >=76% of the reducing agent, can residual ash≤1%, fugitive constituent
10%~16%, moisture≤8% can extend one times or so of furnace life.But the reactivity of petroleum coke needs in the reducing agent
It improves.
CN105329897A discloses a kind of preparation method of complex reducing agent applied to smelting industrial silicon production,
In, the grain size proportion of petroleum coke material: partial size is 0.1mm petroleum coke accounting below 60~75wt%, partial size 0.1mm or more
Account for 25~40wt%；Anthracite/bituminous coal material grain size proportion: partial size is that the proportion of 0.15~0.3mm accounts for 55~75%,
The proportion of 0.15mm or less partial size accounts for 25~45%；Charcoal powder and biomass carbon/semicoke are mixed to get powdered carbon in any proportion
Mixed material, powdered carbon mixed material grain size proportion: 0.075mm or less partial size proportion accounts for 75~90%, and 0.075mm or more partial size is matched
Than accounting for 10~25%；Configured petroleum coke material, anthracite/bituminous coal material, powdered carbon mixed material are mixed
Material is closed, mixture is added into organic adhesive, additive, water and is stirred evenly, pelletizing is then prepared into, is prepared after drying multiple
Close reducing agent.
Above-mentioned patent application mainly designs reduction agent prescription, and considers in formula the grain size distribution of various materials and shared
Ratio.
Summary of the invention
It is of the existing technology the purpose of the invention is to overcome the problems, such as, provide a kind of petroleum coke method of modifying and by
This obtained modified petroleum coke and a kind of carbonaceous reducing agent and a kind of smelting process of industrial silicon, are obtained using method of modifying of the present invention
Carbonaceous reducing agent component of the modified petroleum coke substitution charcoal arrived as industrial silicon, is able to solve petroleum coke as smelting industrial silicon
The deficiencies of reactivity is relatively low, volatile matter is relatively low existing for carbonaceous reducing agent group timesharing, improves its adaptability.
To achieve the goals above, in a first aspect, the present invention provides a kind of method of modifying of petroleum coke, the method packet
It includes: modifying agent is mixed with petroleum coke, then by mixture drying, molding, wherein the modifying agent is pitch and/or heavy oil.
Second aspect, the modified petroleum being prepared the present invention provides method of the present invention are burnt.
The third aspect, the present invention provides a kind of carbonaceous reducing agent, the carbonaceous reducing agent includes bituminous coal and/or smokeless
Coal and petroleum coke, on the basis of the weight of the carbonaceous reducing agent, bituminous coal and/or anthracitic content are 10-90 weight %,
The content of petroleum coke is 10-90 weight %, wherein the petroleum coke is that modified petroleum of the present invention is burnt.
Fourth aspect, the present invention provides a kind of smelting processes of industrial silicon, this method comprises: under smelting condition, it will
Silicon source is contacted with carbonaceous reducing agent of the present invention.
The modified petroleum coke substitution charcoal obtained using method of modifying of the present invention as the carbonaceous reducing agent component of industrial silicon,
Petroleum coke is able to solve as reactivity is relatively low, volatile matter is relatively low existing for smelting industrial silicon carbonaceous reducing agent group timesharing etc.
Deficiency improves its adaptability.
Without containing charcoal, capable of guaranteeing the needs of production and life being greatly reduced in the composition of carbonaceous reducing agent of the invention
Cost is produced, and obtained silicon grade is high, yield is high, that is, using petroleum coke substitution charcoal as the carbonaceous reducing agent group of industrial silicon
Point, it is a kind of solution to protect forest resources with ecological environment.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of method of modifying of petroleum coke, which comprises by modifying agent and petroleum
Coke mixing, then by mixture drying, molding, wherein the modifying agent is pitch and/or heavy oil.
In the present invention, modifying agent is liquid and/or solid-state at normal temperature, under preferable case, pitch be asphalt and/or
Coal tar pitch, heavy oil are at least one in ethylene bottom oil, coal tar, reduced crude, decompression residuum, mink cell focus and catalytic cracked oil pulp
Kind.Wherein, it will be understood by those skilled in the art that when modifying agent is two or more substances, the dosage between each substance can
Think arbitrary proportion, and the content of ashes of aforementioned each modifying agent is below 0.3 weight %.
Under preferable case, petroleum coke to be modified is the petroleum coke of Conventional delayed coking device production, and volatile matter content is
5-12 weight %, further preferably 6-10 weight %.
Under preferable case, the content of ashes of petroleum coke to be modified is lower than 0.3 weight %, further preferably 0-0.2 weight
Measure %.
Under preferable case, the weight ratio of modifying agent and petroleum coke is 1:0.1-20, further preferably 1:0.1-10.
It include: to add the mixture of modifying agent and petroleum coke by the method that modifying agent is mixed with petroleum coke under preferable case
The modification temperature of heat to 50-200 DEG C, and the modifying agent is liquid under the modification temperature.Those skilled in the art should
Understand, in aforementioned modifiers, ethylene bottom oil and coal tar are liquid at normal temperature, when modifying agent be ethylene bottom oil and/or
When coal tar, modification temperature can be 50-80 DEG C；In aforementioned modifiers, at normal temperature asphalt, coal tar pitch, reduced crude,
Decompression residuum, mink cell focus and catalytic cracked oil pulp be solid-state, when modifying agent contain under aforementioned room temperature be in solid substance extremely
When few a kind of, modification temperature can be 20-50 DEG C of softening point of the temperature higher than the modifying agent.Wherein, specific modified temperature
Degree can be selected between 50-200 DEG C according to the type difference of modifying agent, as long as guaranteeing that modifying agent has under the modification temperature
Good mobility can be such that petroleum coke and modifying agent is uniformly mixed.
Preferably, the mixing carries out under stiring, uniformly mixed to achieve the purpose that, wherein mixing speed can be
80-200rpm。
Under preferable case, the condition of the drying includes: that temperature is 100-200 DEG C, time 1-5h.Wherein, at drying
Reason can not only improve the volatile matter of petroleum coke, additionally it is possible to improve its reactivity worth as carbonaceous reducing agent.
Wherein, for molding method, there is no particular limitation, can be various forming methods commonly used in the art, this is
As it is known to those skilled in the art that details are not described herein.
Second aspect, the modified petroleum being prepared the present invention provides method of the present invention are burnt.
Preferably, the volatile matter content of the modified petroleum coke is 12-20 weight %, further preferably 14-18 weight
Measure %.
The third aspect, the present invention provides a kind of carbonaceous reducing agent, the carbonaceous reducing agent includes bituminous coal and/or smokeless
Coal and petroleum coke, on the basis of the weight of the carbonaceous reducing agent, bituminous coal and/or anthracitic content are 10-90 weight %,
The content of petroleum coke is 10-90 weight %, wherein the petroleum coke is that modified petroleum of the present invention is burnt.
Under preferable case, on the basis of the weight of the carbonaceous reducing agent, bituminous coal and/or anthracitic content are 25-50
Weight %, the content of petroleum coke are 50-75 weight %.
In carbonaceous reducing agent of the invention, bituminous coal and/or anthracite can be respectively in this field for carbonaceous reducing agent
Common various bituminous coal and anthracite.Wherein, it will be understood by those skilled in the art that in carbonaceous reducing agent of the invention
It does not include charcoal.
Fourth aspect, the present invention provides a kind of smelting processes of industrial silicon, this method comprises: under smelting condition, it will
Silicon source is contacted with carbonaceous reducing agent of the present invention.
In method of the invention, silicon source is various silicon sources commonly used in the art, such as silica.
In method of the invention, smelting condition can be various smelting conditions commonly used in the art, such as smelting condition can
To include: temperature for 2350-3000 DEG C, preferably 2600-2800 DEG C.
In the case of process of the present invention it is preferred, the weight ratio of silicon source and carbonaceous reducing agent is 1:0.8-2, further excellent
It is selected as 1:1-1.4.
Embodiment
The present invention will be described in detail by way of examples below, but is not intended to limit the present invention.Following embodiment
In, unless otherwise instructed, each material used is commercially available, and each method used is the conventional method of this field.
Wherein, bituminous coal comes from Ningxia, China, and volatile matter content is 25 weight %, and content of ashes is 7.5 weight %.
The measuring method of volatile matter content in petroleum coke are as follows: SH/T0026-1990 volatile fraction in petroleum coke measuring method.
The measuring method of volatile matter content in bituminous coal are as follows: GB-T 212-2008 proximate analysis of coal.
The measuring method of content of ashes in petroleum coke are as follows: SH/T 0029-1990 petroleum coke Ash determination method.
The measuring method of content of ashes in modifying agent are as follows: GB508 oil product Ash determination method.
The measuring method of content of ashes in bituminous coal are as follows: GB-T 212-2008 proximate analysis of coal.
The measuring method of petroleum coke air reactive are as follows: YS/T587.1-587.14 carbon anode after-smithing petroleum coke detection side
Method.
The classification method of silicon grade are as follows: classified according to iron, aluminium, calcium content in silicon, represent the purity of silicon: such as 553
Grade, 442 grades, 441 grades, 421 grades etc.；By taking 553 grades as an example, first digit represents highest iron content, i.e. iron
Content is not higher than 0.5 weight %, and second digit represents highest aluminium content, i.e. aluminium content is not higher than 0.5 weight %, third
Number represents highest calcium content, i.e. calcium content is not higher than 0.3 weight %.
Embodiment 1
Will volatilize point content is 8.9 weight %, content of ashes is 0.29 weight % petroleum coke and content of ashes is 0.06
The asphalt of weight % heats at 105 DEG C, and stirring is uniformly mixed it at 100 rpm, wherein petroleum coke and petroleum
The weight ratio of pitch is 4:1, and mixture is then dried 2h at 150 DEG C, is formed, and obtaining volatile matter content is 14.2 weights
Measure %, the modified petroleum coke A that content of ashes is 0.25 weight %.
The reactivity of petroleum coke before modified and gained modified petroleum coke A is measured respectively, as a result respectively 60% He
78%.That is, method through this embodiment is modified petroleum coke, the volatile matter content of modified petroleum coke improves 5.3
Weight %, reactivity improve 18%, can better meet the requirement of industrial silicon carbonaceous reducing agent.
Embodiment 2
Will volatilize point content is 8.9 weight %, content of ashes is 0.29 weight % petroleum coke and content of ashes is 0.24
The catalytic cracked oil pulp of weight % heats at 80 DEG C, and at 100 rpm stirring make its be uniformly mixed, wherein petroleum coke with urge
The weight ratio for changing cracking slurry oil is 1:1, and mixture is then dried 4h at 100 DEG C, is formed, obtaining volatile matter content is
14.8 weight %, the modified petroleum coke B that content of ashes is 0.27 weight %.
The reactivity of petroleum coke before modified and gained modified petroleum coke B is measured respectively, as a result respectively 60% He
82%.That is, method through this embodiment is modified petroleum coke, the volatile matter content of modified petroleum coke improves 5.9
Weight %, reactivity improve 22%, can better meet the requirement of industrial silicon carbonaceous reducing agent.
Embodiment 3
Will volatilize point content is 9.1 weight %, content of ashes is 0.21 weight % petroleum coke and content of ashes is 0.12
The modifying agent of weight % heats at 95 DEG C, and stirring is uniformly mixed it at 100 rpm, wherein modifying agent is asphalt
With the mixture of ethylene bottom oil, the weight ratio of asphalt and ethylene bottom oil is 3:1, and the weight ratio of petroleum coke and modifying agent is
Then mixture is dried 1h at 180 DEG C by 10:1, molding obtains that volatile matter content is 14.5 weight %, content of ashes is
The modified petroleum coke C of 0.20 weight %.
The reactivity of petroleum coke before modified and gained modified petroleum coke C is measured respectively, as a result respectively 62% He
84%.That is, method through this embodiment is modified petroleum coke, the volatile matter content of modified petroleum coke improves 5.4
Weight %, reactivity improve 22%, can better meet the requirement of industrial silicon carbonaceous reducing agent.
Embodiment 4
Will volatilize point content is 9.1 weight %, content of ashes is 0.21 weight % petroleum coke and content of ashes is 0.17
The modifying agent of weight % heats at 105 DEG C, and stirring is uniformly mixed it at 100 rpm, wherein modifying agent is that catalysis is split
The mixture of carburetion slurry and decompression residuum, the weight ratio of catalytic cracked oil pulp and decompression residuum are 1:1, petroleum coke and modifying agent
Weight ratio is 1.5:1, and mixture is then dried 1.5h at 140 DEG C, molding, obtain volatile matter content be 14.9 weight %,
Content of ashes is the modified petroleum coke D of 0.19 weight %.
The reactivity of petroleum coke before modified and gained modified petroleum coke D is measured respectively, as a result respectively 62% He
86%.That is, method through this embodiment is modified petroleum coke, the volatile matter content of modified petroleum coke improves 5.8
Weight %, reactivity improve 24%, can better meet the requirement of industrial silicon carbonaceous reducing agent.
Embodiment 5
Will volatilize point content is 9.1 weight %, content of ashes is 0.21 weight % petroleum coke and content of ashes is 0.005
The coal tar of weight % heats at 50 DEG C, and stirring is uniformly mixed it at 100 rpm, wherein petroleum coke and coal tar
Weight ratio is 9:1, and mixture is then dried 1.5h at 160 DEG C, molding, and obtaining volatile matter content is 14.8 weight %, ash
Dividing content is the modified petroleum coke E of 0.19 weight %.
The reactivity of petroleum coke before modified and gained modified petroleum coke E is measured respectively, as a result respectively 62% He
88%.That is, method through this embodiment is modified petroleum coke, the volatile matter content of modified petroleum coke improves 5.7
Weight %, reactivity improve 26%, can better meet the requirement of industrial silicon carbonaceous reducing agent.
Embodiment 6
According to the method for embodiment 1, unlike, the weight ratio of petroleum coke and asphalt is 0.1:1, obtains volatile matter
The modified petroleum coke F that content is 15.2 weight %, content of ashes is 0.08 weight %.
The reactivity of petroleum coke before modified and gained modified petroleum coke F is measured respectively, as a result respectively 60% He
85%.
Embodiment 7
According to the method for embodiment 1, unlike, the weight ratio of petroleum coke and asphalt is 20:1, obtains volatile matter
The modified petroleum coke G that content is 9.8 weight %, content of ashes is 0.29 weight %.
The reactivity of petroleum coke before modified and gained modified petroleum coke is measured respectively, as a result respectively 60% and 67%.
Embodiment 8
Silica is uniformly mixed with carbonaceous reducing agent, carbonaceous reducing agent includes bituminous coal and modified petroleum coke A, wherein with carbon
On the basis of the weight of matter reducing agent, the content of bituminous coal is 40 weight %, and the content of modified petroleum coke A is 60 weight %, silica with
The weight ratio of carbonaceous reducing agent is 1:1.2, and mixture is put into and carries out smelting heat treatment in mineral hot furnace.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 29.8%, silicon product grade is 442 grades out.
Embodiment 9
Silica is uniformly mixed with carbonaceous reducing agent, carbonaceous reducing agent includes bituminous coal and modified petroleum coke B, wherein with carbon
On the basis of the weight of matter reducing agent, the content of bituminous coal is 25 weight %, and the content of modified petroleum coke B is 75 weight %, silica with
The weight ratio of carbonaceous reducing agent is 1:1.4, and mixture is put into and carries out smelting heat treatment in mineral hot furnace.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 30.2%, silicon product grade is 442 grades out.
Embodiment 10
Silica is uniformly mixed with carbonaceous reducing agent, carbonaceous reducing agent includes bituminous coal and modified petroleum coke C, wherein with carbon
On the basis of the weight of matter reducing agent, the content of bituminous coal is 50 weight %, and the content of modified petroleum coke C is 50 weight %, silica with
The weight ratio of carbonaceous reducing agent is 1:1.3, and mixture is put into and carries out smelting heat treatment in mineral hot furnace.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 30.5%, silicon product grade is 441 grades out.
Embodiment 11
Silica is uniformly mixed with carbonaceous reducing agent, carbonaceous reducing agent includes bituminous coal and modified petroleum coke D, wherein with carbon
On the basis of the weight of matter reducing agent, the content of bituminous coal is 30 weight %, and the content of modified petroleum coke D is 70 weight %, silica with
The weight ratio of carbonaceous reducing agent is 1:1.5, and mixture is put into and carries out smelting heat treatment in mineral hot furnace.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 30.6%, silicon product grade is 421 grades out.
Embodiment 12
Silica is uniformly mixed with carbonaceous reducing agent, carbonaceous reducing agent includes bituminous coal and modified petroleum coke E, wherein with carbon
On the basis of the weight of matter reducing agent, the content of bituminous coal is 40 weight %, and the content of modified petroleum coke E is 60 weight %, silica with
The weight ratio of carbonaceous reducing agent is 1:1.3, and mixture is put into and carries out smelting heat treatment in mineral hot furnace.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 30.2%, silicon product grade is 421 grades out.
Embodiment 13
According to the method for embodiment 8, the difference is that, modified petroleum coke A is replaced with modified petroleum coke F.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 29.7%, silicon product grade is 421 grades out.
Embodiment 14
According to the method for embodiment 8, the difference is that, modified petroleum coke A is replaced with modified petroleum coke G.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 28.9%, silicon product grade is 553 grades out.
Embodiment 15
According to the method for embodiment 8, the difference is that, on the basis of the weight of carbonaceous reducing agent, the content of bituminous coal is 10 weights
% is measured, the content of modified petroleum coke A is 90 weight %.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 29.5%, silicon product grade is 442 grades out.
Embodiment 16
According to the method for embodiment 8, the difference is that, on the basis of the weight of carbonaceous reducing agent, the content of bituminous coal is 90 weights
% is measured, the content of modified petroleum coke A is 10 weight %.
Have no that furnace bottom rising, thorn fire, charge level send out bad phenomenon of waiting indefinitely in smelting process.The working of a furnace is good in smelting process:
It can be observed that electrode is deep and is quietly embedded in furnace charge, charge level subsidence velocity is fast, and gas is equably emerged through upper furnace, electric current
Steady load, silicon is smooth out, and for silicon rate up to 29.8%, silicon product grade is 553 grades out.
Comparative example 1
According to the method for embodiment 8, the difference is that, modified petroleum coke A is replaced with unmodified petroleum coke.
Charge level is excessively loose in smelting process, easily thorn fire, and welding arc sound is big, and furnace bottom easily goes up, and causes normally smelt life
It produces.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method of modifying of petroleum coke, which is characterized in that this method comprises: modifying agent is mixed with petroleum coke, then will
Mixture drying, molding, wherein the modifying agent is pitch and/or heavy oil.
2. the heavy oil is second according to the method described in claim 1, wherein, the pitch is asphalt and/or coal tar pitch
At least one of alkene tar, coal tar, reduced crude, decompression residuum, mink cell focus and catalytic cracked oil pulp.
3. method according to claim 1 or 2, wherein the volatile matter content of the petroleum coke is 5-12 weight %, and/
Or
The content of ashes of the petroleum coke is lower than 0.3 weight %.
4. method described in any one of -3 according to claim 1, wherein the weight ratio of the modifying agent and the petroleum coke
For 1:0.1-20, preferably 1:0.1-10.
5. method described in any one of -4 according to claim 1, wherein the method packet for mixing modifying agent with petroleum coke
It includes: the mixture of modifying agent and petroleum coke is heated to 50-200 DEG C of modification temperature, and described under the modification temperature change
Property agent be liquid；
Preferably, the mixing carries out under stiring.
6. method described in any one of -5 according to claim 1, wherein the condition of the drying includes: that temperature is 100-
200 DEG C, time 1-5h.
7. the modified petroleum that method described in any one of claim 1-6 is prepared is burnt；
Preferably, the volatile matter content of the modified petroleum coke is 12-20 weight %, further preferably 14-18 weight %.
8. a kind of carbonaceous reducing agent, which is characterized in that the carbonaceous reducing agent includes bituminous coal and/or anthracite and petroleum coke,
On the basis of the weight of the carbonaceous reducing agent, bituminous coal and/or anthracitic content are 10-90 weight %, the content of petroleum coke
For 10-90 weight %, wherein the petroleum coke is that modified petroleum as claimed in claim 7 is burnt.
9. carbonaceous reducing agent according to claim 8, wherein on the basis of the weight of the carbonaceous reducing agent, bituminous coal and/
Or anthracitic content is 25-50 weight %, the content of petroleum coke is 50-75 weight %.
10. a kind of smelting process of industrial silicon, which is characterized in that this method comprises: wanting silicon source and right under smelting condition
The contact of carbonaceous reducing agent described in asking 8 or 9.
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| CN201710595989.9A CN109279609B (en) | 2017-07-20 | 2017-07-20 | Modification method of petroleum coke, modified petroleum coke obtained by modification method, carbonaceous reducing agent and smelting method of industrial silicon |
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Citations (9)
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