CN102381708B - Smelting process of industrial silicon - Google Patents
Smelting process of industrial silicon Download PDFInfo
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- CN102381708B CN102381708B CN 201010274754 CN201010274754A CN102381708B CN 102381708 B CN102381708 B CN 102381708B CN 201010274754 CN201010274754 CN 201010274754 CN 201010274754 A CN201010274754 A CN 201010274754A CN 102381708 B CN102381708 B CN 102381708B
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Abstract
The invention provides a smelting process of industrial silicon. The smelting process of the industrial silicon comprises the following steps of: a. uniformly mixing petroleum coke particles, an oxidant and an intercalator, and reacting at the temperature of 25-65 DEG C; b. impregnating a reaction product in the step a in a water solution of a finishing agent, and then filtering to obtain modified petroleum coke particles, wherein the finishing agent is a potassium compound and/or sodium compound ; and c. mixing silica and a reducing agent, then carrying out smelting thermal treatment, wherein the reducing agent comprises the modified petroleum coke particles and unmodified petroleum coke particles. When the method is used for smelting industrial silicon, the air permeability and the reactivity of furnace charge are good.
Description
Technical field
The present invention relates to a kind of smelting process of industrial silicon.
Background technology
Industrial silicon is information, new forms of energy, the most basic functional material of new material industry.Serve as the basis Industrial products of deriving with it, various in style, the field that relates to is extensive, is described as " magic metal ", " industrial monosodium glutamate ".Its main application fields has four aspects: the one, as the additive of smelting aluminium and steel, the 2nd, for the synthesis of various organosilicon materials, the 3rd, after purifying, generate the high-purity industrial silicon of electronic-grade and the high-purity industrial silicon of solar level, the 4th, for the manufacture of novel materials such as semiconductor silicon, silicon pottery, silicon carbide, silicon nitrides.And along with science and technology development, the Application Areas of industrial silicon also will further enlarge.
All the time, industrial silicon is to get with the carbothermic method preparation, is about to silica and charcoal reductive agent and is crushed to suitable granularity, mixes to smelt in the hot stove in input ore deposit, back obtaining industrial silicon according to a certain percentage.Reductive agent is based on charcoal in early days, adds a spot of refinery coke, and the charcoal of producing one ton of industrial silicon consumption can be up to 1.5 tons even higher, the destruction that has consumed a large amount of forest reserves, caused ecotope.Along with the exhaustion day by day of charcoal resource, and the enforcement of the relevant policies of the state guarantee forest reserves and measure, limit industrial silicon manufacturing enterprise and used charcoal in a large number.After last century the mid-1960s, bring into use charcoal, refinery coke and bituminous coal to mix as reductive agent.After the seventies, adopt wooden unit to replace the part charcoal as the proportioning of reductive agent with expansion refinery coke and bituminous coal, the bad problem of ventilation property that the while wooden unit also brings with the solution refinery coke as raising agent.Chinese patent application CN1876567 discloses and a kind ofly has been reductive agent, is the method for raising agent smelting commercial silicon with the wooden unit with refinery coke and bituminous coal; this method has more or less added wooden unit; consumed timber, on the angle that protects forest resources, this method exists not enough.
On the angle of matallurgical products, because refinery coke is that ash oontent is minimum in all reductive agents, be conducive to the raising of product grade as reductive agent manufacture silicon with full oil coke.In addition, refinery coke fixed carbon content height, wide material sources, low price etc. all are conducive to it as reductive agent use of smelting commercial silicon.Therefore, replace charcoal as reductive agent with refinery coke, improved the grade of product simultaneously protecting forest resources, can obtain low cost, high-grade industrial silicon product.Yet, as reductive agent, be unfavorable for the effusion of byproduct of reaction CO and to the absorption of reaction intermediate SiO with refinery coke; In addition, a little less than the refinery coke reactivity, be unfavorable for the raising of production efficiency.Therefore, with full oil coke as the reductive agent smelting commercial silicon, poor, the reactive relatively poor problem of ventilation property in the time of must solving full oil coke and smelt.
Summary of the invention
When smelting manufacture silicon in order to overcome in the prior art full oil coke, the problem of furnace charge air permeability and reactive difference the invention provides a kind of smelting process of industrial silicon.Furnace charge air permeability and reactive good during by this method smelting commercial silicon.
The smelting process of industrial silicon disclosed by the invention comprises:
A, petroleum coke particles and oxygenant, intercalator are mixed, and under 25-65 ℃ temperature, react;
B, the reaction product of step a is flooded in the aqueous solution for the treatment of agent, filter then; Described treatment agent is potassium compound and/or sodium compound, obtains the modification petroleum coke particles;
C, silica is mixed with reductive agent, smelt thermal treatment then; Wherein, described reductive agent comprises described modification petroleum coke particles and unmodified petroleum coke particles.
The method of full oil coke smelting commercial silicon provided by the invention, the reductive agent of employing comprise described modification petroleum coke particles and unmodified petroleum coke particles, and do not add any charcoal or wood materials, have protected the forest reserves effectively.Simultaneously, because the ash content of refinery coke is minimum in known reductive agent, use full oil coke to smelt the raising that is conducive to product grade.The contriver finds that petroleum coke particles again in conjunction with the dipping for the treatment of agent, can make petroleum coke particles form good pore texture through the processing of oxygenant and intercalator, and through after the above-mentioned treatment agent processing, has improved the reactivity of refinery coke greatly.The reductive agent that drops into the hot stove in ore deposit comprises modification petroleum coke particles and unmodified petroleum coke particles, acting in conjunction by modification petroleum coke particles and unmodified petroleum coke particles, in smelting process along with the sinking of furnace charge, the rising of temperature, modification petroleum coke particles volume increases, and is conducive to the effusion of reactant gases CO, is conducive to the absorption to smelting intermediate product SiO simultaneously, promote the carrying out of reaction, thereby improved the productive rate of silicon greatly.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The smelting process of industrial silicon disclosed by the invention comprises:
A, petroleum coke particles and oxygenant, intercalator are mixed, and under 25-65 ℃ temperature, react;
B, the reaction product of step a is flooded in the aqueous solution for the treatment of agent, filter then; Described treatment agent is potassium compound and/or sodium compound, obtains the modification petroleum coke particles;
C, silica is mixed with reductive agent, smelt thermal treatment then; Wherein, described reductive agent comprises described modification petroleum coke particles and unmodified petroleum coke particles.
In the smelting process disclosed by the invention, described petroleum coke particles is material known in those skilled in the art.It is crude oil after distillation separates lightweight oil, the product that mink cell focus is transformed through hot tearing again.For example can adopt sponge coke, its microtexture of sponge coke is good, and micropore is more, is subjected to ability strong to catching of middle product S iO, is conducive to improve the silicon rate.Further, in order better to improve the reactivity of smelting process, the granularity of described petroleum coke particles is the 30-150 order, fixed carbon content 〉=90%, ash content≤0.3%, the granularity that is preferably petroleum coke particles is the 50-100 order, fixed carbon content is 〉=92%, and ash content is≤0.2%.
Among the present invention, when petroleum coke particles is carried out the modification processing, comprise petroleum coke particles is mixed with oxygenant, intercalator.Above-mentioned oxygenant is well known in the art, for example can be the H of concentration 20-40wt%
2O
2Solution is or/and concentration is the HNO of 40-68wt%
3Solution.Further, described intercalator is preferably the H that concentration is 80-98wt%
2SO
4Solution.
When mixing among the step a, each component concentration can change in a big way, under the preferable case, every 1g petroleum coke particles mixes with the above-mentioned oxygenant of 0.4-1.2ml and the above-mentioned intercalator of 1-5ml, and more preferably every 1g petroleum coke particles mixes with the above-mentioned oxygenant of 0.7-1.0ml and the above-mentioned intercalator of 2-4ml.
After petroleum coke particles and oxygenant, intercalator mixed, under 25-65 ℃ temperature, react, the structure of petroleum coke particles is carried out modification.Under the preferable case, the time of described reaction is 1-3 hour.In order to reduce above-mentioned oxygenant and intercalator to the influence of subsequent disposal, can also adopt deionized water to clean to above-mentioned reacted product.Clean be 7 to PH after, with the product drying for standby.
According to the present invention, after step a processing, the reaction product of step a is flooded in the aqueous solution for the treatment of agent.Above-mentioned treatment agent potassium compound and/or sodium compound.Potassium compound can adopt the various compound that contains potassium of the prior art, for example can be oxyhydroxide of sylvite, potassium etc., and under the preferable case, described potassium compound is sylvite, more preferably salt of wormwood.Same, sodium compound can adopt the various compound that contains sodium of the prior art, for example can be for the oxyhydroxide of sodium salt, sodium etc., and under the preferable case, described sodium compound is sodium salt, more preferably yellow soda ash.In the aqueous solution of this treatment agent, the content for the treatment of agent is 5-20wt%, is preferably 8-15wt%.Above-mentioned content is the total content for the treatment of agent, and namely when treatment agent contained potassium compound and sodium compound simultaneously, above-mentioned content range was the total content of potassium compound and sodium compound, and simultaneously, the content of potassium compound and sodium compound each other without limits.
Under the preferable case, among the described step b, dipping time is 5-15min.
The contriver finds, the petroleum coke particles that the aforementioned oxygenant of process and intercalator were handled, adopt the aqueous solution of above-mentioned treatment agent to flood again, make potassium or sodium and petroleum coke particles middle sheet arrange the higher structure of ordering degree and constitute intercalation compound, interfloor distance is increased, produce volumetric expansion, cause air vent wall loose, crackle increases.Simultaneously, the above-mentioned comprehensive treating process of process also can reduce the beginning temperature of reaction of the molten reaction of carbon, makes reaction in advance, improves the reactivity of modification petroleum coke particles.
In above-mentioned impregnation steps, will be immersed in through the petroleum coke particles that step a handled in the aqueous solution for the treatment of agent and get final product.After dipping is finished, petroleum coke particles is filtered out, namely obtain the modification petroleum coke particles.
When smelting, need reduce to silica.In step c, silica is mixed with reductive agent, smelt thermal treatment then.Can obtain product silicon.
Wherein, silica is material known in those skilled in the art, and its main component is silicon-dioxide.Adopt silica as the silicon source among the present invention.The preferred silicon-dioxide purity of silica of the present invention is greater than the silica of 99wt%.
Among the present invention, the petroleum coke particles that reductive agent adopts non-modified commonly used in above-mentioned modification petroleum coke particles and the prior art to handle simultaneously.By the acting in conjunction of modification petroleum coke particles and unmodified petroleum coke particles, guaranteeing that smelting process is more effective carries out, and, improve productive rate greatly.
Above-mentioned unmodified petroleum coke particles can adopt the petroleum coke particles identical with modification petroleum coke particles before, and namely unmodified petroleum coke particles is all identical with granularity, fixed carbon content and the ash content of modification petroleum coke particles before; Simultaneously, this unmodified petroleum coke particles also can adopt the petroleum coke particles different with the petroleum coke particles before the modification.At this moment, this unmodified petroleum coke particles is similarly petroleum coke particles commonly used in the prior art, its granularity is not more than 10mm, namely in actual mechanical process, as long as the granularity of unmodified petroleum coke particles is not more than 10mm, it is not carried out the screening of particle diameter, and, unmodified petroleum coke particles fixed carbon content 〉=90%, ash content≤0.3%.
In the smelting process, the content of silica and reductive agent can change in a big way, and under the preferable case, the mass ratio of described silica and reductive agent is 2.2-2.7: 1, be preferably 2.35-2.55: 1.And in described reductive agent, the content of modification petroleum coke particles is 5-50wt%, is preferably 10-25wt%.
Silica with after reductive agent mixes, can be smelted thermal treatment, preparing product silicon, under the preferable case, among the step c, described smelting thermal treatment temp is 2350-3000 ℃, more preferably 2600-2800 ℃.
As to further improvement of the present invention, under the preferable case, before described step a, also comprise petroleum coke particles at 1150-1550 ℃ of temperature lower calcination, more preferably with petroleum coke particles at 1200-1400 ℃ of temperature lower calcination.The contriver finds that petroleum coke particles is through after the high-temperature calcination, and porosity increases, and intensity increases greatly, and with the structure that is conducive to stablize when follow-up modification is handled petroleum coke particles.
From smelting operation: adopt method disclosed by the invention to smelt, can significantly reduce the reductive agent powder in smelting process scaling loss, blow damage.And be conducive to the adsorptive power of the intermediate product SiO in the smelting process is strengthened, can improve and the silicon amount.Because its specific surface area is big, has bigger ratio resistance, thereby is conducive to the buried of electrode, is conducive to reduce calorific loss, prevents furnace bottom rising.The invention will be further elaborated below in conjunction with specific embodiment.
Embodiment 1
Present embodiment is used for the smelting process of explanation industrial silicon disclosed by the invention.
H with petroleum coke particles (granularity is the 30-100 order, and fixed carbon content is 90%, and ash content is 0.25%), 20wt%
2O
2The H of solution, 85wt%
2SO
4Solution mixes, with petroleum coke particles, H
2O
2Solution, H
2SO
4Solution carries out proportioning by 1g: 1.2ml: 2ml, mixes.Reaction is 3 hours under 60 ℃ temperature, and reaction is stirred.Reacted petroleum coke powder is to dry after 7 with deionized water rinsing to pH value.
Petroleum coke particles after the above-mentioned processing in being dipping 5 minutes in the potassium hydroxide solution of 10wt% in concentration under the normal temperature and pressure, is taken out after-filtration, obtain modification petroleum coke particles A1.
(granularity is not more than 6mm with modification petroleum coke particles A1 and unmodified petroleum coke particles, fixed carbon content is 90%, ash content is 0.25%), silica allocates in the furnace charge, wherein the mass ratio of silica and reductive agent (comprising modification petroleum coke particles A1 and unmodified petroleum coke particles) is 2.5: 1 in the furnace charge, and modification petroleum coke particles A1 accounts for 5% of reductive agent total mass.
At last the furnace charge for preparing is mixed, put in the hot stove in ore deposit and smelt thermal treatment, smelting thermal treatment temp is 2350 ℃.
Do not see that in smelting process thorn is fiery, charge level is sent out the phenomenon of waiting indefinitely.The working of a furnace is good in the smelting process: can observe electrode and buy deeply and quietly in furnace charge, the charge level sinking velocity is fast, and gas is emerged equably through upper furnace, and current load is stable, and it is smooth and easy to go out silicon, and the silicon product grade reaches 99.49%.
Embodiment 2
Present embodiment is used for the smelting process of explanation industrial silicon disclosed by the invention.
With petroleum coke particles (granularity is the 50-100 order, and fixed carbon content is 91%, and ash content is 0.20%) at 1500 ℃ of temperature lower calcinations.
HNO with burnt petroleum coke particles and 68wt%
3The H of solution, 95wt%
2SO
4Solution mixes, with petroleum coke particles, HNO
3Solution, H
2SO
4Solution carries out proportioning by 1g: 0.6ml: 3ml, mixes.Reaction is 1 hour under 40 ℃ temperature, and reaction is stirred.Reacted petroleum coke powder is to dry after 7 with deionized water rinsing to pH value.
Petroleum coke particles after the above-mentioned processing in being dipping 15 minutes in the solution of potassium carbonate of 10wt% in concentration under the normal temperature and pressure, is taken out after-filtration, obtain modification petroleum coke particles A2.
(granularity is not more than 5mm with modification petroleum coke particles A2 and unmodified petroleum coke particles, fixed carbon content is 91%, ash content is 0.20%), silica allocates in the furnace charge, wherein the mass ratio of silica and reductive agent (comprising modification petroleum coke particles A2 and unmodified petroleum coke particles) is 2.45: 1 in the furnace charge, and modification petroleum coke particles A2 accounts for 8% of reductive agent total mass.
At last the furnace charge for preparing is mixed, put in the hot stove in ore deposit and smelt thermal treatment, smelting thermal treatment temp is 2900 ℃.
Do not see that in smelting process thorn is fiery, charge level is sent out the phenomenon of waiting indefinitely.The working of a furnace is good in the smelting process: can observe electrode and buy deeply and quietly in furnace charge, the charge level sinking velocity is fast, and gas is emerged equably through upper furnace, and current load is stable, and it is smooth and easy to go out silicon, and the silicon product grade reaches 99.58%.
Embodiment 3
Present embodiment is used for the smelting process of explanation industrial silicon disclosed by the invention.
With petroleum coke particles (granularity is the 50-100 order, and fixed carbon content is 90%, and ash content is 0.28%) at 1500 ℃ of temperature lower calcinations.
H with burnt petroleum coke particles, 40wt%
2O
2The H of solution, 85wt%
2SO
4Solution mixes, with petroleum coke particles, H
2O
2Solution, H
2SO
4Solution carries out proportioning by 1g: 1ml: 2ml, mixes.Reaction is 3 hours under 60 ℃ temperature, and reaction is stirred.Reacted petroleum coke powder is to dry after 7 with deionized water rinsing to pH value.
Petroleum coke particles after the above-mentioned processing in being dipping 10 minutes in the sodium carbonate solution of 18wt% in concentration under the normal temperature and pressure, is taken out after-filtration, obtain modification petroleum coke particles A3.
(granularity is not more than 8mm with modification petroleum coke particles A3 and unmodified petroleum coke particles, fixed carbon content is 90%, ash content is 0.28%), silica allocates in the furnace charge, wherein the mass ratio of silica and reductive agent (comprising modification petroleum coke particles A3 and unmodified petroleum coke particles) is 2.5: 1 in the furnace charge, and modification petroleum coke particles A3 accounts for 35% of reductive agent total mass.
At last the furnace charge for preparing is mixed, put in the hot stove in ore deposit and smelt thermal treatment, smelting thermal treatment temp is 2800 ℃.
Do not see that in smelting process thorn is fiery, charge level is sent out the phenomenon of waiting indefinitely.The working of a furnace is good in the smelting process: can observe electrode and buy deeply and quietly in furnace charge, the charge level sinking velocity is fast, and gas is emerged equably through upper furnace, and current load is stable, and it is smooth and easy to go out silicon, and the silicon product grade reaches 99.52%.
Embodiment 4
Present embodiment is used for the smelting process of explanation industrial silicon disclosed by the invention.
With petroleum coke particles (granularity is the 100-150 order, and fixed carbon content is 91%, and ash content is 0.25%) at 1150 ℃ of temperature lower calcinations.
H with burnt petroleum coke particles, 40wt%
2O
2The H of solution, 85wt%
2SO
4Solution mixes, with petroleum coke particles, H
2O
2Solution, H
2SO
4Solution carries out proportioning by 1g: 1ml: 2ml, mixes.Reaction is 3 hours under 60 ℃ temperature, and reaction is stirred.Reacted petroleum coke powder is to dry after 7 with deionized water rinsing to pH value.
Petroleum coke particles after the above-mentioned processing was flooded 10 minutes in the solution of the salt of wormwood of the yellow soda ash that is containing 4wt% under the normal temperature and pressure and 4wt%, take out after-filtration, obtain modification petroleum coke particles A4.
(granularity is not more than 6mm with modification petroleum coke particles A4 and unmodified petroleum coke particles, fixed carbon content is 92%, ash content is 0.25%), silica allocates in the furnace charge, wherein the mass ratio of silica and reductive agent (comprising modification petroleum coke particles A4 and unmodified petroleum coke particles) is 2.7: 1 in the furnace charge, and modification petroleum coke particles A4 accounts for 50% of reductive agent total mass.
At last the furnace charge for preparing is mixed, put in the hot stove in ore deposit and smelt thermal treatment, smelting thermal treatment temp is 2500 ℃.
Do not see that in smelting process thorn is fiery, charge level is sent out the phenomenon of waiting indefinitely.The working of a furnace is good in the smelting process: can observe electrode and buy deeply and quietly in furnace charge, the charge level sinking velocity is fast, and gas is emerged equably through upper furnace, and current load is stable, and it is smooth and easy to go out silicon, and the silicon product grade reaches 99.50%.
Embodiment 5
Present embodiment is used for the smelting process of explanation industrial silicon disclosed by the invention.
With petroleum coke particles (granularity is the 50-100 order, and fixed carbon content is 92%, and ash content is 0.26%) at 1550 ℃ of temperature lower calcinations.
H with burnt petroleum coke particles, 40wt%
2O
2The H of solution, 85wt%
2SO
4Solution mixes, with petroleum coke particles, H
2O
2Solution, H
2SO
4Solution carries out proportioning by 1g: 1ml: 2ml, mixes.Reaction is 3 hours under 60 ℃ temperature, and reaction is stirred.Reacted petroleum coke powder is to dry after 7 with deionized water rinsing to pH value.
Petroleum coke particles after the above-mentioned processing in being dipping 10 minutes in the solution of potassium carbonate of 10wt% in concentration under the normal temperature and pressure, is taken out after-filtration, obtain modification petroleum coke particles A5.
(granularity is not more than 6mm with modification petroleum coke particles A5 and unmodified petroleum coke particles, fixed carbon content is 92%, ash content is 0.26%), silica allocates in the furnace charge, wherein the mass ratio of silica and reductive agent (comprising modification petroleum coke particles A5 and unmodified petroleum coke particles) is 2.2: 1 in the furnace charge, and modification petroleum coke particles A5 accounts for 35% of reductive agent total mass.
At last the furnace charge for preparing is mixed, put in the hot stove in ore deposit and smelt thermal treatment, smelting thermal treatment temp is 2500 ℃.
Do not see that in smelting process thorn is fiery, charge level is sent out the phenomenon of waiting indefinitely.The working of a furnace is good in the smelting process: can observe electrode and buy deeply and quietly in furnace charge, the charge level sinking velocity is fast, and gas is emerged equably through upper furnace, and current load is stable, and it is smooth and easy to go out silicon, and the silicon product grade reaches 99.54%.
Comparative Examples 1
This Comparative Examples is used for the smelting process of explanation industrial silicon of the prior art.
Silica: SiO
2Content is the silica of 99.5wt%, is crushed to granularity less than 10mm.
Refinery coke: ash content is crushed to granularity less than 10mm less than the refinery coke of 0.3wt%.
Binding agent: coal-tar pitch
Silica, refinery coke and the coal-tar pitch of fragmentation are mixed, the quality proportioning of silica, refinery coke, coal-tar pitch is 2.4: 1: 0.34, compound is pressed into the block with certain intensity at press, block is of a size of 5cm*4cm*3cm, block is dropped in the hot stove in ore deposit then and smelt manufacture silicon, smelting temperature is 2800 ℃.
Smelting process electric arc sound is bigger, and easily thorn fire, and charge level descends slower, and it is less to go out the silicon amount, and going out the silicon rate is 26%.
Comparative Examples 2
This Comparative Examples is used for the smelting process of explanation industrial silicon of the prior art.
The smelting process of industrial silicon is identical with embodiment 3, and different is that reductive agent all adopts unmodified petroleum coke particles.
Electric arc sound is big in the smelting process, and charge level is clamminess, and ventilation property is poor, and easily the thorn fire is lifted on the electrode, and furnace bottom rising causes normally smelting production.
Comparative Examples 3
This Comparative Examples is used for the smelting process of comparative illustration industrial silicon disclosed by the invention.
The smelting process of industrial silicon is identical with embodiment 3, and different is that reductive agent all adopts modification petroleum coke particles A3.
Charge level is too loose in the smelting process, easy thorn fire, electric arc sound is big, the modification refinery coke blow damage, scaling loss is big, furnace bottom easily goes up, and causes normally smelting production.
By above embodiment and Comparative Examples as can be seen, problems such as thorn fire and furnace bottom rising do not appear in embodiment, and in the Comparative Examples smelting process, charge level more easily sting fire, and charge level descends slowly, and it is less to go out the silicon amount, even can not normally smelt owing to working of a furnace difference.Thereby illustrate that throwing furnace charge of the present invention and smelting process can solve the problem that full oil coke is poor as the reactivity that reductive agent brings, ventilation property is poor, furnace bottom easily goes up effectively, and product silicon amount is big.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the smelting process of an industrial silicon comprises:
A, with the stone coke tar particles at 1150-1550 ℃ of temperature lower calcination, petroleum coke particles and oxygenant, intercalator after the calcining are mixed, and under 25-65 ℃ temperature, react;
B, the reaction product of step a is flooded in the aqueous solution for the treatment of agent, filter then; Described treatment agent is potassium compound and/or sodium compound, obtains the modification petroleum coke particles;
C, silica is mixed with reductive agent, smelt thermal treatment then; Wherein, described reductive agent comprises described modification petroleum coke particles and unmodified petroleum coke particles.
2. smelting process according to claim 1 is characterized in that, described potassium compound is sylvite, and described sodium compound is sodium salt; In the aqueous solution of described treatment agent, the content for the treatment of agent is 5-20wt%.
3. smelting process according to claim 1 and 2 is characterized in that, described potassium compound is salt of wormwood, and described sodium compound is yellow soda ash; In the aqueous solution of described treatment agent, the content for the treatment of agent is 8-15wt%.
4. smelting process according to claim 1 and 2 is characterized in that, among the step b, described dipping time is 5-15min.
5. smelting process according to claim 1 is characterized in that, the granularity of described petroleum coke particles is the 30-150 order, fixed carbon content 〉=90%, ash content≤0.3%.
6. smelting process according to claim 1 or 5 is characterized in that described oxygenant is the H of concentration 20-40wt%
2O
2Solution is or/and concentration is the HNO of 40-68wt%
3Solution; Described intercalator is that concentration is the H of 80-98wt%
2SO
4Solution.
7. smelting process according to claim 6 is characterized in that, the burnt particle of described step a PetroChina Company Limited. is with oxygenant, when intercalator mixes, and every 1g petroleum coke particles mixes with 0.4-1.2mLl oxygenant and 1-5mL intercalator.
8. smelting process according to claim 1 is characterized in that, among the step c, the mass ratio of silica and reductive agent is 2.2-2.7:1; In the described reductive agent, the content of modification petroleum coke particles is 5-50wt%.
9. according to claim 1 or 8 described smelting processes, it is characterized in that among the step c, described smelting thermal treatment temp is 2350-3000 ℃.
10. according to any described smelting process in the claim 1,2,5,7,8, it is characterized in that the granularity of described unmodified petroleum coke particles is not more than 10mm, fixed carbon content 〉=90%, ash content≤0.3%.
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|---|---|---|---|---|
| CN1281819A (en) * | 2000-08-31 | 2001-01-31 | 齐国庆 | New method for smelting industrial silium and ferro-silicon and its equipment |
| CN1472137A (en) * | 2002-07-29 | 2004-02-04 | 王清东 | Method for preparing silicon metal |
| CN1935641A (en) * | 2006-09-13 | 2007-03-28 | 大连理工大学 | Method for preparing carbon molecular sieve by intercalation of petrol coke |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281819A (en) * | 2000-08-31 | 2001-01-31 | 齐国庆 | New method for smelting industrial silium and ferro-silicon and its equipment |
| CN1472137A (en) * | 2002-07-29 | 2004-02-04 | 王清东 | Method for preparing silicon metal |
| CN1935641A (en) * | 2006-09-13 | 2007-03-28 | 大连理工大学 | Method for preparing carbon molecular sieve by intercalation of petrol coke |
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