CN113060736A - Method for preparing industrial silicon reducing agent by using biomass and additive to synergistically strengthen natural fermentation of petroleum coke - Google Patents
Method for preparing industrial silicon reducing agent by using biomass and additive to synergistically strengthen natural fermentation of petroleum coke Download PDFInfo
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- 239000002006 petroleum coke Substances 0.000 title claims abstract description 84
- 239000002028 Biomass Substances 0.000 title claims abstract description 76
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 61
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 55
- 239000010703 silicon Substances 0.000 title claims abstract description 55
- 238000000855 fermentation Methods 0.000 title claims abstract description 51
- 230000004151 fermentation Effects 0.000 title claims abstract description 51
- 239000000654 additive Substances 0.000 title claims abstract description 50
- 230000000996 additive effect Effects 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 239000000853 adhesive Substances 0.000 claims abstract description 31
- 230000001070 adhesive effect Effects 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000000227 grinding Methods 0.000 claims abstract description 28
- 239000008188 pellet Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000011300 coal pitch Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 7
- 239000001095 magnesium carbonate Substances 0.000 claims description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 claims description 5
- 244000276331 Citrus maxima Species 0.000 claims description 5
- 235000001759 Citrus maxima Nutrition 0.000 claims description 5
- 244000060011 Cocos nucifera Species 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 5
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 5
- 244000241235 Citrullus lanatus Species 0.000 claims 1
- 240000008790 Musa x paradisiaca Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000003723 Smelting Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 241000219109 Citrullus Species 0.000 description 4
- 241000234295 Musa Species 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a method for preparing an industrial silicon reducing agent by using biomass and an additive to synergistically strengthen natural fermentation of petroleum coke, and belongs to the technical field of efficient clean utilization of resources. The method comprises the steps of grinding and uniformly mixing biomass, alkali metal and petroleum coke to obtain a mixture A, placing the mixture A at the temperature of 15-35 ℃, sealing and naturally fermenting for 15-40 days to obtain a fermented material B, drying and grinding the fermented material B to obtain fermented powder, uniformly mixing the fermented powder, an adhesive and water, performing cold press molding to obtain pellets, and drying the pellets to obtain the industrial silicon reducing agent pellets. The composite reducing agent has the advantages of high fixed carbon content, high chemical reaction activity, low ash content and volatile matter content, and the like, can improve the reaction performance of petroleum coke through biomass fermentation, and has important guiding significance for the optimized production of industrial silicon and the high-quality and high-efficiency recovery of waste resources.
Description
Technical Field
The invention relates to a method for preparing an industrial silicon reducing agent by using biomass and an additive to synergistically strengthen natural fermentation of petroleum coke, and belongs to the technical field of efficient clean utilization of resources.
Background
The raw materials for producing industrial silicon comprise coal, petroleum coke, charcoal and the like which are mixed according to any proportion. But the charcoal is derived from trees, has limited sources and high price, and is not beneficial to the development of enterprises. Petroleum coke is a byproduct generated during crude oil cracking, has low ash content, porosity second to that of charcoal and high fixed carbon content, and can replace the charcoal to become a reducing agent for producing industrial silicon. However, petroleum coke has the disadvantages of too strong conductivity, low reactivity, small specific resistance and the like, and is not beneficial to the production of industrial silicon. And as the demand of silicon is continuously increased, the using amount of petroleum coke is gradually increased, which brings huge environmental pollution and energy consumption demand.
Most of the current methods for studying petroleum coke reducing agents required for silicon production are as follows: the method comprises the steps of grinding petroleum coke and low-ash coal, uniformly mixing, adding a binder and water, pressing into pellets under the pressure condition of 5-10 MPa, drying the pellets, and then preparing the composite carbonaceous reducing agent. The industrial silicon carbon reducing agent is obtained by drying, crushing, hot-pressing and molding a biomass raw material, heating and carbonizing the biomass raw material to obtain biomass carbon, uniformly mixing the biomass carbon with petroleum coke, and hot-pressing and pelletizing the biomass carbon into pellets. The method is characterized in that the petroleum coke material, the anthracite/bituminous coal material and the carbon powder are mixed to obtain a carbon reducing agent material, the granularity and the proportion of the material are main contents, and the problems of the formula and the proportion of the reducing agent are mainly solved.
Therefore, research and development of a high-quality composite reducing agent applied to industrial silicon smelting production are urgently needed, so that the high-quality composite reducing agent is beneficial to low carbon and energy conservation.
Disclosure of Invention
The invention provides a method for preparing an industrial silicon reducing agent by using biomass and additive to synergistically strengthen petroleum coke natural fermentation, aiming at the problem of preparation of the petroleum coke reducing agent in the prior art, the invention takes petroleum coke as a full-coke reducing agent, natural fermentation is carried out by mixing biomass, additives (potassium carbonate, calcium carbonate, sodium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide, sodium chloride and the like) and petroleum coke, the additive is utilized to cooperate with biomass fermentation, the structural characteristics of the petroleum coke are changed, the biomass is compatible with the petroleum coke, and the reactivity of the petroleum coke is greatly improved; the method is beneficial to reducing high temperature and high energy consumption, improving the reactivity of the ore raw material, reducing the cost of the raw material and reducing the dependence on fossil fuel.
The fixed carbon content of petroleum coke is high, the ash content is low, but the sulfur content is high, the gasification is difficult, the reaction activity is low, and the reaction can be carried out only by high temperature and high energy consumption; the additive (potassium carbonate, calcium carbonate, sodium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide, sodium chloride and the like) and the biomass are used for synergistically strengthening petroleum coke fermentation to improve the gasification reaction rate, reduce the gasification temperature, modulate the distribution of gas products, relieve the problem of furnace bottom rising and improve the effective utilization rate of resources.
A method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing the biomass, the additive and the petroleum coke to obtain a mixture A; wherein the additive is one or more of potassium carbonate, calcium carbonate, sodium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide and sodium chloride;
(2) placing the mixture A in the step (1) at the temperature of 15-35 ℃, and sealing and naturally fermenting for 15-40 days to obtain a fermented material B;
(3) drying and grinding the fermentation material B in the step (2) to obtain fermentation powder;
(4) uniformly mixing the fermented powder, the adhesive and water in the step (3), performing cold press molding to obtain pellets, and drying the pellets to obtain industrial silicon reducing agent pellets;
the fixed carbon content of the petroleum coke in the step (1) is not lower than 80%, and the petroleum coke with the particle size not larger than 0.075mm accounts for 50-80 wt%; the water content of the biomass is 60-90%, and the biomass is pericarp;
the biomass in the step (1) is one or more of banana peel, shaddock peel, orange peel, apple peel, orange peel, watermelon peel and coconut peel;
the biomass content is 5-30 wt% and the additive amount is 1-3 wt% based on the total mass of the biomass and the petroleum coke being 100%;
the fermented powder in the step (3) accounts for 50-80 wt% and has the particle size not larger than 0.075 mm;
the adhesive accounts for 2-3% and the water accounts for 5-10% of the total mass of the fermented powder, the adhesive and the water as 100%;
the adhesive is modified medium-temperature coal pitch or an organic-inorganic composite adhesive, wherein the inorganic adhesive accounts for 30-50 wt% of the organic-inorganic composite adhesive, and the organic adhesive accounts for 50-70%;
the inorganic adhesive is water glass, and the organic adhesive is cellulose adhesive;
the pellet particle size in the step (4) is 60-110 mm.
The principle of the synergy of the biomass and the additive is as follows: the additive (potassium carbonate, calcium carbonate, sodium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide, sodium chloride) has good migration property, K+、Ca2+、Na+When cations migrate to the surface of the biomass particles or enter the pores of the biomass particles, the cations and organic macromolecules form an organic complex through quasi-crosslinking, the macromolecule structure, oxygen-containing functional groups are split and side chains are easy to fall off in the heating process, and more alkane gas and H are generated2A large amount of active hydrogen is transferred to the surface of the biomass particles and reacts with part of organic matters; in addition, along with the rise of the temperature, the generation of gaseous products promotes the formation of a large number of micropores on the surfaces of biomass particles, additive molecules in a molten state can be continuously diffused, the cracking of the biomass is further promoted, the activation energy of the thermal cracking reaction is reduced, and the reaction rate is improved.
The invention has the beneficial effects that:
(1) the method takes petroleum coke as the total coke reducing agent, and the carbonaceous reducing agent is prepared by adding the additive and the biomass peel for natural fermentation, so that the fixed carbon content is high, the chemical reaction activity is high, the energy consumption of the submerged arc furnace is reduced in the using process, the activation energy of the carbon material is reduced, the reaction activity is enhanced, the temperature required by pyrolysis is reduced, the gasification reaction rate is obviously improved, and the problems of overhigh energy consumption and resource waste of the submerged arc furnace are effectively solved;
(2) the carbonaceous reducing agent has high chemical reaction activity, so that the carbon material synergistic effect is enhanced, the power required in the pyrolysis process of the submerged arc furnace is reduced, the temperature required by pyrolysis is reduced, and the problems of overhigh energy consumption and resource waste of the submerged arc furnace are effectively solved;
(3) the waste biomass and the additive have synergistic effect, so that the chemical reaction activity of the carbon material is improved, the effective utilization rate of the reducing agent is further improved, the raw material cost of industrial silicon smelting is reduced, and the problems of high energy consumption and large pollution are effectively solved;
(4) the method comprehensively utilizes the waste biomass raw materials, improves the economic utilization value of waste resources, solves the problems of environmental problems and resource waste caused by waste biomass, and further reduces the cost of industrial silicon smelting raw materials.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing banana peel, potassium carbonate and petroleum coke to obtain a mixture A; wherein the water content in the banana peel is about 65%, the fixed carbon in the banana peel is about 40%, the fixed carbon content of the petroleum coke is not lower than 80%, and the petroleum coke with the particle size not larger than 0.075mm accounts for 50 wt%; based on the total mass of the biomass and the petroleum coke being 100%, the biomass content is 5 wt%, the petroleum coke content is 95 wt%, and the amount of the additive (potassium carbonate) is 1 wt%;
(2) placing the mixture A obtained in the step (1) at the temperature of 30 ℃ for closed natural fermentation for 20d to obtain a fermented material B;
(3) drying the fermentation material B in the step (2) in a drying oven at the temperature of 80 ℃ for 25h, and grinding to obtain fermentation powder; wherein the fermented powder material with particle size not greater than 0.075mm accounts for 70 wt%;
(4) uniformly mixing the fermented powder in the step (3), an adhesive (modified medium-temperature coal pitch) and water, performing cold press molding under the pressure of 6MPa to obtain pellets with the average particle size of 70mm, and drying the pellets in a drying oven at the temperature of 100 ℃ for 24 hours to obtain an industrial silicon reducing agent; wherein the organic-inorganic composite binder comprises 35 wt% of inorganic binder (water glass), 65 wt% of organic binder (cellulose binder), 2.0 wt% of binder and 6 wt% of water, based on 100 wt% of total mass of the fermented powder, the binder (modified medium temperature coal pitch) and the water;
the content of fixed carbon in the industrial silicon reducing agent in the embodiment is 85.3 wt%;
with 2g of Silica (SiO)299.5 wt.%), grinding to powder with a particle size of 0.075mm, sieving, and mixing with 08g of industrial silicon reducing agent is uniformly mixed, added into a submerged arc furnace and smelted at the temperature of more than 1800 ℃, and the component obtained after smelting is Si.
Example 2: a method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing the shaddock peel, the calcium carbonate and the petroleum coke to obtain a mixture A; wherein the water content in the shaddock peel is about 60%, the fixed carbon in the shaddock peel is about 21%, the fixed carbon content in the petroleum coke is not less than 80%, and the petroleum coke with the particle size not more than 0.075mm accounts for 60 wt%; based on the total mass of the biomass and the petroleum coke being 100%, the biomass content is 10 wt%, the petroleum coke content is 90 wt%, and the amount of the additive (calcium carbonate) is 2 wt%;
(2) placing the mixture A obtained in the step (1) at the temperature of 32 ℃ for closed natural fermentation for 30d to obtain a fermented material B;
(3) drying the fermentation material B in the step (2) in a drying oven at the temperature of 90 ℃ for 28h, and grinding to obtain fermentation powder; wherein the fermented powder material with particle size not more than 0.075mm accounts for 65 wt%;
(4) uniformly mixing the fermented powder in the step (3), an adhesive (modified medium-temperature coal pitch) and water, performing cold press molding under the pressure of 7MPa to obtain pellets with the average particle size of 80mm, and drying the pellets in a drying oven at the temperature of 100 ℃ for 24 hours to obtain an industrial silicon reducing agent; wherein the organic-inorganic composite binder comprises 40 wt% of inorganic binder (water glass), 60 wt% of organic binder (cellulose binder), 2.3 wt% of binder and 8 wt% of water, wherein the total mass of the fermented powder, the binder (modified medium-temperature coal pitch) and the water is 100%;
the content of fixed carbon in the industrial silicon reducing agent in the embodiment is 81.5 wt%;
with 2g of Silica (SiO)299.5 wt.%), grinding into powder with a particle size of 0.075mm, sieving, mixing with 0.8g of industrial silicon reducer, adding into a submerged arc furnace, and smelting at a temperature higher than 1800 ℃ to obtain Si.
Example 3: a method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing orange peel, magnesium carbonate and petroleum coke to obtain a mixture A; wherein the water content in the orange peel is about 75 percent, the fixed carbon in the orange peel is about 25 percent, the fixed carbon content of the petroleum coke is not less than 85 percent, and the petroleum coke with the particle size not more than 0.075mm accounts for 70 percent by weight; based on the total mass of the biomass and the petroleum coke being 100%, the biomass content is 15 wt%, the petroleum coke content is 85 wt%, and the amount of the additive (magnesium carbonate) is 1.5 wt%;
(2) placing the mixture A in the step (1) at the temperature of 33 ℃ for closed natural fermentation for 22d to obtain a fermented material B;
(3) drying the fermentation material B in the step (2) in a drying oven at the temperature of 85 ℃ for 28h, and grinding to obtain fermentation powder; wherein the fermented powder material with particle size not greater than 0.075mm accounts for 70 wt%;
(4) uniformly mixing the fermented powder in the step (3), an adhesive (modified medium-temperature coal pitch) and water, performing cold press molding under the pressure of 6MPa to obtain pellets with the average particle size of 90mm, and drying the pellets in a drying oven at the temperature of 100 ℃ for 24 hours to obtain an industrial silicon reducing agent; wherein the organic-inorganic composite binder comprises 45 wt% of inorganic binder (water glass), 55 wt% of organic binder (cellulose binder), 2.5 wt% of binder and 9 wt% of water, based on 100 wt% of total mass of the fermented powder, the binder (modified medium temperature coal pitch) and the water;
the content of fixed carbon in the industrial silicon reducing agent in the embodiment is 83.6 wt%;
with 2g of Silica (SiO)299.5 wt.%), grinding into powder with a particle size of 0.075mm, sieving, mixing with 0.8g of industrial silicon reducer, adding into a submerged arc furnace, and smelting at a temperature higher than 1800 ℃ to obtain Si.
Example 4: a method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing apple peel, sodium hydroxide and petroleum coke to obtain a mixture A; wherein the water content in the apple peel is about 80%, the fixed carbon in the apple peel is about 22%, the fixed carbon content of the petroleum coke is not lower than 80%, and the petroleum coke with the particle size not larger than 0.075mm accounts for 80 wt%; based on the total mass of the biomass and the petroleum coke being 100%, the biomass content is 20 wt%, the petroleum coke content is 80 wt%, and the amount of the additive (sodium hydroxide) is 3 wt%;
(2) placing the mixture A obtained in the step (1) at the temperature of 35 ℃ for closed natural fermentation for 20d to obtain a fermented material B;
(3) drying the fermentation material B in the step (2) in a drying oven at the temperature of 80 ℃ for 25h, and grinding to obtain fermentation powder; wherein the fermented powder material with particle size not greater than 0.075mm accounts for 75 wt%;
(4) uniformly mixing the fermented powder in the step (3), an adhesive (modified medium-temperature coal pitch) and water, performing cold press molding under the pressure of 6MPa to obtain pellets with the average particle size of 90mm, and drying the pellets in a drying oven at the temperature of 100 ℃ for 24 hours to obtain an industrial silicon reducing agent; wherein the organic-inorganic composite binder comprises 50 wt% of inorganic binder (water glass), 50 wt% of organic binder (cellulose binder), 3.0 wt% of binder and 10 wt% of water, based on 100 wt% of total mass of the fermented powder, the binder (modified medium temperature coal pitch) and the water;
the content of fixed carbon in the industrial silicon reducing agent in the embodiment is 83.8 wt%;
with 2g of Silica (SiO)299.5 wt.%), grinding into powder with a particle size of 0.075mm, sieving, mixing with 0.8g of industrial silicon reducer, adding into a submerged arc furnace, and smelting at a temperature higher than 1800 ℃ to obtain Si.
Example 5: a method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing watermelon peel, sodium carbonate and petroleum coke to obtain a mixture A; wherein the water content in the watermelon peel is about 90 percent, the fixed carbon in the watermelon peel is about 21 percent, the fixed carbon content of the petroleum coke is not less than 80 percent, and the petroleum coke with the particle size not more than 0.075mm accounts for 75 percent by weight; based on the total mass of the biomass and the petroleum coke being 100%, the biomass content is 25 wt%, the petroleum coke content is 75 wt%, and the amount of the additive (sodium carbonate) is 2 wt%;
(2) placing the mixture A obtained in the step (1) at the temperature of 32 ℃ for closed natural fermentation for 23d to obtain a fermented material B;
(3) drying the fermentation material B in the step (2) in a drying oven at the temperature of 80 ℃ for 25h, and grinding to obtain fermentation powder; wherein the fermented powder material with particle size not greater than 0.075mm accounts for 80 wt%;
(4) uniformly mixing the fermented powder in the step (3), an adhesive (modified medium-temperature coal pitch) and water, performing cold press molding under the pressure of 8MPa to obtain pellets with the average particle size of 100mm, and drying the pellets in a drying oven at the temperature of 80 ℃ for 25 hours to obtain an industrial silicon reducing agent; wherein the organic-inorganic composite binder comprises 30 wt% of inorganic binder (water glass), 70 wt% of organic binder (cellulose binder), 2.2 wt% of binder and 5 wt% of water, based on 100% of total mass of the fermented powder, the binder (modified medium temperature coal pitch) and the water;
the content of fixed carbon in the industrial silicon reducing agent in the embodiment is 81.5 wt%;
with 2g of Silica (SiO)299.5 wt.%), grinding into powder with a particle size of 0.075mm, sieving, mixing with 0.8g of industrial silicon reducer, adding into a submerged arc furnace, and smelting at a temperature higher than 1800 ℃ to obtain Si.
Example 6: a method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing orange peel, potassium hydroxide and petroleum coke to obtain a mixture A; wherein the water content in the orange peel is about 75 percent, the fixed carbon in the orange peel is about 21 percent by weight, the fixed carbon content of the petroleum coke is not less than 80 percent, and the petroleum coke with the particle size not more than 0.075mm accounts for 80 percent by weight; based on the total mass of the biomass and the petroleum coke being 100%, the biomass content is 10 wt%, the petroleum coke content is 90 wt%, and the amount of the additive (potassium hydroxide) is 1 wt%;
(2) placing the mixture A in the step (1) at the temperature of 31 ℃ for closed natural fermentation for 20d to obtain a fermented material B;
(3) drying the fermentation material B in the step (2) in a drying oven at the temperature of 80 ℃ for 25h, and grinding to obtain fermentation powder; wherein the fermented powder material with particle size not greater than 0.075mm accounts for 70 wt%;
(4) uniformly mixing the fermented powder in the step (3), an adhesive (modified medium-temperature coal pitch) and water, performing cold press molding under the pressure of 10MPa to obtain pellets with the average particle size of 85mm, and drying the pellets in a drying oven at the temperature of 90 ℃ for 22h to obtain an industrial silicon reducing agent; wherein the organic-inorganic composite binder comprises 35 wt% of inorganic binder (water glass), 65 wt% of organic binder (cellulose binder), 2.6 wt% of binder and 10 wt% of water, based on 100 wt% of total mass of the fermented powder, the binder (modified medium temperature coal pitch) and the water;
the content of fixed carbon in the industrial silicon reducing agent in the embodiment is 82 wt%;
with 2g of Silica (SiO)299.5 wt.%), grinding into powder with a particle size of 0.075mm, sieving, mixing with 0.8g of industrial silicon reducer, adding into a submerged arc furnace, and smelting at a temperature higher than 1800 ℃ to obtain Si.
Example 7: a method for preparing an industrial silicon reducing agent by using biomass and an additive to cooperatively strengthen petroleum coke natural fermentation comprises the following specific steps:
(1) grinding and uniformly mixing coconut peel, sodium chloride and petroleum coke to obtain a mixture A; wherein the moisture in the coconut peel is about 60 percent, the fixed carbon in the coconut peel is about 26 percent, the fixed carbon content of the petroleum coke is not less than 85 percent, and the petroleum coke with the particle size not more than 0.075mm accounts for 85 percent by weight; based on the total mass of the biomass and the petroleum coke being 100%, the biomass content is 15 wt%, the petroleum coke content is 85 wt%, and the amount of the additive (sodium chloride) is 3 wt%;
(2) placing the mixture A obtained in the step (1) at the temperature of 35 ℃ for closed natural fermentation for 20d to obtain a fermented material B;
(3) drying the fermentation material B in the step (2) in a drying oven at the temperature of 80 ℃ for 25h, and grinding to obtain fermentation powder; wherein the fermented powder material with particle size not more than 0.075mm accounts for 65 wt%;
(4) uniformly mixing the fermented powder, the adhesive (organic-inorganic composite adhesive) and water in the step (3), performing cold press molding under the pressure of 7MPa to obtain pellets with the average particle size of 100mm, and drying the pellets in a drying oven at the temperature of 100 ℃ for 24 hours to obtain an industrial silicon reducing agent; wherein the organic-inorganic composite binder comprises 45 wt% of inorganic binder (water glass), 55 wt% of organic binder (cellulose binder), 2.0 wt% of binder and 10 wt% of water, wherein the total mass of the fermented powder, the binder and the water is 100%;
the content of fixed carbon in the industrial silicon reducing agent in the embodiment is 85.8 wt%;
with 2g of Silica (SiO)299.5 wt.%), grinding into powder with a particle size of 0.075mm, sieving, mixing with 0.8g of industrial silicon reducer, adding into a submerged arc furnace, and smelting at a temperature higher than 1800 ℃ to obtain Si.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (9)
1. A method for preparing an industrial silicon reducing agent by natural fermentation of petroleum coke reinforced by synergy of biomass and additives is characterized by comprising the following specific steps:
(1) grinding and uniformly mixing the biomass, the additive and the petroleum coke to obtain a mixture A; wherein the additive is one or more of potassium carbonate, calcium carbonate, sodium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide and sodium chloride;
(2) placing the mixture A in the step (1) at the temperature of 15-35 ℃, and sealing and naturally fermenting for 15-40 days to obtain a fermented material B;
(3) drying and grinding the fermentation material B in the step (2) to obtain fermentation powder;
(4) and (4) uniformly mixing the fermented powder, the adhesive and water in the step (3), performing cold press molding to obtain pellets, and drying the pellets to obtain the industrial silicon reducing agent pellets.
2. The method for preparing the industrial silicon reducing agent by using the biomass and the additive to synergistically strengthen natural fermentation of petroleum coke according to claim 1, wherein the biomass and the additive are characterized in that: the fixed carbon content of the petroleum coke in the step (1) is not lower than 80%, and the petroleum coke with the particle size not larger than 0.075mm accounts for 50-80 wt%; the water content of the biomass is 60-90%, and the biomass is pericarp.
3. The method for preparing the industrial silicon reducing agent by using the biomass and the additive to synergistically strengthen natural fermentation of petroleum coke according to claim 2, wherein the biomass and the additive are characterized in that: the biomass in the step (1) is one or more of banana peel, shaddock peel, orange peel, apple peel, orange peel, watermelon peel and coconut peel.
4. The method for preparing the industrial silicon reducing agent by using the biomass and the additive to synergistically strengthen natural fermentation of petroleum coke according to claim 1, wherein the biomass and the additive are characterized in that: the biomass content is 5-30 wt% and the additive amount is 1-3 wt% based on the total mass of the biomass and the petroleum coke being 100%.
5. The method for preparing the industrial silicon reducing agent by using the biomass and the additive to synergistically strengthen natural fermentation of petroleum coke according to claim 1, wherein the biomass and the additive are characterized in that: the fermented powder in the step (3) has a particle size of not more than 0.075mm and accounts for 50-80 wt%.
6. The method for preparing the industrial silicon reducing agent by using the biomass and the additive to synergistically strengthen natural fermentation of petroleum coke according to claim 1, wherein the biomass and the additive are characterized in that: the adhesive accounts for 2-3% and the water accounts for 5-10% of the total mass of the fermented powder, the adhesive and the water as 100%.
7. The method for preparing the industrial silicon reducing agent by naturally fermenting the petroleum coke through the synergy of the biomass and the additive according to claim 1 or 6, is characterized in that: the adhesive is modified medium-temperature coal pitch or an organic-inorganic composite adhesive, wherein the inorganic adhesive accounts for 30-50 wt% of the organic-inorganic composite adhesive, and the organic adhesive accounts for 50-70%.
8. The method for preparing the industrial silicon reducing agent by using the biomass and the additive to synergistically strengthen natural fermentation of petroleum coke according to claim 7, wherein the biomass and the additive are characterized in that: the inorganic adhesive is water glass, and the organic adhesive is cellulose adhesive.
9. The method for preparing the industrial silicon reducing agent by using the biomass and the additive to synergistically strengthen natural fermentation of petroleum coke according to claim 1, wherein the biomass and the additive are characterized in that: the particle size of the pellets in the step (4) is 60-110 mm.
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