CN108342637B - Method for producing polysilane/siloxene and ferrosilicon by reacting carbide slag iron with acid - Google Patents

Method for producing polysilane/siloxene and ferrosilicon by reacting carbide slag iron with acid Download PDF

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CN108342637B
CN108342637B CN201810151846.3A CN201810151846A CN108342637B CN 108342637 B CN108342637 B CN 108342637B CN 201810151846 A CN201810151846 A CN 201810151846A CN 108342637 B CN108342637 B CN 108342637B
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ferrosilicon
siloxene
polysilane
carbide slag
carbide
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CN108342637A (en
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刘振宇
李正科
刘清雅
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C35/00—Master alloys for iron or steel
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B33/04—Hydrides of silicon

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Abstract

The invention provides a method for simultaneously obtaining polysilane/siloxene and ferrosilicon, belonging to the field of comprehensive utilization of wastes. The method mainly comprises the following steps: mixing and reacting carbide slag iron which is a byproduct in the production of calcium carbide with a halogen-containing acidic solution at the temperature of-35-70 ℃, converting silicon and calcium in the carbide slag iron into yellow powdery polysilane/siloxene, and obtaining black ferrosilicon as a remainder. And (3) separating yellow powder from black residue according to density difference, washing and drying to obtain yellow polysilane/siloxene and black ferrosilicon. The method provided by the invention can simultaneously obtain high-value polysilane/siloxene and high-purity ferrosilicon, realizes high-value utilization of carbide slag iron, and has wide industrial application prospect.

Description

Method for producing polysilane/siloxene and ferrosilicon by reacting carbide slag iron with acid
Technical Field
The invention relates to a comprehensive utilization method of carbide slag iron, in particular to separation of acid treatment carbide slag iron and solid products.
Background
Raw materials of coke and calcium oxide for producing the calcium carbide generally contain impurities such as silicon dioxide, iron oxide and the like. Under the high-temperature reaction condition for producing the calcium carbide, the impurities and calcium generate iron slag. The carbide slag iron is also called carbide iron, carbide ferrosilicon or carbide ferrosilicon, and the main component is silicon calcium (CaSi)2) Silicon iron (Fe-Si), and other metals (magnesium, aluminum, and titanium). The mass fraction of the ferrosilicon is generally more than 50 percent, and the mass fraction of the calcium is between 1 and 20 percent. In the process of producing acetylene and calcium hydroxide by the reaction of calcium carbide and water, the calcium carbide slag iron is not changed and is deposited at the bottom of the slag slurry due to larger granularity and density. About 2730 million tons of calcium carbide are produced in China in 2016, and the iron content of the calcium carbide slag as a byproduct is about 27-110 million tons (which is 1-4 wt% of the calcium carbide yield). At present, carbide slag iron is mainly used as a raw material for iron making or partially replaces ferrosilicon, but the application value is not high because the carbide slag iron is an alloy (or a mixture) of various substances.
Numerous reports have shown that calcium silicate reacts topologically with hydrochloric acid to form polysilane (polysilane) or siloxene (siloxene) in the form of yellow powder. The reaction temperature is lower than-20 ℃ to obtain the main polysilane (Si)6H6) When the reaction temperature is higher than-20 ℃, polysilane can be hydrolyzed to generate oxygen-containing siloxene (Si)6H3-x(OH)3+xX is more than or equal to 0 and less than or equal to 3), the higher the reaction temperature is, the longer the reaction time is, and the higher the oxygen content is.
The polysilane and siloxene can react with organic matter to prepare organosilicon material, or dissociate into two-dimensional nano silicon plane material. Compared with bulk silicon materials, the two-dimensional nano silicon planar material has special surface functional groups and quantum effects, and has application in catalysis, electrodes, semiconductors, photovoltaic and lithium ion battery materials and other aspects.
Ferrosilicon does not react with halogen-containing acids such as hydrochloric acid. The density of polysilanes and siloxenes is about 1.8g/cm3The ferrosilicon density is generally more than 3.3g/cm3The two can be separated by a density difference.
Disclosure of Invention
The present invention was completed based on the following research works of the inventors:
calcium-containing carbide slag iron can react with halogen-containing acid solutions such as hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid and the like to generate polysilane or siloxene. The conversion rate of calcium silicon is above 90%, and the aluminum and magnesium compounds are dissolved in the acid solution. The ferrosilicon does not participate in the reaction, so the purity of the ferrosilicon is improved. Polysilane/siloxenes prepared from carbide slag iron and those prepared using commercial calcium silicates have the same composition and properties, but the particle size of the polysilane/siloxenes is smaller. In view of the above research, the present invention aims to provide a method for producing polysilane/siloxene and ferrosilicon by reacting carbide slag iron with acid, so as to realize high-value utilization of carbide slag iron.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
a method for producing polysilane/siloxene and ferrosilicon by reacting carbide slag iron with acid comprises the following steps:
reacting carbide slag iron with an acid solution in an oxygen-free atmosphere to obtain yellow powdery polysilane/siloxene and black granular ferrosilicon, and separating, washing and drying to obtain the product.
Preferably, the carbide slag iron is obtained from carbide slag or carbide slag.
Preferably, the carbide slag iron can be directly utilized or can be crushed to be less than 20mm for utilization. More preferably, the material is crushed to 10mm or less.
Preferably, the acid solution may be a mixture of one or more halogen-containing acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, and perchloric acid.
Preferably, the reaction temperature is-35 to-20 ℃, the reaction time is 10 to 200 hours, and the obtained yellow powder is polysilane with the composition of Si6H6。
Preferably, the reaction temperature is-20-70 ℃, the reaction time is 0.2-120 h, and the obtained yellow powder is siloxene, and the composition of the yellow powder is Si6H3-x(OH)3+xWherein x is more than or equal to 0 and less than or equal to 3. More preferably, the reaction temperature is 0-30 ℃, the reaction time is 1-10 h, and the obtained yellow powder is siloxene, and the composition of the yellow powder is Si6H3-x(OH)3+xWherein x is more than or equal to 0 and less than or equal to 3.
Preferably, the atmosphere free of oxygen may be a mixed gas of one or more of carbon dioxide, nitrogen, argon and helium.
Preferably, the mass ratio of the carbide slag iron to the acid solution is 1: 1-200, the mass fraction of the acid solution is 1-40%, and the reaction can be accelerated by stirring. More preferably, the mass ratio of the carbide slag iron to the acid solution is 1: 5-20, and the mass fraction of the acid solution is 5-30%.
Preferably, the solid product separation may be a heavy liquid separation, gravity driven settling, or hydrocyclone, among other methods.
Preferably, the drying of the yellow powder is completed under vacuum or under protection of an oxygen-free atmosphere.
The method treats the carbide slag iron by using the halogen-containing acid solution under the oxygen-free condition to obtain yellow powdery polysilane/siloxene and black ferrosilicon. The conversion rate of the silicon and the calcium is more than 90 percent. The process simultaneously dissolves calcium, magnesium and aluminum compounds in the carbide slag iron, but more than 95 wt% of iron-containing components are insoluble, so that the obtained ferrosilicon has high purity.
Detailed Description
Example 1
Crushing certain carbide slag iron to be less than 10mm, adding hydrochloric acid solution with the concentration of 12 wt% according to the solid-liquid mass ratio of 1:20, reacting for 3 hours in an argon atmosphere at the temperature of 20 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by utilizing heavy liquid. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 4.2 wt%, and the yield of ferrosilicon was 93.8 wt%.
Example 2
Crushing certain carbide slag iron to be less than 3mm, adding 3 wt% hydrochloric acid and 5 wt% recycled mixed acid solution according to the solid-liquid mass ratio of 1:100, reacting for 0.2h in an argon atmosphere at 60 ℃, and separating the reacted solution by using a hydrocyclone to obtain yellow powder polysilane/siloxene of overflow and black ferrosilicon of underflow. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 3.1 wt%, and the yield of ferrosilicon was 94.3 wt%.
Example 3
Crushing certain carbide slag iron to be less than 5mm, adding 12 wt% hydriodic acid solution according to the solid-liquid mass ratio of 1:20, reacting for 5 hours in the argon atmosphere at 10 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by heavy liquid separation. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 4.0 wt%, and the yield of ferrosilicon was 94.0 wt%.
Example 4
Crushing certain carbide slag iron to be less than 10mm, adding a hydrobromic acid solution with the concentration of 2 wt% according to the solid-liquid mass ratio of 1:50, reacting for 1h in a mixed atmosphere of carbon dioxide and nitrogen at 70 ℃, and separating by using gravity-driven settling equipment to obtain yellow powdery polysilane/siloxene and black ferrosilicon. The polysilane/siloxene was dried under vacuum after filtration and washing respectively, and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 3.0 wt%, and the yield of ferrosilicon was 94.0 wt%.
Example 5
Crushing certain carbide slag iron to be less than 10mm, adding hydrochloric acid solution with the concentration of 37 wt% according to the solid-liquid mass ratio of 1:5, reacting for 120 hours in an argon atmosphere at the temperature of minus 30 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by heavy liquid separation and centrifugation. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 2.9 wt%, and the yield of ferrosilicon was 94.4 wt%.
Example 6
Crushing certain carbide slag iron to be less than 10mm, adding 1 wt% perchloric acid solution according to the solid-liquid mass ratio of 1:200, reacting for 5 hours in a nitrogen atmosphere at 10 ℃, and separating by using a hydrocyclone to obtain yellow powdery polysilane/siloxane of overflow and black ferrosilicon of underflow. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 3.7 wt%, and the yield of ferrosilicon was 94.4 wt%.
Example 7
Crushing certain carbide slag iron to below 10mm, adding 12 wt% hydrochloric acid and 11 wt% hydrochloric acid mixed solution according to the solid-liquid mass ratio of 1:20, stirring for 3 hours at the temperature of 20 ℃ in an argon atmosphere at the speed of 50r/min, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by utilizing heavy liquid. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 4.0 wt%, and the yield of ferrosilicon was 94.0 wt%.
Example 8
Crushing certain carbide slag iron to be less than 20mm, adding 40 wt% hydrobromic acid solution according to the solid-liquid mass ratio of 1:5, reacting for 200 hours in an argon atmosphere at-35 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by utilizing heavy liquid separation. After filtration and washing respectively, the polysilane/siloxene was dried in a nitrogen atmosphere and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 3.6 wt%, and the yield of ferrosilicon was 94.2 wt%.
Example 9
Crushing certain carbide slag iron to be less than 3mm, adding hydrochloric acid solution with the concentration of 20 wt% according to the solid-liquid mass ratio of 1:10, reacting for 10 hours in an argon atmosphere at the temperature of minus 20 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by heavy liquid separation and centrifugation. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 2.5 wt%, and the yield of ferrosilicon was 95.2 wt%.
Example 10
Crushing certain carbide slag iron to be less than 10mm, adding a hydriodic acid solution with the concentration of 30 wt% according to the solid-liquid mass ratio of 1:1, reacting for 1h in a helium atmosphere at the temperature of 20 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by heavy liquid separation. After filtration and washing respectively, the polysilane/siloxene was dried in an argon atmosphere and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 4.0 wt%, and the yield of ferrosilicon was 94.0 wt%.
Example 11
Crushing certain carbide slag iron to below 5mm, adding hydrochloric acid solution with the concentration of 12 wt% according to the solid-liquid mass ratio of 1:10, stirring for 1h at 400r/min in a helium atmosphere at the temperature of 20 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by heavy liquid separation. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 7.0 wt%, and the yield of ferrosilicon was 82.1 wt%.
Example 12
Crushing certain carbide slag iron to be less than 20mm, adding a mixed acid solution of hydrochloric acid and hydroiodic acid with the concentration of 20 wt% according to the solid-liquid mass ratio of 1:4, reacting for 20 hours in a mixed atmosphere of argon and nitrogen at the temperature of 0 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by utilizing heavy liquid. After filtration and washing respectively, the polysilane/siloxene was dried in a carbon dioxide atmosphere and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 6.8 wt%, and the yield of ferrosilicon was 81.8 wt%.
Example 13
Crushing certain carbide slag iron to be less than 20mm, adding hydrochloric acid solution with the concentration of 12 wt% according to the solid-liquid mass ratio of 1:20, reacting for 3 hours in an argon atmosphere at the temperature of 20 ℃, and separating yellow powdery polysilane/siloxane and black ferrosilicon products from the reacted solution by using gravity-driven settling equipment. The two products were filtered and washed separately, the polysilane/siloxene dried under a nitrogen atmosphere, and the ferrosilicon dried under conventional conditions. The yield of polysilane/siloxene was 11.6 wt%, and the yield of ferrosilicon was 51.0 wt%.
Example 14
Crushing certain carbide slag iron to below 10mm, adding a mixed acid solution of hydrochloric acid, hydrobromic acid and hydroiodic acid with the concentration of 10 wt% according to the solid-liquid mass ratio of 1:50, reacting for 120 hours in an argon atmosphere at the temperature of minus 20 ℃, filtering to obtain a mixture of yellow powdery polysilane/siloxene and black ferrosilicon, and separating the yellow powdery polysilane/siloxene and the black ferrosilicon by using a heavy liquid separation and centrifugation method. After filtration and washing respectively, the polysilane/siloxene was dried under vacuum and the ferrosilicon was dried under conventional conditions. The yield of polysilane/siloxene was 9.9 wt%, and the yield of ferrosilicon was 51.9 wt%.
The particular features or characteristics described in this specification may be combined in any suitable manner in any one or more embodiments.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for producing polysilane/siloxene and ferrosilicon by reacting carbide slag iron with acid is characterized in that:
reacting carbide slag iron with an acid solution in an oxygen-free atmosphere to obtain yellow powdery polysilane/siloxene and black granular ferrosilicon, separating, washing and drying the obtained solid product to obtain the polysilane/siloxene and the ferrosilicon.
2. The method of claim 1, wherein the carbide slag iron is a by-product of carbide production, and is obtained from carbide or carbide slag, also known as carbide iron, ferrosilicon carbide, or carbide ferrosilicon.
3. The method of claim 1, wherein the carbide slag iron is used directly or is crushed to less than 20 mm.
4. The method of claim 1, wherein the acid solution is a mixture of one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, and perchloric acid.
5. The method according to claim 1, wherein the reaction temperature is-35 to-20 ℃ and the reaction time is 10 to 200 hours, and the obtained yellow powder is polysilane with Si composition6H6。
6. The method of claim 1, wherein the reaction temperature is-20 to 70 ℃ and the reaction time is 0.2 to 120 hours, and the obtained yellow powder is siloxene with Si composition6H3-x(OH)3+xWherein x is more than or equal to 0 and less than or equal to 3.
7. The method of claim 1, wherein the oxygen-free atmosphere is a mixture of one or more of carbon dioxide, nitrogen, argon, and helium.
8. The method according to claim 1, wherein the mass ratio of the carbide slag iron to the acid solution is 1: 1-200, the mass fraction of the acid solution is 1-40%, and the reaction is accelerated by stirring.
9. The process according to claim 1, 5 or 6, characterized in that the separation of the product yellow powder from black particles uses heavy liquid separation, gravity driven sedimentation or hydrocyclone.
10. The method of claim 1, 5 or 6, wherein the yellow powder is dried under vacuum or under oxygen-free atmosphere.
CN201810151846.3A 2018-02-14 2018-02-14 Method for producing polysilane/siloxene and ferrosilicon by reacting carbide slag iron with acid Active CN108342637B (en)

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