CN116425121A - Sodium sulfide production method - Google Patents
Sodium sulfide production method Download PDFInfo
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- CN116425121A CN116425121A CN202310579292.8A CN202310579292A CN116425121A CN 116425121 A CN116425121 A CN 116425121A CN 202310579292 A CN202310579292 A CN 202310579292A CN 116425121 A CN116425121 A CN 116425121A
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- sodium sulfate
- sodium sulfide
- mixed gas
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- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052979 sodium sulfide Inorganic materials 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 230000019086 sulfide ion homeostasis Effects 0.000 title abstract description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 119
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 119
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 118
- 239000007789 gas Substances 0.000 claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000001257 hydrogen Substances 0.000 claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 239000000725 suspension Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 239000011261 inert gas Substances 0.000 claims abstract description 33
- 230000009467 reduction Effects 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000007599 discharging Methods 0.000 claims abstract description 12
- 238000004321 preservation Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- 238000006722 reduction reaction Methods 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 19
- 238000005192 partition Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000008247 solid mixture Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 5
- 238000009423 ventilation Methods 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 235000010265 sodium sulphite Nutrition 0.000 description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 description 7
- 238000005273 aeration Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/24—Preparation by reduction
- C01B17/26—Preparation by reduction with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/24—Preparation by reduction
- C01B17/28—Preparation by reduction with reducing gases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application relates to the technical field of sodium sulfide production, and particularly discloses a sodium sulfide production method, which comprises the following steps: s1, under the condition of continuously introducing inert gas, heating sodium sulfate to 890-900 ℃ to enable the sodium sulfate to be completely melted to form liquid, then continuously introducing carbon suspension gas-solid mixed gas to react under the condition of continuously heating, and simultaneously heating to 980-990 ℃; s2, continuously introducing a reduction mixed gas under heat preservation for reaction, continuously introducing air for 30-50min, standing for 10-20min, discharging, and cooling to obtain a sodium sulfide product; the carbon suspension gas-solid mixed gas is a mixture of carbon powder, hydrogen and inert gas; the reduction mixed gas is a mixture of hydrogen and inert gas. The production method has the advantages of high conversion rate, high sodium sulfide purity, low side reaction, low hydrogen consumption and high hydrogen utilization rate, and meets the market demand.
Description
Technical Field
The application relates to the technical field of sodium sulfide production, in particular to a sodium sulfide production method.
Background
Sodium sulfide is an inorganic compound and is also an important chemical raw material, especially in the dye industry, which is a raw material of green sulfide and blue sulfide. The production methods of sodium sulfide in the current market mainly comprise a coal dust reduction method, an absorption method, a barium sulfide method and a gas reduction method. The pulverized coal reduction method is to react pulverized coal and sodium sulfate to form sodium sulfide and carbon dioxide, the purity of the obtained product is about 60%, the product is required to be further purified, and the operation is complicated. The absorption method is to react sodium hydroxide and hydrogen sulfide waste gas to form sodium sulfide and water, and the hydrogen sulfide waste gas is toxic and has limited sources. The barium sulfide method is to react barium sulfide and sodium sulfate to form barium sulfate and sodium sulfide, and the barium sulfate content in the product is obtained and needs further purification. The gas reduction method is to react barium sulfide with reducing gas to form sodium sulfide, wherein the reducing gas is carbon monoxide, hydrogen and methane, and if the reducing gas is carbon monoxide, the sodium sulfide and the carbon monoxide react to form sodium sulfide and carbon dioxide; if the reducing gas is hydrogen, sodium sulfate reacts with the hydrogen to form sodium sulfide and water; if the reducing gas is methane, sodium sulfate reacts with hydrogen to form sodium sulfide, carbon dioxide and water. The sodium sulfide product obtained by the gas reduction method has the advantages of high purity and rich raw material sources, and is widely focused and applied.
In the method for producing sodium sulfide by the gas reduction method of the related art, firstly, sodium sulfate is heated to 1100 ℃ to enable the sodium sulfate to be melted to form liquid, then a large amount of hydrogen is introduced, and the introduced amount of the hydrogen is 1.5-2.5 times of the theoretical value. At this time, a part of the hydrogen gas contacts and reacts with the molten sodium sulfate, and a part of the hydrogen gas is directly exhausted, so that the hydrogen gas is wasted. If the hydrogen gas inflow amount is reduced, although the waste of hydrogen gas can be reduced, the sodium sulfate content in the sodium sulfide product is higher, and the purity of the sodium sulfide product is reduced.
Disclosure of Invention
On the basis of reducing the hydrogen gas inlet amount, in order to improve the purity and quality of sodium sulfide products, the application provides a sodium sulfide production method, which adopts the following technical scheme:
a method for producing sodium sulfide, comprising the following steps:
s1, under the condition of continuously introducing inert gas, heating sodium sulfate to 890-900 ℃ to enable the sodium sulfate to be completely melted to form liquid, then stopping introducing the inert gas, continuously introducing carbon suspension gas-solid mixed gas to react under the condition of continuously heating, continuously heating for 10-30min, and simultaneously heating to 980-990 ℃;
s2, stopping introducing the carbon suspension gas-solid mixed gas, continuously introducing the reduction mixed gas under heat preservation for reaction, wherein the continuous ventilation time is 30-50min, stopping introducing the reduction mixed gas, standing for 10-20min, discharging, cooling to 930-940 ℃, heat preservation for 20-30min, and continuing cooling to obtain a sodium sulfide product;
the carbon suspension gas-solid mixed gas is a mixture of carbon powder, hydrogen and inert gas; the reduction mixed gas is a mixture of hydrogen and inert gas.
According to the sodium sulfide production method, firstly, sodium sulfate is melted, and then carbon suspension gas-solid mixed gas is introduced, wherein the carbon suspension gas-solid mixed gas is a mixture of carbon powder, hydrogen and inert gas. At this time, in the first aspect, carbon powder enters molten sodium sulfate for reaction, and the molar ratio of the sodium sulfate to the carbon powder is 1:2, so that sodium sulfide and carbon dioxide are generated; in the second aspect, hydrogen gas is contacted with molten sodium sulfate and reacts with the molten sodium sulfate, and the molar ratio of the sodium sulfate to the carbon powder is 1:4 to generate sodium sulfide and water vapor; in the third aspect, the inert gas increases raw material disturbance, improves the contact area of hydrogen and molten sodium sulfate, reduces the discharge condition of the unreacted hydrogen, reduces the hydrogen waste and improves the hydrogen utilization rate; in the fourth aspect, because the carbon powder is granular, the complete reaction of the carbon powder needs a certain time, the granular carbon powder not only increases raw material disturbance and increases the utilization rate of hydrogen, but also increases the contact time and contact area of carbon suspension gas-solid mixed gas and molten sodium sulfate, thereby facilitating the reaction of raw materials; in the fourth aspect, the disturbance of carbon dioxide and water vapor generated by the reaction can be increased, so that the hydrogen utilization rate is improved; in the fifth aspect, carbon dioxide, steam and inert gas generated by the reaction are mixed to form tail gas, the inert gas increases the gas quantity, the tail gas is convenient to discharge, the side reaction is reduced, and the purity and quality of sodium sulfide products are improved.
And secondly, stopping introducing the carbon suspension gas-solid mixed gas, and continuing introducing the reduction mixed gas which is a mixture of hydrogen and inert gas. At this time, in the sixth aspect, the hydrogen gas is contacted with the molten sodium sulfate and the reaction is continued, increasing the conversion rate of sodium sulfate; in the seventh aspect, as the molten sodium sulfate contains the carbon powder with residual particles, the carbon powder is not added into the reducing mixed gas, so that the residual carbon powder can react with the molten sodium sulfate, the carbon powder can completely react, carbon powder impurities can not be introduced into the sodium sulfide product, and the influence of the carbon powder on the purity of the sodium sulfide product is reduced; in the eighth aspect, the inert gas in the mixed gas is reduced, so that raw material disturbance can be increased, the hydrogen utilization rate is improved, and side reactions are reduced.
Meanwhile, compared with the prior art that the reaction is carried out at the temperature of 1100 ℃, in the production method of the application, sodium sulfate is heated to 890-900 ℃, and then after carbon suspension gas-solid mixed gas is introduced, the temperature is synchronously raised, and the temperature is raised to 980-990 ℃. The reaction temperature is reduced while the raw material reaction is maintained, the cost is saved, and the side reaction of sodium sulfate caused by pyrolysis is reduced. Meanwhile, the temperature is not directly raised to 980-990 ℃, but is raised while carbon suspension gas-solid mixed gas is introduced, so that the time of sodium sulfate at 890-990 ℃ is reduced, the condition of side reaction is also reduced, and the purity and quality of sodium sulfide products are improved.
According to the sodium sulfide production method, from multiple aspects, the hydrogen utilization rate is improved while the hydrogen inflow is reduced, the sodium sulfide product has excellent comprehensive performance, the sodium sulfide content is more than 98%, the sodium sulfate content is less than 0.15%, the sodium sulfite content is less than 0.25%, and the sodium thiosulfate content is less than 0.35%, so that the production method has the advantages of high conversion rate, high sodium sulfide purity, low side reaction, low hydrogen consumption and high hydrogen utilization rate, and the market demand is met.
Optionally, in the carbon suspension gas-solid mixed gas, the molar ratio of sodium sulfate to carbon powder to hydrogen to inert gas is 3 (1.9-2.1): 3.8-4.2): 1.9-2.1;
in the reduction mixed gas, the molar ratio of sodium sulfate to hydrogen to inert gas is 3 (4.1-4.3) (8.2-8.6).
By adopting the technical scheme, the addition amount of carbon powder and hydrogen in the carbon suspension gas-solid mixed gas is optimized by taking sodium sulfate as a reference, so that the reaction of the carbon powder, the hydrogen and the molten sodium sulfate is facilitated. Meanwhile, the addition amount of inert gas in the carbon suspension gas-solid mixed gas is optimized, so that carbon powder is suspended in the carbon suspension gas-solid mixed gas, raw material disturbance is increased, the hydrogen utilization rate is improved, meanwhile, exhaust generated by the reaction is conveniently discharged, side reaction is reduced, and the purity of sodium sulfide products is increased.
And the addition amount of hydrogen in the reduction mixed gas is optimized by taking sodium sulfate as a reference, so that the hydrogen reacts with molten sodium sulfate, the addition amount of the hydrogen is excessive compared with a theoretical value, the conversion rate of sodium sulfate is increased, and the purity of sodium sulfide products is improved. And the addition amount of inert gas in the reducing mixed gas is optimized, so that side reaction is reduced.
Optionally, the ash content of the carbon powder is less than or equal to 1wt percent, and the average granularity is 30-60 mu m.
By adopting the technical scheme, the ash content of the carbon powder is limited, and the influence of impurities in the carbon powder on the quality of sodium sulfide products is reduced. And the granularity of the carbon powder is limited, so that the carbon powder is suspended in the carbon suspension gas-solid mixed gas, and the regulation and control of the carbon suspension gas-solid mixed gas are facilitated.
Optionally, the content of the sodium sulfate is more than or equal to 95%, and/or the inert gas is nitrogen.
By adopting the technical scheme, the content of sodium sulfate is limited, and the influence of impurities in sodium sulfate on the quality of sodium sulfide products is reduced. In addition, the inert gas is nitrogen, so that the source is rich and easy to obtain.
Optionally, the carbon suspension gas-solid mixture is preheated before use, and the preheating temperature is 440-460 ℃.
Optionally, the reducing mixture is preheated before use, and the preheating temperature is 440-460 ℃.
The applicant finds that when the normal-temperature carbon suspension gas-solid mixture or the normal-temperature reduction gas mixture is contacted with molten sodium sulfate, a great amount of heat exchange can occur, the temperature of the sodium sulfate is reduced, and part of molten sodium sulfate is solidified to form solid particles, at the moment, the mixing and reaction of raw materials are affected, and the content of sodium sulfide in a sodium sulfide product is reduced. On the basis, the carbon suspension gas-solid mixed gas and the reduction mixed gas are preheated, so that the heat exchange energy between the carbon suspension gas-solid mixed gas and the molten sodium sulfate is reduced, the mixing and the reaction of raw materials are facilitated, and the influence of the heat exchange on the quality of sodium sulfide products is reduced. Furthermore, the preheating temperature is optimized, so that the influence on the quality of sodium sulfide products caused by too low preheating temperature is reduced, and the potential safety hazard of preheating caused by too high preheating temperature is also reduced. In the application, the preheating temperature is selected in the range of 440-460 ℃, and the expected effect can be achieved.
Optionally, the sodium sulfate is subjected to the following pretreatment prior to use: heating sodium sulfate to 30-40 ℃, carrying out heat preservation treatment for 20-30min, then heating to 110-120 ℃, and carrying out heat preservation treatment for 40-60min to obtain pretreated sodium sulfate.
By adopting the technical scheme, the sodium sulfate has certain moisture absorption and has crystal water. At this time, the sodium sulfate is pretreated, so that the crystallization water in the sodium sulfate is effectively removed, and the sodium sulfate is heated more uniformly when being melted.
Optionally, in the production method, the tail gas generated by the reduction reaction of sodium sulfate is subjected to heat exchange and then is introduced into alkali liquor for tail gas treatment.
The tail gas generated by the reduction reaction of sodium sulfate contains more heat, and at the moment, after the tail gas is subjected to heat exchange, the recovery of the heat of the tail gas is realized, and the waste of resources is reduced. Meanwhile, the acid components in the tail gas are absorbed by the alkali liquor, so that the pollution of the tail gas to the environment is reduced.
Further, the tail gas generated by the reduction reaction of sodium sulfate is cooled to 310-330 ℃ after primary heat exchange, then cooled to 110-130 ℃ after secondary heat exchange, then cooled to 40-60 ℃ after tertiary heat exchange, and then is introduced into alkali liquor. The tail gas is cooled step by step, so that the heat is conveniently recovered.
Optionally, in the production method, the reduction reaction of sodium sulfate is performed in a converting furnace, the converting furnace comprises a hollow furnace body, a partition plate is arranged in the furnace body along the vertical direction, a material passing gap is formed between the bottom end of the partition plate and the bottom wall of the furnace body, the furnace body is divided into a first reaction cavity and a second reaction cavity, a feeding pipe for feeding sodium sulfate, a first air inlet spray gun for feeding carbon suspension gas-solid mixed gas and a second air inlet spray gun for feeding inert gas or reducing mixed gas are arranged at the first reaction cavity of the furnace body, and an exhaust pipe is arranged at the second reaction cavity of the furnace body.
By adopting the technical scheme, sodium sulfate is added through the feed pipe, carbon suspension gas-solid mixed gas is introduced through the first air inlet spray gun, and inert gas or reduction mixed gas is introduced through the second air inlet spray gun. And the first reaction cavity and the second reaction cavity form a U-shaped channel under the action of the partition plate, at the moment, carbon dioxide, water vapor and inert gas generated by the reaction are mixed and form tail gas, the tail gas is discharged through the U-shaped channel, the disturbance of raw materials is improved, the contact time and the contact area of carbon suspension gas-solid mixed gas, reduction mixed gas and molten sodium sulfate are increased, and the hydrogen utilization rate is further improved.
Optionally, the outer wall of furnace body is provided with refractory lining and heating member, the bottom of furnace body is provided with the discharging pipe that is used for the ejection of compact.
Through adopting above-mentioned technical scheme, the refractory lining can keep warm the furnace body, and the heating body can be to furnace body heating, and the ejection of compact of sodium sulfide product is convenient for to the discharging pipe. The control of the converting furnace is facilitated through the arrangement of the refractory lining, the heating body and the discharging pipe.
In summary, the present application has at least the following beneficial effects: the sodium sulfide production method comprises the steps of heating sodium sulfate to 890-900 ℃, then heating to 980-990 ℃, and introducing carbon suspension gas-solid mixed gas which is a mixture of carbon powder, hydrogen and inert gas. And then introducing a reduction mixed gas which is a mixture of hydrogen and inert gas. By means of mutual matching of carbon powder, hydrogen, inert gas and temperature, the method has the advantages of reducing the hydrogen consumption, improving the hydrogen utilization rate, ensuring that the sodium sulfide content of sodium sulfide products is more than 98%, the sodium sulfate content is less than 0.15%, the sodium sulfite content is less than 0.25% and the sodium thiosulfate content is less than 0.35% on the basis of keeping the higher conversion rate of sodium sulfate in multiple aspects, ensuring that the sodium sulfide yield has excellent quality, and also ensuring that the production method has the advantages of high conversion rate, high sodium sulfide purity, low side reaction, low hydrogen consumption and high hydrogen utilization rate, and meeting market demands.
Drawings
Fig. 1 is a schematic view of a converting furnace of the present application.
In the figure, 1, a furnace body; 11. a refractory lining; 12. a heating body; 2. a discharge pipe; 3. a partition plate; 4. a feed pipe; 5. a first air intake lance; 6. a second air intake lance; 7. and an exhaust pipe.
Detailed Description
In order that the present application may be more readily understood, the following examples are presented in conjunction with the following detailed description, which are intended to be illustrative only and are not intended to limit the scope of application of the present application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Examples
Example 1
A method for producing sodium sulfide, comprising the following steps:
s0, heating the sodium sulfate to 35 ℃, and preserving the temperature for 25min. Then heating to 115 ℃, and preserving heat for 50min to obtain pretreated sodium sulfate.
Wherein, the content of sodium sulfate is 99 percent.
S1, introducing nitrogen into the converting furnace, replacing air in the converting furnace with the nitrogen, and forming nitrogen protection. Then 90kg of sodium sulfate is added, and the sodium sulfate is heated to 895 ℃ under the condition of continuously introducing nitrogen gas which is preheated to 450 ℃ so as to lead the sodium sulfate to be completely melted to form liquid. And stopping introducing nitrogen, continuously introducing carbon suspension gas-solid mixed gas preheated to 450 ℃ under the condition of continuously heating to react, continuously introducing the carbon suspension gas-solid mixed gas for 20min, and heating to 985 ℃.
The carbon suspension gas-solid mixture is a mixture of carbon powder, hydrogen and nitrogen, and the molar ratio of the sodium sulfate to the carbon powder to the hydrogen to the nitrogen is 3:2:4:2. The ash content of the carbon powder was 0.05wt% and the average particle size was 50. Mu.m. After the carbon suspension gas-solid mixed gas is introduced, carbon powder enters molten sodium sulfate for reaction to generate sodium sulfide and carbon dioxide, hydrogen contacts with the molten sodium sulfate for reaction to generate sodium sulfide and water vapor, and carbon dioxide, water vapor and nitrogen generated by the reaction are mixed to form tail gas and are discharged.
S2, stopping introducing the carbon suspension gas-solid mixed gas, and continuously introducing the reduction mixed gas preheated to 450 ℃ at the temperature of 985 ℃ for reaction, wherein the continuous aeration time is 40min. And stopping introducing the reduction mixed gas, and standing for 15min. And then discharging, pouring into a mould, cooling to 935 ℃, carrying out heat preservation treatment for 25min, and continuously cooling to 25 ℃ to obtain a sodium sulfide product.
The reducing mixture is a mixture of hydrogen and nitrogen, and the molar ratio of sodium sulfate to hydrogen to nitrogen is 3:4.2:8. After the reduction mixed gas is introduced, the hydrogen gas and the molten sodium sulfate are contacted and react, the water vapor and the nitrogen generated by the reaction are mixed to form tail gas, and the tail gas is discharged.
In the whole process of the sodium sulfate reduction reaction, the generated tail gas is cooled to 320 ℃ after passing through a primary heat exchanger, cooled to 120 ℃ after passing through a secondary heat exchanger, cooled to 50 ℃ after passing through a tertiary heat exchanger, and then introduced into alkali liquor for tail gas treatment.
In step S1, referring to fig. 1, the converting furnace includes a hollow furnace body 1, sodium sulfate is melted into a liquid in the furnace body 1, and a further reduction reaction is performed to obtain a sodium sulfide product. The outer wall of the furnace body 1 is fixedly provided with a refractory lining 11 and a heating body 12, the refractory lining 11 is used for preserving heat of the furnace body 1, and the heating body 12 is used for heating the furnace body 1. The bottom of the furnace body 1 is fixedly provided with a discharging pipe 2 communicated with the inside of the furnace body, and the discharging pipe 2 is provided with a valve so as to control the discharge of sodium sulfide products.
Referring to fig. 1, a partition plate 3 is arranged in a furnace body 1 along a vertical direction, the top end of the partition plate 3 is fixedly connected with the top wall of the furnace body 1, the side end of the partition plate 3 is fixedly connected with the side wall of the furnace body 1, a material passing gap is formed between the bottom end of the partition plate 3 and the bottom wall of the furnace body 1, and the bottom end of the partition plate 3 extends into the top of molten sodium sulfate. At this time, the partition plate 3 divides the furnace body 1 into two chambers, namely a first reaction chamber and a second reaction chamber, and forms a U-shaped channel. The top wall of the furnace body 1 is fixedly provided with a feed pipe 4, a first air inlet spray gun 5 and a second air inlet spray gun 6 at the first reaction cavity, the feed pipe 4 is used for introducing sodium sulfate, so that the sodium sulfate enters the furnace body 1, the first air inlet spray gun 5 is used for introducing carbon suspension gas-solid mixed gas, and the second air inlet spray gun 6 is used for introducing nitrogen or reduction mixed gas. An exhaust pipe 7 is fixedly arranged on the top wall of the furnace body 1 at the second reaction cavity, and the exhaust pipe 7 is used for discharging tail gas. Valves are respectively arranged on the feed pipe 4, the first air inlet spray gun 5, the second air inlet spray gun 6 and the exhaust pipe 7 so as to control the flow of sodium sulfate, carbon suspension gas-solid mixed gas, nitrogen, reduction mixed gas and tail gas.
Example 2
A method for producing sodium sulfide, which is different from example 1 in that in step S1, the duration of aeration is 10min; in step S2, the duration of aeration is 50min.
Example 3
A method for producing sodium sulfide, which is different from example 1 in that in step S1, the duration of aeration is 30min; in step S2, the duration of ventilation was 30min.
Comparative example
Comparative example 1
The production method of sodium sulfide is different from the embodiment 1 in that in the step S1, hydrogen is used for replacing carbon suspension gas-solid mixed gas, and the molar ratio of sodium sulfate to hydrogen is 3:8; in the step S2, the reducing mixture is replaced by hydrogen, and the molar ratio of sodium sulfate to hydrogen is 3:4.2.
Comparative example 2
The difference between the production method of sodium sulfide and the embodiment 1 is that in the step S1, the carbon suspension gas-solid mixture is a mixture of carbon powder and hydrogen, and the molar ratio of sodium sulfate to carbon powder to hydrogen is 3:2:4; in the step S2, the reducing mixture is replaced by hydrogen, and the molar ratio of sodium sulfate to hydrogen is 3:4.2.
Comparative example 3
A process for the production of sodium sulphide differs from example 1 in that step S1 is different.
The step S1 specifically comprises the following steps: and (3) introducing nitrogen into the converting furnace, replacing air in the converting furnace with the nitrogen, and forming nitrogen protection. Then 90kg of sodium sulfate and carbon powder are added, and under the condition of continuously introducing nitrogen gas preheated to 450 ℃, the sodium sulfate is heated to 895 ℃ to ensure that the sodium sulfate is completely melted to form liquid. And stopping introducing nitrogen, continuously introducing carbon suspension gas-solid mixed gas preheated to 450 ℃ under the condition of continuously heating to react, continuously introducing the carbon suspension gas-solid mixed gas for 20min, and heating to 985 ℃.
Wherein, the molar ratio of the sodium sulfate to the carbon powder is 3:2; the carbon suspension gas-solid mixture is a mixture of hydrogen and nitrogen, and the molar ratio of sodium sulfate to hydrogen to nitrogen is 3:4:2.
Comparative example 4
A process for the production of sodium sulphide differs from example 1 in that step S1 is different.
The step S1 specifically comprises the following steps: and (3) introducing nitrogen into the converting furnace, replacing air in the converting furnace with the nitrogen, and forming nitrogen protection. Then 90kg of sodium sulfate is added, and the sodium sulfate is heated to 985 ℃ under the condition of continuously introducing nitrogen gas which is preheated to 450 ℃ so as to enable the sodium sulfate to be completely melted to form liquid. And stopping introducing nitrogen, and continuously introducing carbon suspension gas-solid mixed gas preheated to 450 ℃ for reaction, wherein the continuous aeration time is 20min.
Comparative example 5
A process for the production of sodium sulphide differs from example 1 in that step S1 is different.
The step S1 specifically comprises the following steps: and (3) introducing nitrogen into the converting furnace, replacing air in the converting furnace with the nitrogen, and forming nitrogen protection. Then 90kg of sodium sulfate is added, and the sodium sulfate is heated to 895 ℃ under the condition of continuously introducing nitrogen gas which is preheated to 450 ℃ so as to lead the sodium sulfate to be completely melted to form liquid. And stopping introducing nitrogen, continuously introducing carbon suspension gas-solid mixed gas preheated to 450 ℃ under the condition of continuously heating to react, continuously introducing the carbon suspension gas-solid mixed gas for 20min, and heating to 1105 ℃.
Performance test
The sodium sulfide products obtained in examples 1 to 3 and comparative examples 1 to 5 were each taken as a sample, and the following performance tests were carried out on the samples, and the test results are shown in Table 1.
Wherein, the higher the sodium sulfide content, the higher the purity of the sodium sulfide product; the lower the sodium sulfate content, the higher the sodium sulfate conversion; the higher the content of sodium sulfite and sodium thiosulfate, the more side reactions are indicated.
TABLE 1 detection results
As can be seen from Table 1, the sodium sulfide product obtained by the sodium sulfide production method has the sodium sulfide content of 98.12-99.13%, the sodium sulfate content of 0.05-0.12%, the sodium sulfite content of 0.18-0.23%, the sodium thiosulfate content of 0.19-032% and the water insoluble matter content of 0.09-0.11%, so that the sodium sulfide product shows better quality and meets the market demand.
Example 1 and comparative examples 1-2 were compared and are based on comparative example 1. Comparative example 2 compared with comparative example 1, carbon powder was used to replace part of the hydrogen in the carbon suspension gas-solid mixture during the entire sodium sulfate reduction reaction. From this, it can be seen that although the sodium sulfite and sodium thiosulfate contents are increased, the sodium sulfate content is significantly reduced, and the sodium sulfide content is improved, probably due to the addition of carbon powder, the contact time and contact area of the carbon suspension gas-solid mixture and molten sodium sulfate are increased, and the sodium sulfate conversion rate and the hydrogen utilization rate are improved. In example 1, compared with comparative example 1, in the whole process of the sodium sulfate reduction reaction, carbon powder was used to replace part of hydrogen in the carbon suspension gas-solid mixture, nitrogen was added, and in the reduction mixture, nitrogen was also added. From this, it can be seen that the contents of sodium sulfate, sodium sulfite and sodium thiosulfate are significantly reduced, which may be due to the fact that the addition of carbon powder and nitrogen further increases the contact time and contact area of the carbon suspension gas-solid mixed gas, the reduction mixed gas and the molten sodium sulfate, improves the hydrogen utilization rate, accelerates the exhaust of tail gas, reduces side reactions, improves the purity of sodium sulfide products, and makes the sodium sulfide products exhibit better quality.
Comparing example 1 with comparative example 3, in the production method of comparative example 3, carbon powder is added into sodium sulfate in advance, then carbon suspension gas-solid mixture is introduced, carbon powder is not added into the carbon suspension gas-solid mixture, and the content of water insoluble matters is higher, which is probably due to the fact that the carbon powder and the sodium sulfate are agglomerated in the heating process, the contact area is reduced, and the reaction is affected. In the production method of the embodiment 1, carbon powder is added into carbon suspension gas-solid mixed gas, and can be fully contacted and dispersed with molten sodium sulfate, so that the uniformity of raw material mixing is improved, the sodium sulfate conversion rate is improved, and the water insoluble content is reduced.
Example 1 was compared with comparative example 4 and comparative example 5. In the production method of comparative example 4, sodium sulfate was heated to 985 ℃. In the production method of comparative example 5, sodium sulfate was first heated to 895℃and then to 1105 ℃. The production process of example 1 was followed by heating sodium sulfate to 895 ℃ and then 985 ℃. Therefore, the adoption of one-step heating and overhigh heating can increase the occurrence of side reaction, and the adoption of the two-step heating mode can obviously reduce the content of sodium sulfite and sodium thiosulfate, namely reduce the side reaction, improve the purity of sodium sulfide products and meet the market demand.
It should be noted that the above-described embodiments are only for explaining the present application, and do not constitute any limitation to the present application. The present application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the present application as defined within the scope of the claims of the present application, and the invention may be modified without departing from the scope and spirit of the present application. Although the present application is described herein with reference to particular methods, materials and embodiments, the present application is not intended to be limited to the particular examples disclosed herein, but rather, the present application is intended to extend to all other methods and applications having the same functionality.
Claims (10)
1. A method for producing sodium sulfide, which is characterized in that: the method comprises the following steps:
s1, under the condition of continuously introducing inert gas, heating sodium sulfate to 890-900 ℃ to enable the sodium sulfate to be completely melted to form liquid, then stopping introducing the inert gas, continuously introducing carbon suspension gas-solid mixed gas to react under the condition of continuously heating, continuously heating for 10-30min, and simultaneously heating to 980-990 ℃;
s2, stopping introducing the carbon suspension gas-solid mixed gas, continuously introducing the reduction mixed gas under heat preservation for reaction, wherein the continuous ventilation time is 30-50min, stopping introducing the reduction mixed gas, standing for 10-20min, discharging, cooling to 930-940 ℃, heat preservation for 20-30min, and continuing cooling to obtain a sodium sulfide product;
the carbon suspension gas-solid mixed gas is a mixture of carbon powder, hydrogen and inert gas; the reduction mixed gas is a mixture of hydrogen and inert gas.
2. A method for producing sodium sulfide according to claim 1, wherein: in the carbon suspension gas-solid mixed gas, the molar ratio of sodium sulfate to carbon powder to hydrogen to inert gas is 3 (1.9-2.1) (3.8-4.2) (1.9-2.1);
in the reduction mixed gas, the molar ratio of sodium sulfate to hydrogen to inert gas is 3 (4.1-4.3) (8.2-8.6).
3. A method for producing sodium sulfide according to claim 1, wherein: the ash content of the carbon powder is less than or equal to 1 weight percent, and the average granularity is 30-60 mu m.
4. A method for producing sodium sulfide according to claim 1, wherein: the content of the sodium sulfate is more than or equal to 95 percent, and/or the inert gas is nitrogen.
5. A method for producing sodium sulfide according to claim 1, wherein: the carbon suspension gas-solid mixture is preheated before use, and the preheating temperature is 440-460 ℃.
6. The method for producing sodium sulfide according to claim 5, wherein: the reducing mixture is preheated before use, and the preheating temperature is 440-460 ℃.
7. A method for producing sodium sulfide according to claim 1, wherein: the sodium sulfate was subjected to the following pretreatment prior to use: heating sodium sulfate to 30-40 ℃, carrying out heat preservation treatment for 20-30min, then heating to 110-120 ℃, and carrying out heat preservation treatment for 40-60min to obtain pretreated sodium sulfate.
8. A method for producing sodium sulfide according to claim 1, wherein: in the production method, the tail gas generated by the reduction reaction of sodium sulfate is subjected to heat exchange and then is introduced into alkali liquor for tail gas treatment.
9. A method for producing sodium sulfide according to claim 1, wherein: in the production method, the reduction reaction of sodium sulfate is carried out in a converting furnace, the converting furnace comprises a hollow furnace body (1), a partition plate (3) is arranged in the furnace body (1) along the vertical direction, the bottom end of the partition plate (3) and the bottom wall of the furnace body (1) form a passing gap, the furnace body (1) is divided into a first reaction cavity and a second reaction cavity, the furnace body (1) is provided with a feeding pipe (4) for introducing sodium sulfate, a first air inlet spray gun (5) for introducing carbon suspension gas-solid mixed gas and a second air inlet spray gun (6) for introducing inert gas or reducing mixed gas at the first reaction cavity, and the furnace body (1) is provided with an exhaust pipe (7) at the second reaction cavity.
10. A method for producing sodium sulfide according to claim 9, wherein: the outer wall of the furnace body (1) is provided with a fireproof lining (11) and a heating body (12), and the bottom of the furnace body (1) is provided with a discharging pipe (2) for discharging.
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