CN1244493A - Production technology of yellow flaky sodium sulfide with low carbon and iron contents - Google Patents
Production technology of yellow flaky sodium sulfide with low carbon and iron contents Download PDFInfo
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- CN1244493A CN1244493A CN 99119362 CN99119362A CN1244493A CN 1244493 A CN1244493 A CN 1244493A CN 99119362 CN99119362 CN 99119362 CN 99119362 A CN99119362 A CN 99119362A CN 1244493 A CN1244493 A CN 1244493A
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Abstract
Raw materials of saltpeter and anthracite are mixed in the ratio of 3 to 1 and high-temperature calcined to produce stock sodium sulfide which is hot dissolved to obtain sodium sulfide solution as intermediate. Compounded barium sulfide and zinc sulfate solution is added to the intermediate to eliminate impurities, the precipitated and clarified sodium sulfide solution is evaporated for concentration, and the concentrate is tabletted and packaged as product. The said technological process has obvious iron eliminating effect, and through the application of special steel smelting technology, the ultimate product has an iron content not more than 80 ppm.
Description
The invention belongs to the field of chemical industry, and particularly relates to a production process of low-carbon low-iron yellow flaky sodium sulfide.
The molecular formula of the sodium sulfide is as follows: na (Na)2S·nH2O, molecular weight 78.06 (as Na)2S) and is known as sodium sulfide, which is highly corrosive and is mainly used in industries such as sulfur dyes, paper making, leather, ore flotation, metallurgy, organic synthesis, and the like. With the development of the times, the international quality requirements on daily-use and chemical products, particularly on the bleaching and coloring of copper plate paper, high-grade newsprint, wool and cashmere, and the like are higher and higher. Red sodium sulfide with very high iron content (greater than 400PPM) has not been satisfactory and is gradually replaced by yellow (or orange) sodium sulfide with low carbon and low iron (less than 80 PPM). At present, the production process for producing low-carbon and low-iron yellow sodium sulfide in China comprises the following steps: the process comprises the steps of raw material → calcination → hot melting → mud clarification → chemical impurity removal → precipitation → evaporation concentration → tablet production and packaging, and the existing chemical impurity removal process, such as manganese dioxide deironing (more than 3000 yuan per ton of manganese dioxide) used in Tianshan chemical plant in Xinjiang, has high cost, and the iron content of the finished product after deironing is still high and reaches 150PPM; the evaporation and concentration process usually adopts a tubular evaporator for evaporation, and the material is made of pure nickel tubes. Practice shows that iron ions in the sodium sulfide semi-finished product solution cannot be effectively removed due to technological defects, and the quality of a final product is directly influenced.
The invention aims to provide a production process of low-carbon low-iron yellow flaky sodium sulfide, which has an obvious iron removal effect, can effectively control the iron ion content in a specified range in each procedure after iron removal, and ensures that the iron content of a final product does not exceed 80 PPM.
According to the above object requirements: sodium carbonate (Na) in the semi-finished product must be removed2CO3) The content is reduced to below 1%, and the iron ions (Fe)3+) The content is reduced to below 30PPM, and the final product can be qualified. And according to Wherein:the high content of sodium carbonate is not beneficial to evaporation concentration and is also removed; because the zinc sulfide has the performance of adsorbing the ferric hydroxide in the sodium sulfide semi-finished product solution, the colloidal zinc sulfide has negative charges, and adsorbs the ferric hydroxide colloid with positive charges, so that the ferric hydroxide colloid is precipitated at the bottom of the solution, and the content of iron ions in the sodium sulfide solution is reduced. The production process of the low-carbon low-iron yellow flaky sodium sulfide adopted by the invention comprises the following steps: mixing the raw materials, namely sodium nitrate (Na)2SO4Mixing weathered saltpeter with content greater than 85% with anthracite (carbon content greater than 65%) at 3: 1 ratio, calcining at high temperature (850-1250 deg.C) to obtain sodium sulfide alkali blank, hot dissolving, washing the alkali blank with water to obtain solution with sodium sulfide content greater than 280 g/L, clarifying to obtain sodium sulfide semi-finished product solution, and removing impurities, wherein the removing impurities comprises ① adding 150 kg of barium sulfide (BaS content is 60%) into each cubic of water, dissolving barium sulfide (BaS) to 12-16 Be' (Boume degree), cooling at 80 deg.C, precipitating for 40-60 min, and collecting clear solution for use2S) adding the semi-finished solution0.058-0.078 cubic barium sulfide solution, ② preparing zinc sulfate solution per cubic sodium sulfide (Na)2S) semi-finished product solution is added with zinc sulfate (ZnSO)498 percent of zinc sulfate and 3-20 kg of zinc sulfate (ZnSO)4) ③ adding above two solutions into the semi-finished sodium sulfide solution, stirring at 80 r/min for 20-40 min, controlling the reaction temperature at 80 deg.C, precipitating for 12-16 hr, removing impurities, clarifying to obtain sodium sulfide solution with iron ion content of 3-30PPM, evaporating, concentrating, tabletting, and packaging to obtain final product with sodium sulfide content of 60% and iron content not more than 80 PPM.
In order to ensure that the iron content of the final product is controlled within a required range, all containers, pipelines, valves and water pumps which are in contact with the alkali liquor are made of 316L steel (namely 00Cr17Ni14Mo2) or lined before evaporation and concentration of the sodium sulfide solution after impurity removal, so that the iron ion content is not increased by more than 2PPM in the process; in the process from the evaporation concentration process to the flaking and packaging process, all the containers, evaporators, pipelines, flaking machines and other equipment which are in contact with the alkali liquor and the finished products are made of special steel 000Cr30Mo2, so as to ensure that the iron content is increased by only 1.2-2 times of the original iron content in the process. In the evaporation and concentration process, a free falling film plate evaporator (a patent product of Lanzhou environmental protection and energy saving equipment company) made of special steel 000Cr30Mo2 is particularly selected.
The invention is further illustrated by the following examples:
taking the production of 5 tons of low-carbon low-iron yellow flaky sodium sulfide first-grade products as an example:
(the production of sodium sulfide per ton of finished product needs to consume 2.4 tons/ton of raw material nitre, 0.8 tons/ton of raw material coal and 2.4 meters of sodium sulfide semi-finished product solution3Per ton. )
Mixing 12 tons of sodium nitrate (Na)2SO4Weathered saltpeter with content morethan 85 percent) and 4 tons of anthracite (carbon content more than 65 percent) are evenly mixed according to the proportion of 3: 1, then the mixture is added into a rotary kiln for high-temperature (850-The program is as follows:
①
②
③
hot dissolving, namely washing the alkali blank into a sodium sulfide solution by using water, and clarifying to obtain a semi-finished product solution with the sodium sulfide content of more than 280 g/L;
mixing 12m3The sodium sulfide semi-finished product solution is sent to a storage tank in the impurity removal process, and the following steps are firstly carried out:
(1) preparing barium sulfide (BaS) solution in 1#In the preparation tank, 150 kg of barium sulfide (BaS content is 60%) is added into each cubic of water, the water temperature is more than or equal to 80 ℃, the barium sulfide is dissolved to Be 12-16 Be' (plum degree), after the barium sulfide is dissolved, the stirring is stopped, the barium sulfide is precipitated for 40-60 minutes, and clear liquid is taken for later use. In the production practice, 0.058m is required to be added into each cubic of sodium sulfide semi-finished product solution3Barium sulfide solution, 12m3Adding 0.7m barium sulfide solution into the sodium sulfide semi-finished product solution3。
(2) Preparing zinc sulfate (ZnSO)4) The solution is in 2#In the preparation tank, 72-102kg of zinc sulfate (ZnSO)4Content 98%) was added 1m3Water (6-8.5 kg per cubic sodium sulfide semi-finished product solution, 12 m)372-102kg of sodium sulfide semi-finished product solution is added, the water temperature is more than or equal to 80 ℃, stirring is started for about 30 minutes, and the prepared zinc sulfate solution is obtained.
(3) Slowly adding the prepared two solutions into the sodium sulfide semi-finished product solution in the reactor at the same time, stirring for 20-30 minutes at a stirring speed of 80 revolutions per minute, and reacting at a temperature higher than 80 ℃, wherein:
removing sodium carbonate (Na)2CO3)：
According to the examination, the sodium sulfide semi-finished product solution contains various impurities: na (Na)2CO3、Fe2+、Na2SO4、Na2S2O3Etc. except Fe3+Outer, Na2CO3The high content is not favorable for evaporation concentration and should be removed.
Removing iron ions (Fe)2+)： Wherein: because the zinc sulfide has the performance of adsorbing the ferric hydroxide in the sodium sulfide semi-finished product solution, the colloidal zinc sulfide has negative charges, and adsorbs the ferric hydroxide colloid with positive charges, so that the ferric hydroxide colloid is precipitated at the bottom of the solution, and the content of iron ions in the sodium sulfide solution is reduced.
After the impurity removal process, precipitating in a precipitation tank for 12-16 hours, ensuring that the iron ion content in the solution is 8-12PPM, then sending to an evaporation concentration process, evaporating and concentrating by a free falling film plate evaporator (a product of Lanzhou environmental protection and energy saving equipment company) made of special steel 000Cr30Mo2, tabletting and packaging to obtain a superior product with the sodium sulfide content of 60% and the iron content of no more than 30 PPM.
The production process of the low-carbon low-iron yellow flaky sodium sulfide provided by the invention has the advantages of reasonable design, advanced technology and obvious iron removal effect, and organically combines special steel with relevant equipment in each step after iron removal, especially with a free falling film plate evaporator in an evaporation concentration process, so that the iron ion content in a sodium sulfide semi-finished product solution is effectively controlled within a specified range, and the iron content of the low-carbon low-iron yellow flaky sodium sulfide of a final product is ensured to be not more than 80 PPM. The high-quality product with the first national yield (3 ten thousand tons per year) and the quality meeting the international standard is produced, and the high-quality product is at the leading level in the same industry all over the country. Compared with the existing pure nickel tube evaporator, the free falling film plate evaporator especially made of special steel (000Cr30Mo2) in the process has the following advantages: (evaporation area is the same 300 m)2)
Attached: enterprise standard for low-carbon and low-iron yellow flaky sodium sulfide products
| Item | Plate evaporator (000Cr30Mo2) | Tube evaporator (Ni)6) |
| 1. Steam pressure Mpa | 0-0.45 | 0-0.7 |
| 2. Installed capacity KW | 16.5 | 30 |
| 3. Daily output (ton) | 90-120 | 30-45 |
| 4. Maintenance | Is easy to use | Difficulty in |
| 5. Weldability after alkali bonding | Good effect | Difference (D) |
| 6. Material ton price (Wanyuan) | 11 (sheet material) | 26 (tube) |
| 7. Iron ion growth factor after evaporation | 1.2-2 times of | 2.5-3 times of |
| Item | Index (I) | |||
| Super-high-grade product | First-grade product | Superior and secondary product | Superior and tertiary product | |
| Sodium sulfide (Na)2S) content ≧ S | 60.0 | 60.0 | 60.0 | 60.0 |
| The content PPM of iron (Fe) is less than or equal to | 15 | 30 | 50 | 80 |
| Sodium sulfite (Na)2SO3) The content is less than or equal to | 1.0 | / | / | / |
| Sodium thiosulfate (Na)2S2O3) The content is less than or equal to | 2.5 | / | / | / |
| Sodium carbonate (Na)2CO3) The content is less than or equal to | 2.0 | 2.5 | 3.0 | 4.0 |
Claims (3)
1. A production process of low-carbon low-iron yellow flaky sodium sulfide is characterized by comprising the following steps: mixing the raw materials, namely sodium nitrate (Na)2SO4Weathered saltpeter with the content of more than 85 percent) and anthracite (the carbon content of more than 65 percent) are mixed according to the proportion of 3: 1 and then calcined at high temperature (850-; hot dissolving, namely washing the alkali blank into a solution with the sodium sulfide content of more than 280 g/L by using water, and clarifying to obtain a sodium sulfide semi-finished product solution; the sodium sulfide semi-finished product solution is sent to remove impurities① preparing barium sulfide solution, adding 150-250kg barium sulfide (BaS content 60%) into each cubic of water, dissolving barium sulfide (BaS) to 12-16 Be' (Baume degree), the water temperature is not less than 80 deg.C, precipitating for 40-60 min, collecting clear solution for use, and collecting sodium sulfide (Na) for each cubic2S) adding barium sulfide solution in 0.058-0.078 cubic volume, ② preparing zinc sulfate solution per cubic volume of sodium sulfide (Na)2S) semi-finished product solution is added with zinc sulfate (ZnSO)460 percent of zinc sulfate, 3-20 kg of zinc sulfate (ZnSO)4) ③ adding above two solutions into the semi-finished sodium sulfide solution, stirring at 80 r/min for 20-40 min, controlling the reaction temperature at 80 deg.C, precipitating for 12-16 hr, removing impurities, clarifying to obtain sodium sulfide solution with iron ion content of 3-30PPM, evaporating, concentrating, tabletting, and packaging to obtain final product with sodium sulfide content of 60% and iron content not more than 80 PPM.
2. The process for producing low-carbon low-iron yellow flake sodium sulfide as claimed in claim 1, wherein the sodium sulfide solution after impurity removal is subjected to evaporation concentration, and all containers, pipelines, valves and water pumps which are in contact with the alkali liquor are made of 316L steel, namely 00Cr17Ni14Mo2 or lined, so as to ensure that the iron ion content is not increased by more than 2PPM in the process; and after the evaporation concentration process, performing a flaking and packaging process, and manufacturing all the containers, evaporators, pipelines, flaker and other equipment which are in contact with the alkali liquor and the finished product by adopting special steel 000Cr30Mo2 so as to ensure that the iron content is increased by only 1.2-2 times of the original iron content in the process.
3. The process for producing low-carbon low-iron yellow flaky sodium sulfide according to claim 1 or 2, wherein in the evaporation concentration step, a free falling film plate evaporator made of a special steel material 000Cr30Mo2 is particularly selected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119362A CN1086361C (en) | 1999-09-13 | 1999-09-13 | Production technology of yellow flaky sodium sulfide with low carbon and iron contents |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119362A CN1086361C (en) | 1999-09-13 | 1999-09-13 | Production technology of yellow flaky sodium sulfide with low carbon and iron contents |
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| CN1244493A true CN1244493A (en) | 2000-02-16 |
| CN1086361C CN1086361C (en) | 2002-06-19 |
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| CN99119362A Expired - Fee Related CN1086361C (en) | 1999-09-13 | 1999-09-13 | Production technology of yellow flaky sodium sulfide with low carbon and iron contents |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267689A (en) * | 2011-07-08 | 2011-12-07 | 甘肃锦世化工有限责任公司 | Production method of sodium sulfide with iron content of less than 30 ppm |
| CN104445090A (en) * | 2013-09-22 | 2015-03-25 | 南风化工集团股份有限公司 | One step method for preparing anhydrous sodium sulfide through reduction of sodium sulfate by using carbon black or ultralow ash pure coal |
| CN105905871A (en) * | 2016-07-01 | 2016-08-31 | 马琴 | Preparation method of anhydrous sodium sulfide |
| CN106185836A (en) * | 2016-07-01 | 2016-12-07 | 马艳玲 | High-pure anhydrous sodium sulfide production method |
| CN106185838A (en) * | 2016-07-01 | 2016-12-07 | 马琴 | Sodium sulfide preparation method |
| CN106185839A (en) * | 2016-07-01 | 2016-12-07 | 深州嘉信化工有限责任公司 | A kind of production method of ultralow ferrum industrial sodium sulfide |
| CN106395758A (en) * | 2016-07-01 | 2017-02-15 | 马艳玲 | A method of producing high-purity sodium sulfide |
| CN106395759A (en) * | 2016-07-01 | 2017-02-15 | 马艳玲 | A method of producing high-purity sodium sulfide |
| CN106430113A (en) * | 2016-10-31 | 2017-02-22 | 重庆市南川区庆岩福利碱厂 | Production process capable of lowering sodium sulfide oxidation degree |
| CN106517101A (en) * | 2016-10-31 | 2017-03-22 | 重庆市南川区庆岩福利碱厂 | Preparation process of sodium sulfide with low content of iron |
| CN109455676A (en) * | 2019-01-21 | 2019-03-12 | 范冲天 | A kind of environmentally friendly refining methd of akali sulphide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1159880A1 (en) * | 1983-01-28 | 1985-06-07 | Kushnir Mikhail M | Method of obtaining sodium sulfide |
| CN1094012A (en) * | 1993-04-17 | 1994-10-26 | 内蒙古国营巴盟农管局化工厂 | The manufacture craft of low iron sodium sulfide |
| RU2090496C1 (en) * | 1995-07-03 | 1997-09-20 | Ткачев Константин Васильевич | Method of sodium sulfide production |
-
1999
- 1999-09-13 CN CN99119362A patent/CN1086361C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267689A (en) * | 2011-07-08 | 2011-12-07 | 甘肃锦世化工有限责任公司 | Production method of sodium sulfide with iron content of less than 30 ppm |
| CN102267689B (en) * | 2011-07-08 | 2012-10-03 | 甘肃锦世化工有限责任公司 | Production method of sodium sulfide with iron content of less than 30 ppm |
| CN104445090A (en) * | 2013-09-22 | 2015-03-25 | 南风化工集团股份有限公司 | One step method for preparing anhydrous sodium sulfide through reduction of sodium sulfate by using carbon black or ultralow ash pure coal |
| CN104445090B (en) * | 2013-09-22 | 2018-02-23 | 南风化工集团股份有限公司 | The method that carbon black or ultra low-ash pure coal reduction sodium sulphate one-step method prepare anhydrous sodium sulfide |
| CN106395759A (en) * | 2016-07-01 | 2017-02-15 | 马艳玲 | A method of producing high-purity sodium sulfide |
| CN106185838A (en) * | 2016-07-01 | 2016-12-07 | 马琴 | Sodium sulfide preparation method |
| CN106185839A (en) * | 2016-07-01 | 2016-12-07 | 深州嘉信化工有限责任公司 | A kind of production method of ultralow ferrum industrial sodium sulfide |
| CN106395758A (en) * | 2016-07-01 | 2017-02-15 | 马艳玲 | A method of producing high-purity sodium sulfide |
| CN106185836A (en) * | 2016-07-01 | 2016-12-07 | 马艳玲 | High-pure anhydrous sodium sulfide production method |
| CN105905871A (en) * | 2016-07-01 | 2016-08-31 | 马琴 | Preparation method of anhydrous sodium sulfide |
| CN106430113A (en) * | 2016-10-31 | 2017-02-22 | 重庆市南川区庆岩福利碱厂 | Production process capable of lowering sodium sulfide oxidation degree |
| CN106517101A (en) * | 2016-10-31 | 2017-03-22 | 重庆市南川区庆岩福利碱厂 | Preparation process of sodium sulfide with low content of iron |
| CN106430113B (en) * | 2016-10-31 | 2018-07-13 | 重庆市南川区庆岩福利碱厂 | A kind of manufacture craft reducing oxidizing sodium sulphide degree |
| CN106517101B (en) * | 2016-10-31 | 2019-02-22 | 重庆市南川区庆岩福利碱厂 | The manufacture craft of low-iron sodium sulfide |
| CN109455676A (en) * | 2019-01-21 | 2019-03-12 | 范冲天 | A kind of environmentally friendly refining methd of akali sulphide |
| CN109455676B (en) * | 2019-01-21 | 2022-05-27 | 范冲天 | Environment-friendly refining method of sodium sulfide |
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| CN1086361C (en) | 2002-06-19 |
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