CN104445090B - The method that carbon black or ultra low-ash pure coal reduction sodium sulphate one-step method prepare anhydrous sodium sulfide - Google Patents
The method that carbon black or ultra low-ash pure coal reduction sodium sulphate one-step method prepare anhydrous sodium sulfide Download PDFInfo
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- CN104445090B CN104445090B CN201310428231.8A CN201310428231A CN104445090B CN 104445090 B CN104445090 B CN 104445090B CN 201310428231 A CN201310428231 A CN 201310428231A CN 104445090 B CN104445090 B CN 104445090B
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
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- C01B17/26—Preparation by reduction with carbon
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Abstract
The present invention relates to the new method that a kind of one-step method reaction prepares anhydrous sodium sulfide.It uses carbon black or ultra low-ash pure coal as reducing agent first, and is reacted with sodium sulphate, and one-step method obtains anhydrous sodium sulfide of the content more than 90%.Corrosion during to prevent the oxidation of vulcanized sodium and high temperature high content to reactor material, reaction is carried out in a kind of homemade reactor made of special material, and uses inert gas shielding atmosphere.The technique has advantages below：First, raw material is pure, reaction condition is special, one-step method can obtain product, avoids the series of processes such as the follow-up molten leaching of existing vulcanized sodium production, sedimentation, separation, evaporation, shortens technological process, be especially omitted evaporation process, energy consumption is greatly lowered；Second, discharged substantially without waste water, waste residue and waste gas in whole production process；Third, products obtained therefrom sodium sulfide content is high, application field is wide, added value increase.The implementation of the technique changes cumbersome conventional vulcanized process for producing sodium for many years, high energy consumption, the present situation of high pollution by thorough, energy-conserving and environment-protective, meet modern production strategic requirement, there is significant economic benefit and social benefit, the research at home and abroad without correlation at present is reported.
Description
Technical field
The present invention relates to a kind of new method for preparing anhydrous sodium sulfide, more particularly, to one kind carbon black or ultra low-ash pure coal
Reacted for reducing agent and sodium sulphate, and by creating special reaction condition, one-step method can obtain anhydrous sodium sulfide finished product
New technology.
Background technology
The production of current domestic vulcanized sodium mainly obtains " grey black " with common ash coal reduction sodium sulphate, then leads to again
Cross molten leaching, sedimentation, evaporation, film-making etc. series of processes and finally obtain the vulcanized sodium that content is 60%.Due to by raw material and technology
Limitation, problems be present in the production technology：
（1）Complex technical process is tediously long, troublesome in poeration, and labor intensity is big；
（2）It is required for consuming substantial amounts of fire coal, high energy consumption in calcination reaction and evaporation process；
（3）Whole production process pollution is very serious, and the discharge of a large amount of sulphur-containing exhaust gas, waste water and waste residue is given birth to nearby residents
Living and ecological environment, which generates, to be had a strong impact on, is difficult to thoroughly solve for many years.
（4）Products obtained therefrom sodium sulfide content is typically 60% or so, and content is low, single varieties.It is and high recently as some
The development of sciemtifec and technical sphere, more and more higher is required to becoming more meticulous for vulcanized sodium product, existing product far can not meet the market demand.
Vulcanized sodium in face of this high energy consumption, high pollution produces, at present under the strong request of national energy-saving emission reduction situation,
The akali sulphide enterprise of the country more than 95% is all listed among environmentally friendly " blacklist ", the crisis for be faced with stopping production, changing the line of production.
For sustainable development, change akali sulphide production technology and technology that existing tradition falls behind, the present invention propose with
Pure carbon black or ultra low-ash pure coal（The coal of the low high carbon sequestration of ash）React, and pass through for reducing agent, and 99% industrial sulphuric acid sodium
The measure One-step productions such as control process conditions go out anhydrous sodium sulfide product of the content more than 90%, follow-up so as to eliminate（Bag
Include and molten soak, settle, washing mud, evaporation etc.）Sequence of operations so that whole technological process shortens dramatically, and energy consumption reduces, three wastes
Discharge.And the raising of product sodium sulfide content can not only save packing cost and slow down transport pressure, the what is more important height
Content vulcanized sodium also can apply to other high-tech areas, such as high-grade engineering plastics polyphenylene sulfide（Abbreviation PPS resin）
Synthesis etc. so that added value of product greatly increases.It may be said that the invented technology overcomes a variety of disadvantages of existing vulcanized sodium production
End, no matter at home or external, the production technology progress to vulcanized sodium all has epoch-making meaning.Up to the present, state
It is inside and outside that research report was carried out to this vulcanized sodium technology without an enterprise or research institution.
Meanwhile for the preparation of anhydrous sodium sulfide product, domestic and international currently used method be all with aqueous vulcanized sodium,
Such as Na2S.9H2O、Na2S.5.5H2O、Na2S.3H2O etc. obtains by vacuum dehydration or addition dehydration of organic solvent
Arrive, these technologies have been known.Such as EP-B-0345 136, EP-B-0361 998, P00116141.5 etc., but they
Production premise is required for obtaining aqueous vulcanized sodium first being used as dry raw material, so still not escaping fundamentally existing
There is a production technology category of vulcanized sodium, and small scale, yield poorly.In addition, in generation twentieth century 30 or 40 years, the Soviet Union, Germany, day
Sheet, China etc. have ever done gas（H2, CO, natural gas etc.）The numerous studies report of sodium sulphate production anhydrous sodium sulfide is reduced,
But it could not finally realize industrialization because the viscous wall of material be present or add the problem of catalyst etc. is various.
The content of the invention
It is an object of the invention to provide it is a kind of not only can effectively overcome at present it is traditional using common coal be reducing agent warp
Series of processes produces vulcanized sodium seriously pollution and the defects of high energy consumption to caused by environment, and can obtain sodium sulfide content and exist
More than 90% product preparation process.It using carbon black or ultra low-ash pure coal be raw material that it, which is, and industrial sulphuric acid sodium reacts, and is passed through
Select and create special reaction condition one-step method and obtain the anhydrous sodium sulfide of high content.
The present invention is implemented by following technical scheme：The preparation method includes having the following steps：
1）The ultra low-ash pure coal of carbon black or particle diameter in below 0.1mm is pressed into Na with industrial sulphuric acid sodium2SO4：2C=1：1 etc.
Molar ratio ingredient, it is placed in after being sufficiently mixed in the atmosphere protection reduction furnace made with special material.
2）Be passed through inertia protection air-blowing sweep the air about 30min in stove after, by certain heating rate temperature programming, about
Reaction starts at 823 DEG C, is continuously heating to 1150 DEG C and is incubated 40min, course of reaction protection gas and caused CO2Tail gas alkali
Liquid is protected gas to return and recycled after absorbing.
3）Discharge system is opened under the conditions of atmosphere protection to be discharged, and is molded and is packed after slightly cold, is vulcanized
Sodium finished product, it is block in loose honeycomb.
Carbon black or ultra low-ash pure coal is used to ensure the water-insoluble of lower content in product, general warranty coal for reducing agent
Middle ash content is even lower below 3%, then in product water-insoluble below 1.0%；Requiring to obtain the production of lower water-insoluble
During product then selection carbon black as reducing agent；During with carbon black, wherein carbon containing >=97%；During with ultra low-ash pure coal, ash content therein≤
3%th, fixed carbon >=88%；Sodium sulphate is using the regulation of the class Grade A of GB 6009-2003 industrial sulphuric acids sodium I or high-class product, Na2SO4
≥99%。
Material carbon reacts with sodium sulphate in strict accordance with equimolar than dispensing, and otherwise unnecessary raw material will remain in the product
As impurity, especially excessive carbon presence can cause the raising of water insoluble matter content in product and influence product appearance.Simultaneously
Such equimolar dispensing also causes the existing production reduction coal dosage of the amount ratio of reduction coal to reduce about 40%；
React, efficiently avoid because of O in air in atmosphere of inert gases2、H2O etc. presence and occur a series of
Side reaction, so as to ensure the raising of the main content of vulcanized sodium.It is preferred that nitrogen；
Reactor linings are made using special substance, it can the corrosion of resistance to vulcanized sodium and seepage at high temperature well, from
And ensure that reaction be smoothed out with product because of material corrosion and caused by impurity effect；
Reaction about peaks in 823 DEG C of beginnings, 920 DEG C, and being warming up to 1150 DEG C can ensure that reaction can be carried out thoroughly,
It is easy to discharge；
Experiment proves the reaction within a very short time, can typically be completed in 20 min, material increase the reaction time
Can proper extension；
Reaction terminate after when atmosphere protection bottom discharge can reduce high temperature the aerial oxidation of vulcanized sodium and deliquescence；
Product appearance is red or light red, loose cellular；
Sodium sulfide content is 90%, and typically more than 92%, and 60% current vulcanized sodium product compares, and can not only save bag
This is dressed up, slows down transport pressure, while the anhydrous product is not easy to aoxidize, so it has excellent accumulating performance.
The advantage of the invention is that：On the one hand it has used purer reducing agent, carbon black or ultra low-ash pure coal, the opposing party
The conditions such as reactor of the face further through creation inert reaction atmosphere and using special material, fundamentally overcome reduction process institute
Side reaction caused by being possible to and avoid raw material and reactor material impurity effect caused by product, one-step method are obtained
More pure product, it is no longer necessary to which follow-up processing procedure, flow is short, and energy consumption is low, three-waste free discharge, and sodium sulfide content carries
Height has not only saved packaging and cost of transportation, and its application field is also wider, for example, high-grade engineering can be advantageously applied to
Synthesis of plastics polyphenylene sulfide etc., profit is higher.
Brief description of the drawings：
Fig. 1 is that the present invention prepares anhydrous sodium sulfide process chart, and Fig. 2 is current production technology of sodium sulfide flow chart.
Embodiment：
Embodiment 1：The method that carbon black one-step method reduction sodium sulphate prepares anhydrous high content vulcanized sodium, it is anhydrous to produce 1 Kg
On the basis of vulcanized sodium, the preparation method includes having the following steps：
1）It is placed in after 0.317Kg carbon blacks and 1.84Kg industrial sulphuric acid sodium are sufficiently mixed in homemade special reaction stove.
2）After being passed through the air about 30min in nitrogen purging stove, start program heating, while with 0.3m3/ h flow after
It is continuous to be passed through nitrogen.About react and start at 823 DEG C, continue to heat up, be incubated 40min, Ran Houting again when temperature reaches 1150 DEG C
Only react.
3）Discharge system discharging, slightly cold aftershaping, packaging are opened under the conditions of atmosphere protection.Gained vulcanized sodium is light red
Loose honeycomb is block, analyzes its sodium sulfide content 94.2%, water-insoluble 0.10%.
Embodiment 2：The method that ultra low-ash pure coal one-step method reduction sodium sulphate prepares anhydrous high content vulcanized sodium, to produce 1
On the basis of Kg anhydrous sodium sulfides, the preparation method includes having the following steps：
1）It is placed in after 0.350Kg ultra low-ash pure coals are sufficiently mixed with 1.84Kg industrial sulphuric acid sodium homemade special anti-
Answer in stove.
2）After being passed through the air about 30min in nitrogen purging stove, start program heating, while with 0.3m3/ h flow after
It is continuous to be passed through nitrogen.About react and start at 823 DEG C, continue to heat up, be incubated 40min, Ran Houting again when temperature reaches 1150 DEG C
Only react.
3）Discharge system discharging, slightly cold aftershaping, packaging are opened under the conditions of atmosphere protection.Gained vulcanized sodium is dredged to be red
Loose honeycomb is block, analyzes its sodium sulfide content 92.8%, water-insoluble 0.68%.
Embodiment 3：The method that ultra low-ash pure coal one-step method reduction sodium sulphate prepares anhydrous high content vulcanized sodium, to produce 10
On the basis of Kg anhydrous sodium sulfides, the preparation method includes having the following steps：
1）Homemade special reaction is placed in after 3.50Kg ultra low-ash pure coals and 18.4Kg industrial sulphuric acid sodium are sufficiently mixed
In stove.
2）After being passed through the air about 30min in nitrogen purging stove, start program heating, while with 0.3m3/ h flow after
It is continuous to be passed through nitrogen.About react and start at 823 DEG C, continue to heat up, be incubated 40min, Ran Houting again when temperature reaches 1150 DEG C
Only react.
3）Discharge system discharging, slightly cold aftershaping, packaging are opened under the conditions of atmosphere protection.
Gained vulcanized sodium is block for red loose honeycomb, analyze its sodium sulfide content be 93.4%, water-insoluble 0.61%.
Fixed carbon is 99.0% in carbon black used in embodiment；Fixed carbon 89.9%, ash content 2.19% in ultra low-ash pure coal used.
Claims (7)
1. carbon black or ultra low-ash pure coal reduction sodium sulphate one-step method prepare anhydrous, high content vulcanized sodium, it is characterised in that by one
The carbon black or ultra low-ash pure coal and sodium sulphate for determining granularity are sufficiently mixed uniformly by certain charge ratio, are placed in special material making
In high-temperature reactor, after being passed through protection gas, certain heating rate is controlled to be reacted after being heated to required temperature, reaction terminates
Discharged afterwards under atmosphere protection, you can obtain the product that sodium sulfide content is more than 90%.
2. the method described in claim 1, it is characterised in that reducing agent used is carbon black or ultra low-ash pure coal, and carbon black reduces gained
Product is more pure, and water-insoluble is lower.
3. the method described in claim 1, it is characterised in that during with carbon black, wherein carbon containing >=97%；During with ultra low-ash pure coal, its
In ash content≤3%, fixed carbon >=88%；Sodium sulphate using the class Grade A of GB 6009-2003 industrial sulphuric acids sodium I or high-class product it
Regulation, Na2SO4≥99%。
4. the method described in claim 1, it is characterised in that reactor used is homemade with special material making, is resistant to
High-temp anti-corrosion antiseep.
5. the method described in claim 1, it is characterised in that reaction is carried out in the atmosphere of inert gas shielding, and first choice is nitrogen
Gas.
6. the method described in claim 1, it is characterised in that using equimolar than dispensing, i.e. Na during reaction2SO4：2C=1：1；Instead
It is 823 DEG C ~ 1150 DEG C, 40 ~ 60min of reaction time to answer temperature, and reaction starts discharge system after terminating under the conditions of atmosphere protection
Discharging.
7. according to claim 1-6 method, it is characterised in that the vulcanized sodium of preparation is block for red loose honeycomb, is divided to two kinds：
Carbon black products obtained therefrom sodium sulfide content is generally more than 94%, and water-insoluble is below 0.2%；Ultra low-ash pure coal products obtained therefrom outward appearance
Take on a red color, sodium sulfide content is generally more than 92%, and water-insoluble is below 1.0%.
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| CN107619025A (en) * | 2016-07-13 | 2018-01-23 | 南风化工集团股份有限公司 | A kind of gas reduction sodium sulphate prepares the new technology of anhydrous sodium sulfide |
| CN112985064A (en) * | 2021-02-05 | 2021-06-18 | 陕西翼飞航智能科技有限公司 | Sintering device and sintering method based on plasma hot blast stove |
| CN113007895A (en) * | 2021-02-05 | 2021-06-22 | 陕西翼飞航智能科技有限公司 | Based on CO2Sodium sulfide production and CO production in plasma hot blast stove2Recovery system and method |
| CN115246629B (en) * | 2022-08-24 | 2023-04-28 | 湖南福尔程环保科技有限公司 | Resource utilization method of crude sodium sulfate |
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|---|---|---|---|---|
| US1540711A (en) * | 1922-08-03 | 1925-06-02 | Merrimac Chemical Co | Process for the manufacture of sodium sulphide |
| US1584597A (en) * | 1925-08-26 | 1926-05-11 | Harry P Bassett | Process of making sodium sulphide |
| CN1056662A (en) * | 1991-07-17 | 1991-12-04 | 王思翔 | Activating process for producing industrial sodium sulfide |
| CN1244493A (en) * | 1999-09-13 | 2000-02-16 | 甘肃亚盛盐化工业集团有限责任公司 | Production technology of yellow flaky sodium sulfide with low carbon and iron contents |
| CN101565173A (en) * | 2009-05-31 | 2009-10-28 | 孔凡逸 | Semi-vertical reverberatory furnace for preparing sodium sulfide and process thereof |
| CN101585512A (en) * | 2009-06-18 | 2009-11-25 | 赵志军 | Method of producing anhydrous sodium sulfide without pollution |
| CN101948100A (en) * | 2010-10-08 | 2011-01-19 | 赵志军 | Clean method for producing anhydrous sodium sulfide |
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2013
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1540711A (en) * | 1922-08-03 | 1925-06-02 | Merrimac Chemical Co | Process for the manufacture of sodium sulphide |
| US1584597A (en) * | 1925-08-26 | 1926-05-11 | Harry P Bassett | Process of making sodium sulphide |
| CN1056662A (en) * | 1991-07-17 | 1991-12-04 | 王思翔 | Activating process for producing industrial sodium sulfide |
| CN1244493A (en) * | 1999-09-13 | 2000-02-16 | 甘肃亚盛盐化工业集团有限责任公司 | Production technology of yellow flaky sodium sulfide with low carbon and iron contents |
| CN101565173A (en) * | 2009-05-31 | 2009-10-28 | 孔凡逸 | Semi-vertical reverberatory furnace for preparing sodium sulfide and process thereof |
| CN101585512A (en) * | 2009-06-18 | 2009-11-25 | 赵志军 | Method of producing anhydrous sodium sulfide without pollution |
| CN101948100A (en) * | 2010-10-08 | 2011-01-19 | 赵志军 | Clean method for producing anhydrous sodium sulfide |
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