CN1228247C - Process for producing super fine barium sulfate and calcium carbonate using chloralkali salt mud - Google Patents
Process for producing super fine barium sulfate and calcium carbonate using chloralkali salt mud Download PDFInfo
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- CN1228247C CN1228247C CN 200310122805 CN200310122805A CN1228247C CN 1228247 C CN1228247 C CN 1228247C CN 200310122805 CN200310122805 CN 200310122805 CN 200310122805 A CN200310122805 A CN 200310122805A CN 1228247 C CN1228247 C CN 1228247C
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- barium sulfate
- salt slurry
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Abstract
The present invention discloses a process for producing superfine barium sulfate and calcium carbonate by utilizing chlorine-alkali salt slurry. The process is characterized in that the process comprises the following steps of filtering salt slurry by a filtering net, drying and calcining the salt slurry, dissolving the salt slurry by hydrochloric acid, separating, washing, drying and pulverizing the salt slurry by airflow to obtain superfine barium sulfate, filtering the obtained filter liquor, adding ammonia to regulate pH for removing impurities, such as ferro manganese and the like, adding ammonium carbonate and surface active agents to clear solution after impurity removal, and agitating the mixtures for reaction to obtain superfine calcium carbonate. The present invention has the advantages for utilizing wastes and reducing environmental pollution, and the superfine barium sulfate and the calcium carbonate produced by using the salt slurry and used as filling materials are added to PVC products, the rigidity, the flexural strength and the impact toughness of materials are enhanced, so the materials have strong application value, and the present invention provides a new way for the comprehensive utilization of the salt slurry.
Description
Technical field
The present invention relates to the preparation method of ultra-fine barium sulfate and lime carbonate, be specifically related to from the chlor-alkali salt slurry, produce the preparation method of ultra-fine barium sulfate and lime carbonate, belong to chemical field.
Background technology
The chlorine industry salt slurry is the pulpous state discharge that is produced in caustic soda, soda ash production salt refining process, and the clarification salt solution of salt solution gained after refining the separation is called refined brine, and sedimentary discharge is called salt slurry.Mainly contain barium sulfate, lime carbonate, magnesium hydroxide, soluble salt and other insolubles in the salt slurry that is produced.Annual 1500 ten thousand tons of the industrial table salts (pressing sodium-chlor 100% calculates) that need of present two alkali industrial production, the salt slurry of national like this two alkali productions discharging amounts up to the hundreds of thousands of ton.
Along with society and enterprise pay attention to day by day to environmental protection, especially after China proposes the strategy of sustainable development, be the urgent problem that domestic two alkali industry face to the comprehensive treating process of salt slurry, the discharging meeting of a large amount of salt slurries causes serious pollution to environment, if enter the river, can silt harbour and river course up.Then need take a large amount of places if stack, after rain drop erosion, easily cause second environmental pollution.
Along with Chinese economic development and market competition aggravation, the product hierarchy of industries such as China's coating, papermaking, rubber, plastics improves constantly, require more and more higher to the additive that uses, as paint, extensively adopt ultra-fine barium sulfate in the coating, and also used ultra-fine and even nano-calcium carbonate to improve the performance of its goods as filler in the plastic industry.The consumption of ultra-fine barium sulfate and lime carbonate increases fast, and with the development of China's plastic industry, its market outlook are wide.Therefore utilize chlor-alkali salt slurry production ultra-fine barium sulfate and lime carbonate to have important social and economic significance.
The comprehensive utilization of salt slurry is a main difficult problem of puzzlement chlorine industry for a long time always, though there is salt slurry to be used for the reported in literature of aspects such as plastic filler and cement baking, but do not see industrializing implementation, the salt slurry of most of enterprises is still thrown aside stacking, has caused environmental pollution.
Summary of the invention
The problem that the present invention need solve is to be the comprehensive utilization of the chlor-alkali salt slurry that enterprise is discharged of raw material with rock salt and sea salt, and a kind of method of therefrom producing ultra-fine barium sulfate and lime carbonate promptly is provided.
The ultimate principle of reaction:
The chlor-alkali salt slurry is that a kind of particle is tiny, and main component is the precipitation mixture of barium, calcium, magnesium salts.Generally contain 60%BaSO in the butt salt slurry
4, 21%CaCO
3, 5%Mg (OH)
2, 2% ferrimanganic and coal ash grit of about 6% etc.According to the chemical constitution of salt slurry, adopt the method for hydrochloric acidolysis solubility in acids such as the calcium in the salt slurry, magnesium salts precipitation and wherein barium sulfate etc. can be separated.The solubleness of oxyhydroxide in water that forms according to different metal ions has than big difference, utilizes this principle, and the calcium magnesium plasma in the acid hydrolysis solution is separated.So the suitable potential of hydrogen of control reaches the isoionic purpose of separating calcium and magnesium in acid-base solution.
Both water insoluble because of barium sulfate, be insoluble to acid again, in salt slurry, add hydrochloric acid, make lime carbonate, magnesium hydroxide become water-soluble muriate, filter and promptly get barium sulfate.It is 9-10 that muriate in the filtrate adds the ammoniacal liquor adjust pH, and precipitated iron, manganese and ion add and can obtain the very high lime carbonate of purity after volatile salt filters.
Step of the present invention is as follows:
(1) the waste residue salt slurry at first is mixed with slurry, through strainer filtering, and oven dry.
(2) salt slurry of oven dry is mixed with 3: 1～4: 1 slurry more earlier through the rotary kiln calcining.
(3) the salt material-mud is poured in the enamel reaction still, stirred and heat temperature raising; Industrial concentrated hydrochloric acid slowly is added in the reactor, and the control reaction pH value is 2.5～3.5, reacts an amount of reductive agent Na of adding after 40-60 minute
2SO
3, continue reaction 10-15 minute, obtain the suspension liquid of barium sulfate and calcium and magnesium salts.
(4) above-mentioned solution is filtered washing, the clear liquid after obtaining white depositions barium sulfate and filtering.
(5), obtain superfine barium sulfate through comminution by gas stream with the barium sulfate drying.
(6) solution after the filter in (4) is moved in the reactor, add strong aqua, stirring, reaction rise to 9～10 up to the pH of solution, filter and discard precipitation.
(7) the clear liquid Returning reactor after the filter adds the tensio-active agent Sodium dodecylbenzene sulfonate, and 50 ℃～60 ℃ of the heating of stirring and heat up add sal volatile again, reacts after 30-40 minute, filters, obtains calcium carbonate superfine powder after the drying, comminution by gas stream.
In aforesaid method, described filter screen is preferably 300～400 orders; The calcining temperature of described rotary kiln is 800 ℃～900 ℃, and calcination time is 40-60 minute; The stir speed (S.S.) of enamel reaction still is 2200-2500rpm in the step (3).
The present invention is a raw material with the chlor-alkali salt slurry, extracts ultra-fine barium sulfate and lime carbonate, has not only improved the pollution of salt slurry to environment, and has turned waste into wealth, and has obtained good economic benefits.The ultra-fine barium sulfate and the lime carbonate that utilize the present invention to make, purity whiteness height, grain diameter is even, can be used for the filler of coating industry or plastics, reduces the cost of plastics greatly.
Description of drawings
Fig. 1 is the size distribution figure of barium sulfate particle, and median size is 1.1 μ m.
Fig. 2 is the size distribution figure of calcium carbonate particles, and median size is less than 1 μ m
Fig. 3 is the SEM photo of barium sulfate particle.
The TEM photo of Fig. 4 calcium carbonate particles.
Further set forth content of the present invention below in conjunction with specific examples:
1. get a certain amount of wet salt mud, be mixed with slurry,, remove mechanical impuritys such as fine sand and coal ash through 300 purpose strainer filterings, behind the slurry filtration after the impurity elimination in 105 ℃ of dryings 1 hour.
2. the butt salt slurry was through 800 ℃ of rotary kiln calcinings 40 minutes.Take by weighing burnt salt slurry 10kg again in enamel reaction still, add the water of 30kg, stir, be mixed with slurry.
3. the temperature of conditioned reaction still makes it be warming up to 90 ℃, and the adjustment stir speed (S.S.) is 2400rpm, adds 31% technical hydrochloric acid simultaneously, and the pH value of control reaction end is reacted after 50 minutes 2.5, adds 0.5% Na
2SO
3, react discharging after 15 minutes, to filter, wash, filtrate is reclaimed, and obtains the white barium sulfate product of about 6kg after the drying precipitate, obtains the ultra-fine barium sulfate that median size is 1.1um behind comminution by gas stream.
4. the filtrate with above-mentioned recovery moves into reactor, stirs, and adds 28% ammoniacal liquor, and the pH of conditioned reaction is 9, and filtering precipitate is warming up to 60 ℃ again, adds the Sodium dodecylbenzene sulfonate of 8g simultaneously, stirs, and the limit adds the (NH for preparing
4)
2CO
3Solution is until reacting completely.Filtration, washing, drying obtain the calcium carbonate superfine powder of about 2.1kg again behind comminution by gas stream.
5. the concrete quality index of ultra-fine barium sulfate that production obtains in the salt slurry and lime carbonate is as follows:
| Project | Test value |
| BaSO 4Content (%) whiteness (%) pH median size (μ m) | 97.4 92 7.5 1.1 |
| Project | Test value |
| CaCO 3(%) 〉=moisture (105 ℃) color impurities content (%)≤median size (μ m)＜specific surface area (m 2/g )＜ | 97.6 2 white powders 31 30 |
We have also carried out wet-process modified to the ultra-fine barium sulfate that extracts and lime carbonate, and with it with unmodified ultra-fine barium sulfate and lime carbonate filling polyvinyl chloride (PVC) sheet material respectively, measure its mechanical property and compare.It is as follows to fill a prescription:
| Form | Umber (phr) |
| PVC(k＝67-68) | 100phr |
| CaCO 3Or BaSO 4ACR (401) three salt disalt Zinic stearas calcium stearate oxidized polyethlene wax | 10phr 1.5phr 3phr 0.8phr 1phr 0.8phr 1phr |
The mechanics performance determining result is as follows:
PVC/CaCO
3And PVC/BaSO
4Performance of composites
| Numbering | Modulus in flexure Mpa | Flexural strength MPa | Tensile modulus MPa | Tensile strength MPa | Shock strength kJ/m 2 |
| A C 1 C 2 B 1 B 2 | 2238.6 2648.0 2825.4 2584.9 2647.5 | 78.2 82.6 82.7 82.2 83.5 | 1450.0 2434.7 2497.3 2027.7 2498.3 | 51.1 45.6 46.7 46.2 48.2 | 4.2 4.5 4.7 5.3 6.6 |
A: pure sample product, B
1: BaSO is untreated
4B
2: the BaSO of processing
4C
1: CaCO is untreated
3C
2: handle CaCO
3
From table as can be seen, ultra-fine BaSO
4, CaCO
3Join in the PVC goods as filler, make rigidity, flexural strength, the impelling strength of material that raising in various degree all be arranged, tensile strength then descends to some extent.And the BaSO after the modification
4, CaCO
3The degree of adding in the PVC goods rigidity to material, flexural strength, impelling strength to is higher than unmodified BaSO
4, CaCO
3, and the influence of the tensile strength of material is less than unmodified BaSO
4, CaCO
3This explanation is to BaSO
4, CaCO
3Modification obvious effects has been arranged.
Claims (4)
1. a method of producing ultra-fine barium sulfate and lime carbonate is characterized in that, utilizing and being discharged the waste residue salt slurry with rock salt and sea salt by the chlor-alkali enterprise of raw material is raw material, and this method comprises the steps:
(1) the waste residue salt slurry at first is mixed with slurry, through strainer filtering, and oven dry;
(2) salt slurry of oven dry is mixed with 3: 1～4: 1 slurry more earlier through the rotary kiln calcining;
(3) the salt material-mud is poured in the enamel reaction still, stirring and keeping feed temperature is 80 ℃～90 ℃, and industrial concentrated hydrochloric acid slowly is added in the reactor, and the pH of control reaction is 2.5～3.5, reacts to add 1%～3% reductive agent Na after 40-60 minute
2SO
3, continue reaction 10-15 minute, obtain the suspension liquid of barium sulfate and calcium and magnesium salts;
(4) above-mentioned solution is filtered washing, the clear liquid after obtaining white depositions barium sulfate and filtering;
(5), obtain superfine barium sulfate through comminution by gas stream with the barium sulfate drying;
(6) solution after the filter in (4) is moved in the reactor, add strong aqua, stirring, reaction rise to 9～10 up to the pH of solution, filter and discard precipitation;
(7) the clear liquid Returning reactor after the filter adds the tensio-active agent Sodium dodecylbenzene sulfonate, stirs and be warming up to 50 ℃～60 ℃, adds sal volatile again, reacts 30-40 minute after-filtration, drying, comminution by gas stream and obtains calcium carbonate superfine powder.
2. the method for production ultra-fine barium sulfate as claimed in claim 1 and lime carbonate is characterized in that, filter screen is 300～400 orders.
3. the method for production ultra-fine barium sulfate as claimed in claim 1 and lime carbonate is characterized in that, the rotary kiln temperature is 800 ℃～900 ℃, and calcination time is 40-60 minute.
4. the method for production ultra-fine barium sulfate as claimed in claim 1 and lime carbonate is characterized in that, the stir speed (S.S.) of enamel reaction still is 2200-2500rpm in step (3).
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|---|---|---|---|
| CN 200310122805 CN1228247C (en) | 2003-12-25 | 2003-12-25 | Process for producing super fine barium sulfate and calcium carbonate using chloralkali salt mud |
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|---|---|---|---|
| CN 200310122805 CN1228247C (en) | 2003-12-25 | 2003-12-25 | Process for producing super fine barium sulfate and calcium carbonate using chloralkali salt mud |
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| CN1554588A CN1554588A (en) | 2004-12-15 |
| CN1228247C true CN1228247C (en) | 2005-11-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624204B (en) * | 2009-01-12 | 2011-05-18 | 王嘉兴 | Four-great circulation method formed by waste gypsum mud and chlor-alkali industry |
Families Citing this family (11)
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|---|---|---|---|---|
| CN101823736B (en) * | 2010-04-30 | 2011-12-07 | 汪晋强 | Method for co-production of calcium carbonate and sodium silicate in preparation of light magnesium carbonate by chlor-alkali brine sludge |
| CN101823738B (en) * | 2010-04-30 | 2012-02-15 | 汪晋强 | Method for co-production of fine calcium carbonate and sodium silicate, in preparation of light magnesium carbonate by chlor-alkali brine sludge |
| CN101823737B (en) * | 2010-04-30 | 2011-12-07 | 汪晋强 | Method for co-production of ultra-fine calcium carbonate and sodium silicate in preparation of light magnesium carbonate by chlor-alkali brine sludge |
| CN102040250B (en) * | 2010-11-17 | 2012-03-28 | 辽宁工程技术大学 | Method for comprehensively utilizing chlor-alkali salt sludge |
| CN102303890A (en) * | 2011-08-19 | 2012-01-04 | 卢长生 | Production process for converting gray black barite into white barite finished product |
| CN106966413A (en) * | 2016-10-17 | 2017-07-21 | 上海新增鼎工业科技有限公司 | A kind of method that utilization potash salt slurry prepares Snow Agent magnesium chloride and barium sulfate byproduct |
| CN109850898A (en) * | 2019-02-20 | 2019-06-07 | 胡芳 | A kind of chlor-alkali industry salt slurry resource technology |
| CN109705880A (en) * | 2019-02-20 | 2019-05-03 | 胡芳 | A kind of chlor-alkali salt sludge recycling technology |
| CN111115666B (en) * | 2020-01-09 | 2021-06-22 | 西安交通大学 | Reduction treatment process for salt mud in chlor-alkali industry |
| CN111348672A (en) * | 2020-03-17 | 2020-06-30 | 湖南楚天钡业有限公司 | Process for producing barium sulfate and calcium chloride by using barite |
| CN112456832A (en) * | 2020-12-09 | 2021-03-09 | 泰安燊豪化工有限公司 | Treatment method of salt mud containing high calcium sulfate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624204B (en) * | 2009-01-12 | 2011-05-18 | 王嘉兴 | Four-great circulation method formed by waste gypsum mud and chlor-alkali industry |
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|---|---|
| CN1554588A (en) | 2004-12-15 |
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