CN105332058B - The method that dissolution method produces gypsum for paper whisker is recycled under ardealite normal pressure - Google Patents
The method that dissolution method produces gypsum for paper whisker is recycled under ardealite normal pressure Download PDFInfo
- Publication number
- CN105332058B CN105332058B CN201510748188.2A CN201510748188A CN105332058B CN 105332058 B CN105332058 B CN 105332058B CN 201510748188 A CN201510748188 A CN 201510748188A CN 105332058 B CN105332058 B CN 105332058B
- Authority
- CN
- China
- Prior art keywords
- lysate
- ardealite
- value
- normal pressure
- calcium sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Abstract
The invention discloses a kind of methods that circulation dissolution method produces gypsum for paper whisker under ardealite normal pressure, under normal pressure, with the SIO in circulation lysate separated and dissolved ardealite2, the elements such as GaO, FeO, to prepare good calcium sulfate crystal whiskers；By the way that in the case where setting lysate pH value, crystallization promoter, precipitated crystal is added, and calcium sulfate crystal whiskers that are good, can partially substituting paper pulp are produced in modification in the rotten lysate of low temperature, normal pressure separation；Low manufacture cost of the present invention, it is economical and practical, industrial waste ardealite can be comprehensively utilized, calcium sulfate crystal whiskers prepared by the present invention, crystallization is sufficiently, crystal is moderate, whiteness is high, high temperature resistant, product are very thin, it is the best additive of the products such as papermaking and rubber, plastics, friction plate building materials, coating for wall surface, tool has been widely used and market prospects.
Description
Technical field
The present invention relates to industrial enterprise's solid waste recycling and Preparation Technique of Powders field, specifically a kind of ardealite normal pressures
The method that lower circulation dissolution method produces gypsum for paper whisker.
Background technique
Ardealite is the waste residue emitted in the production of phosphorous chemical industry enterprise, and processing mode always is stockpiling of building a dam, Yunnan
It saves existing volume of cargo in storage and just crosses hundred million tons or more, the phosphorous chemical industry enterprise discharge amount in annual Yunnan Province is upper kiloton or more, and a large amount of stack is made
At environment, air, water source, forest, massif etc., various pollutions；Heap because of ardealite just occurred for Yunnan chemical plant
Pollution problem is put, plant shutdowns is caused, related personnel enters the environmentally friendly event of punishment to cause a sensation throughout the country；It takes over the land for use, build a dam, transport, manage,
The expense of great number makes enterprise can't bear the heavy load, many enterprise's long-term losses；Number man middle or small phosphorous chemical industry enterprise in Yunnan is just as processing
Ardealite solution never is had to shut down, and also according to the mineral constituent characteristic of ardealite, research is opened for national more chemical companies
All kinds of building material products, such as ardealite making burn-free bricks, ardealite air entrained concrete product are sent out, but because 20% or so in ardealite
Silica active processing cost it is excessively high, so tret is few in using as building materials, be worth low, be not enough to solve enterprise
Practical problem；Chemical company's hydrochloric acid surplus is also the cost pain of enterprise, and prepares calcium sulfate crystalline substance using ardealite hydrochloric acid method
There must be the low value-added height of production cost, extensively equal many advantages, the annual paper pulp notch nearly 50% in China need largely operation strategies
Import will make papermaking enterprise cost decline to a great extent if crystal whisker of gypsum is applied in papermaking, has filled up the insufficient notch of paper pulp, has answered
The fiber addition substitution in the products such as rubber, plastics, friction plate is used by effective volume of cargo in storage for cutting down ardealite, while can be saved
Timber improves environmental quality.
Summary of the invention
The purpose of the present invention is to provide the sides that circulation dissolution method under a kind of ardealite normal pressure produces gypsum for paper whisker
Method has accomplished the regeneration of Industrial Solid Waste resource using ardealite as the raw material for preparing calcium sulfate crystal whiskers；The dissolution of preparation
Extract liquor is at low cost, and production technology is new, and process flow is short, and equipment is simple, and small investment, low energy consumption, can accomplish nothing in production process
Discharging of waste liquid.
To achieve the above object, the invention provides the following technical scheme:
A kind of method that circulation dissolution method produces gypsum for paper whisker under ardealite normal pressure comprising the steps of:
1) it is formulated for the lysate of dissolution ardealite；
2) it in the lysate after ardealite to be put in proportion into heating, stirs to dissolve, is mixed under normal pressure
Liquid；
3) amount addition crystallization promoter merges it with mixed liquor as desired；
4) by settling and being separated by filtration insoluble matter；
5) cooling, crystallize out calcium sulfate crystal whiskers；
6) mixed liquor after separating calcium sulphate whisker is adjusted into pH value, is recycled again as lysate；
7) calcium sulfate crystal whiskers isolated spray modified solvent, realize that object is mutually modified, improve the retention of calcium sulfate crystal whiskers
Making it is suitable for papermaking addition.
As a further solution of the present invention: lysate in the step 1 by following parts by weight material composition: concentration
For 8%-45% 30-85 parts of hydrochloric acid, 5-15 parts of the ammonium sulfate of concentration 95%, 2-10 parts of hydrogen peroxide of concentration 5%, lysate
Concentration is between 10%-40%, and pH value is between 0.2-6.
As further scheme of the invention: ardealite is the discharge of Yunnan part phosphorous chemical industry enterprise in the step 1
High silicon, fluorine-containing all kinds of ardealites.
As further scheme of the invention: the crystallization promoter in the step 3 is magnesium salts solvent.
As further scheme of the invention: the modification solvent in the step 7 is strong base solution, including Ca (OH)2
Solution, Na2SO4Solution and Na2O solution.
As further scheme of the invention: the acid for being used to adjust ph value of mixture in the step 6 is hydrochloric acid or sulphur
Acid is Na for adjusting the alkali of ph value of mixture2O or NH3-H2O obtains the lysate that pH value is 0.2-6 after adjusting.
As further scheme of the invention: the solid-to-liquid ratio of ardealite and lysate is 1:5-1:8 in the step 2,
The heating temperature of lysate is 50-120 DEG C, and for pulp potential value between MV150-500, stirring the miscible reaction time is 3-
30min, miscible rear resulting ph value of mixture is 2-8.
Compared with prior art, the beneficial effects of the present invention are: the present invention is adopted using Industrial Solid Waste ardealite as raw materials for production
The waste ardealite discharged with phosphorous chemical industry enterprise separates various in ardealite under normal pressure with the dissolution liquid dissolution of circulation
Mineral constituent prepares multipurpose, good calcium sulfate crystal whiskers come production of turning waste into wealth；The present invention passes through corresponding properties solvent
Spray attachment changes the surface nature of object phase, and making it is suitable for the additive as papermaking material, and the calcium sulfate crystal whiskers produced are straight
Diameter, length are suitable for the substitution and addition of papermaking, and process flow is short, and equipment investment is few；The present invention can control calcium sulfate
Whisker reaches required size, and the silica isolated has 60% or more activity, can directly make in construction material
With, be comprehensively utilize ardealite economical method；The calcium sulfate crystal whiskers that the present invention prepares have resistance to 1400 degree or more
The performance of high temperature, can be as the substitute of fibrous matter needed for other industrial products；The present invention is separated by filtration, crystallisation by cooling,
The calcium sulfate crystal whiskers that washing is prepared after changing, purity are 95% or more, and whiteness is 90% or more, diameter 300-600um, and length is
100-5000um, copy paper experiment turnover rate is less than 15%, high temperature resistant, the low advantage of production cost；It is used as using ardealite and prepares sulphur
The raw material of sour calcium pyroborate has accomplished the regeneration of Industrial Solid Waste resource, and the dissolution extraction liquid of preparation is at low cost, production technology
Newly, process flow is short, and equipment is simple, and small investment, low energy consumption, can accomplish have and greatly push away without discharging of waste liquid in production process
Wide value.
Specific embodiment
The technical solution of the patent is explained in further detail With reference to embodiment.
A kind of method that circulation dissolution method produces gypsum for paper whisker under ardealite normal pressure comprising the steps of:
1) it is formulated for the lysate of dissolution ardealite；
2) it in the lysate after ardealite to be put in proportion into heating, stirs to dissolve, is mixed under normal pressure
Liquid；
3) amount addition crystallization promoter merges it with mixed liquor as desired；
4) by settling and being separated by filtration insoluble matter；
5) cooling, crystallize out calcium sulfate crystal whiskers；
6) mixed liquor after separating calcium sulphate whisker is adjusted into pH value, is recycled again as lysate；
7) calcium sulfate crystal whiskers isolated spray modified solvent, realize that object is mutually modified, improve the retention of calcium sulfate crystal whiskers
Making it is suitable for papermaking addition.
Lysate in the step 1 by following parts by weight material composition: the hydrochloric acid 30-85 that concentration is 8%-45%
Part, 2-10 parts of hydrogen peroxide of 5-15 parts of the ammonium sulfate of concentration 95%, concentration 5%, the concentration of lysate are PH between 10%-40%
Value is between 0.2-6.
Ardealite is the high silicon of Yunnan part phosphorous chemical industry enterprise discharge, fluorine-containing all kinds of ardealites in the step 1.
Crystallization promoter in the step 3 is magnesium salts solvent.
Modification solvent in the step 7 is strong base solution, including Ca(OH)2Solution, Na2SO4Solution and Na2O solution.
The acid for being used to adjust ph value of mixture in the step 6 is hydrochloric acid or sulfuric acid, for adjusting the alkali of ph value of mixture
For Na2O or NH3-H2O obtains the lysate that pH value is 0.2-6 after adjusting.
The solid-to-liquid ratio of ardealite and lysate is 1:5-1:8 in the step 2, and the heating temperature of lysate is 50-120
DEG C, for pulp potential value between MV150-500, stirring the miscible reaction time is 3-30min, obtains ph value of mixture after miscible
For 2-8, it is separated by filtration, the calcium sulfate crystal whiskers of 95% or more purity, 90% or more whiteness are prepared in crystallisation by cooling, washing after changing,
Calcium Sulfate Whiskers are 300-600um, and length 100-5000um, copy paper experiment turnover rate is less than 15%.
Embodiment 1
The ardealite of two street phosphate fertilizer plant of the Kunming 100g Jinning County stockpiling is weighed, wherein calcium sulphate content 70%, addition prepare
500 milliliters of lysates in, hydrogen peroxide 10ml of the lysate containing the hydrochloric acid 150g of 31% concentration, 3% concentration, tap water 340ml are molten
Solving liquid heating temperature is 60 DEG C, pH value 0.2, pulp potential MV150, stirs 10min with the speed of 30 times/min, 3g is added
Magnesia is stirred for 5min and filters to obtain liquid 380ml, the impurity 30g such as silicon slag after drying, and liquid stands natural cooling 3h, mistake
Filter to obtain calcium sulfate crystal whiskers 56g；Through detecting: sulfate dihydrate calcium content is greater than 95%, 56g crystal whisker of gypsum through with 100ml content Ca
(OH)2: the washing of water=1:10 solution spraying is modified, and required product is made, and whiteness is greater than 90%, 300-500um of diameter of whiskers,
2000-5000um of length.
Embodiment 2
The ardealite of 100g Yuxi river and mountain phosphate fertilizer plant is weighed, wherein calcium sulphate content 68%, is added prepared
In 500ml lysate, lysate contains the hydrochloric acid 140g of 31% concentration, the hydrogen peroxide 10ml of 3% concentration, ammonium sulfate 20g, tap water
340ml, heating temperature are 100 DEG C, pH value 0.25, and pulp potential MV180 stirs 10min with the speed of 30 times/min, adds
Entering 3g magnesium sulfate, be stirred for 5min, filters to obtain liquid 360ml, the impurity 30g such as silicon slag after drying, liquid pressure is cooled to 10 DEG C,
Time-consuming 30min filters to obtain calcium sulfate crystal whiskers 59g, through detecting: sulfate dihydrate calcium content be greater than 95%, 59g crystal whisker of gypsum through with
100ml content is Na2O:Na2SO4: water=1:0.5:10 mixed solution spray washing is modified, and required product is made, and whiteness is big
In 90%, 200-500um of diameter of whiskers, 1500-5000um of length.
The preferred embodiment of the patent is described in detail above, but this patent is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be under the premise of not departing from this patent objective
Various changes can be made.
Claims (1)
1. recycling the method that dissolution method produces gypsum for paper whisker under a kind of ardealite normal pressure, which is characterized in that comprising following
Step:
1) it is formulated for the lysate of dissolution ardealite；
2) it in the lysate after ardealite to be put in proportion into heating, stirs to dissolve under normal pressure, obtains mixed liquor；
3) amount addition crystallization promoter merges it with mixed liquor as desired；
4) by settling and being separated by filtration insoluble matter；
5) cooling, crystallize out calcium sulfate crystal whiskers；
6) mixed liquor after separating calcium sulphate whisker is adjusted into pH value, is recycled again as lysate；
7) calcium sulfate crystal whiskers isolated spray modified solvent, realize that object is mutually modified, improve the retention of calcium sulfate crystal whiskers,
Wherein, the lysate in the step 1 by following parts by weight material composition: concentration be 8%-45% hydrochloric acid 30-
85 parts, 5-15 parts of the ammonium sulfate of concentration 95%, 2-10 parts of hydrogen peroxide of concentration 5%, the concentration of lysate are 10%-40%,
PH value is 0.2-0.25；
The solid-to-liquid ratio of ardealite and lysate is 1:5-1:8 in the step 2, and the heating temperature of lysate is 50-120 DEG C, is mixed
The molten reaction time is 3-30min, and miscible rear gained mixed liquor pH value is 2-8；
Crystallization promoter in the step 3 is magnesium salts solvent；
The acid for being used to adjust mixed liquor pH value in the step 6 is hydrochloric acid or sulfuric acid, is for adjusting the alkali of mixed liquor pH value
Na2O or NH3-H2O obtains the lysate that pH value is 0.2-0.25 after adjusting；And
Modification solvent in the step 7 is strong base solution, including Na2O and Na2SO4Mixed solution, Ca (OH)2Solution, Na2O
Solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510748188.2A CN105332058B (en) | 2015-11-06 | 2015-11-06 | The method that dissolution method produces gypsum for paper whisker is recycled under ardealite normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510748188.2A CN105332058B (en) | 2015-11-06 | 2015-11-06 | The method that dissolution method produces gypsum for paper whisker is recycled under ardealite normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105332058A CN105332058A (en) | 2016-02-17 |
| CN105332058B true CN105332058B (en) | 2019-02-19 |
Family
ID=55282811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510748188.2A Active CN105332058B (en) | 2015-11-06 | 2015-11-06 | The method that dissolution method produces gypsum for paper whisker is recycled under ardealite normal pressure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105332058B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106758499B (en) * | 2017-03-23 | 2019-01-22 | 长沙理工大学 | A method of improving hot-pressing type bedding paper heat resistance |
| CN107190325B (en) * | 2017-05-09 | 2019-10-25 | 武汉理工大学 | A method of anhydrous calcium sulfate whisker is prepared using industrial by-product ardealite |
| CN107557870A (en) * | 2017-09-08 | 2018-01-09 | 云南磷化集团有限公司 | A kind of method with preparing calcium sulphate whiskers from ardealite |
| CN111994938B (en) * | 2020-08-31 | 2022-11-18 | 湖北工业大学 | Method for preparing calcium sulfate whisker from calcium carbide slag modified phosphogypsum |
| CN115043619B (en) * | 2022-06-21 | 2023-09-12 | 宜都兴发化工有限公司 | Preparation method of self-gelling fiber composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311355A (en) * | 2008-04-24 | 2008-11-26 | 云南民族大学 | Process for preparing calcium sulphate whiskers from ardealite |
| CN102383179A (en) * | 2011-10-09 | 2012-03-21 | 昆明理工大学 | Method of comprehensive utilization of industrial waste acid and ardealite |
| CN104562180A (en) * | 2015-01-07 | 2015-04-29 | 西南科技大学 | Method for preparing calcium sulfate whisker from phosphogypsum |
-
2015
- 2015-11-06 CN CN201510748188.2A patent/CN105332058B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311355A (en) * | 2008-04-24 | 2008-11-26 | 云南民族大学 | Process for preparing calcium sulphate whiskers from ardealite |
| CN102383179A (en) * | 2011-10-09 | 2012-03-21 | 昆明理工大学 | Method of comprehensive utilization of industrial waste acid and ardealite |
| CN104562180A (en) * | 2015-01-07 | 2015-04-29 | 西南科技大学 | Method for preparing calcium sulfate whisker from phosphogypsum |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105332058A (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105332058B (en) | The method that dissolution method produces gypsum for paper whisker is recycled under ardealite normal pressure | |
| CN105174760B (en) | A kind of method that dihydrate gypsum prepares αsemiwatergypsum | |
| CN102383179B (en) | A kind of method that industrial waste acid and phosphogypsum fully utilize | |
| CN101311355B (en) | Process for preparing calcium sulphate whiskers from ardealite | |
| CN102925956B (en) | Method for preparing calcium sulfate hemihydrate whiskers by taking ardealite as main raw material | |
| CN102030354B (en) | Treatment method of waste sulfuric acid | |
| CN109179476B (en) | Method for controlling water content of titanium gypsum | |
| CN103332666A (en) | Settling agent in wet-method phosphoric acid concentration processing process | |
| CN104140082A (en) | Method for recycling titanium dioxide waste acid | |
| CN100417594C (en) | Production process of large grain anhydrous sodium sulfate with natural salt lake mirabilite | |
| CN105669926B (en) | A kind of preparation method of high-content naphthalene water reducer | |
| CN101531389B (en) | Method for producing polyaluminium chloride | |
| CN113929328A (en) | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer | |
| CN103395816A (en) | Process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle | |
| CN111118606B (en) | Method for preparing calcium sulfate whiskers by using bone gelatin wastewater | |
| CN112441606B (en) | Method for separating valuable components from calcium sulfate raw material and combining calcium carbonate | |
| CN102115204A (en) | Method for preparing manganese sulfate, ferrous sulfate and calcium sulfate from manganese ore tailings | |
| CN104445281A (en) | Waste residue comprehensive utilization method for trichlorosilane leaching system | |
| CN110304850A (en) | A method of alpha semi-hydrated gypsum is produced based on titanium gypsum | |
| CN110229442A (en) | A kind of preparation method of organic metal salt high polymer composite material | |
| CN101830493A (en) | Method for processing waste salt slurry of calcined soda with sodium carbonate and sodium sulfate | |
| CN102153097B (en) | Method for preparing polyaluminum ferric silicate flocculant, aluminium sulphate and sodium metasilicate pentahydrate by co-generation on oil shale waste residues | |
| CN101696016B (en) | Hydrothermal synthesis method of alkaline lithium pentaborate | |
| CN104071805B (en) | A kind of industry subtracts the processing method of carbon emission and solid waste comprehensive utilization | |
| CN102115197A (en) | Method for preparing manganese chloride and ferrous chloride by using manganese tailings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |