CN107188213B - The preparation method of the calcium sulfite particle of undefined structure - Google Patents
The preparation method of the calcium sulfite particle of undefined structure Download PDFInfo
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- CN107188213B CN107188213B CN201710570482.8A CN201710570482A CN107188213B CN 107188213 B CN107188213 B CN 107188213B CN 201710570482 A CN201710570482 A CN 201710570482A CN 107188213 B CN107188213 B CN 107188213B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/48—Sulfites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to a kind of preparation methods of the calcium sulfite particle of undefined structure, first certain density milk of lime and sodium hexametaphosphate solution are prepared with water respectively, with membrane filtration, remove undissolved impurity, then a certain amount of sodium hexametaphosphate solution is added in milk of lime, and continuing stirring makes the two be uniformly mixed, and finally adjusts pH value of solution=6.8~7.2 with sulfurous acid, it is slowly stirred, generates calcium sulfite.It is fully dry at 60 DEG C after the calcium sulfite precipitation of generation is filtered, is centrifuged and is alternately washed with redistilled water and absolute ethyl alcohol, pass through XRD（X-ray diffraction）Carry out crystal structure detection and SEM（Scanning electron microscope）Unformed calcium sulfite particle is obtained after carrying out morphology observations.The obtained product pattern of the present invention is graininess, and undefined structure is presented in crystal structure, and particle size is evenly distributed in 600~800nm, and preparation process is simple, of low cost, and materials safety is nontoxic, has preferable turbidity removal effect to sugarcane juice.
Description
Technical field
The present invention relates to a kind of preparation methods of the calcium sulfite particle of undefined structure, belong to field of inorganic chemical engineering.
Background technology
Calcium sulfite is a kind of crystalline powder of white, contains 0.5 molecular crystalline water (CaSO at ambient temperature3·
0.5H2O), heating can lose the crystallization water at 360-390 DEG C, be decomposed into calcium oxide and sulfur dioxide at 650 DEG C, be insoluble in
Water, for calcic-plastic composite material, cellulosics bleaching antichlor, food preservative and fermentation fungicide, especially in sugar industry
It has a wide range of applications.It can be passed into milk of lime or calcium chloride by sulfur dioxide and sodium sulfite reaction is made.
Application of the newborn calcium sulfite in sugar industry be mainly reflected in sugarcane juice it is peace and quiet during.Using tradition
The method for preparing calcium sulfite to obtain calcium sulfite particles larger, at a few micrometers or more, and to the peace and quiet effect of sugarcane juice
It is bad.And the calcium sulfite crystallinity of undefined structure is low, particle is small and unordered, has higher surface energy, to sugarcane juice
The colloid particle absorption effect of middle suspension is very strong, to achieve the purpose that peace and quiet syrup.Therefore, calcium sulfite particle morphology and knot
Structure has strong influence to the peace and quiet effect of syrup.
Currently, the preparation in relation to calcium sulfite particle and application, are concentrated mainly on flue gas desulfurization and prepare desulfurated plaster side
Face.Chinese patent（CN102701618A）High-strength environment-friendly brushing gypsum is produced using calcium sulfite desulfurated plaster；Chinese patent
（CN101712484A）A kind of a diameter of 0.5~8mm is prepared, surface has been covered with the column calcium sulfite particles of many fine holes,
So that calcium sulfite can more come into full contact with water, dechlorination effect is improved.Chinese patent（CN101921084A）With sulfurous acid
Calcium is primary raw material, and has been mixed and made into a kind of calcium sulfite skin beautifying ball with organic acid, negative ion powder, binder, and water quality is made to have
There are antibiosis antibacterial characteristics, promote skin pore to receive thin, supplement skin moisture prevents skin aging, U.S. to reach moisturizing skin
The effect of white skin care.However, the research that different-shape and the calcium sulfite of structure are applied in clarifying syrup is fresh both at home and abroad
It has been reported that.
Invention content
The technical problem to be solved by the present invention is to：A kind of preparation method of the calcium sulfite particle of undefined structure is provided,
Product pattern prepared by this method is graininess, and particle is small and unordered, and particle diameter distribution is 600~800nm, has higher surface
Can, it is very strong to the colloid particle absorption effect to suspend in sugarcane juice, to achieve the purpose that peace and quiet syrup.
Solving the technical solution of above-mentioned technical problem is：A kind of preparation method of the calcium sulfite particle of undefined structure,
The lime milk solution and mass concentration for being respectively first 1%~20% with water preparation mass fraction are 1g/L~10g/L calgons
Solution is added based on 0.01~0.04g calgons by 1g milk of limes, sodium hexametaphosphate solution is added to lime milk solution
In, and continuing stirring makes the two be uniformly mixed, and finally adjusts pH value of solution=6.8~7.2 with sulfurous acid, generates calcium sulfite, will give birth to
At the filtering of calcium sulfite precipitation, centrifuge and alternately washed with water and absolute ethyl alcohol after, fully drying obtains unformed sulfurous
Sour calcium particle.
The present invention further technical solution be：After adjusting pH value of solution=6.8~7.2 with sulfurous acid, dodecyl sulphur is added
Sour sodium is simultaneously sufficiently stirred dissolving, generates calcium sulfite；The addition of dodecyl sodium sulfate presses dodecyl sodium sulfate in solution
A concentration of 0.005~0.010mol/L meter.
The sodium hexametaphosphate solution membrane filtration of preparation.
The filter membrane is 0.45 μm of filter membrane.
Sodium hexametaphosphate solution is added in lime milk solution, and continues the mixing time that stirring keeps the two uniformly mixed
For 25~35min.
Drying temperature is 55~65 DEG C.
The lime milk solution calcium oxide or calcium hydroxide are prepared.
It is 600~800nm to obtain unformed calcium sulfite diameter of particle size.
The present invention is easy to operate, raw material environmental protection, safe and non-toxic, has prodigious application value in sugar industry.This hair
The product pattern of bright preparation is graininess, and undefined structure is presented in crystal structure, and for particle size in 600~800nm, distribution is equal
It is even, there is higher surface energy, it is very strong to the colloid particle absorption effect to suspend in sugarcane juice, have to sugarcane juice preferable
Turbidity removal effect.It is found by contrast test, the turbidity removal of the calcium sulfite particle of undefined structure prepared by the present invention to syrup
Effect can reach 73%, and highest can reach 85%, and the CaSO of general crystal structure3Particle turbidity removal rate is compared 60% or so
Calcium sulfite particle turbidity removal rate prepared by the present invention is much higher.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the calcium sulfite particle of undefined structure prepared by the present invention.
Fig. 2 is the X-ray diffractogram of the calcium sulfite particle of undefined structure prepared by the present invention.
Specific implementation mode
Embodiment 1：The six of the lime milk solution and 1g/L for being respectively 5% with water preparation mass fraction in 200mL beakers are partially
Then sodium hexametaphosphate solution is filtered with 0.45 μm of filter membrane, removes undissolved impurity, then take by sodium radio-phosphate,P-32 solution
The sodium hexametaphosphate solution of 20mL is in prepared 20g lime milk solutions, and continuing stirring 30min makes it fully react.Again
Sulfurous acid is added in the solution after reaction, adjusts pH=7.0, and be slowly stirred, generates calcium sulfite.Finally by generation
After calcium sulfite precipitation is filtered, centrifuged and alternately washed three times with redistilled water and absolute ethyl alcohol, under the conditions of 60 DEG C fully
It is dry.Pass through XRD（X-ray diffraction）Carry out crystal structure detection and SEM（Scanning electron microscope）After carrying out morphology observations, obtain
It is 600~800nm to have arrived particle diameter distribution, is evenly distributed, undefined structure, and pattern is granular calcium sulfite particle.
Embodiment 2：The six of the lime milk solution and 2g/L for being respectively 5% with water preparation mass fraction in 200mL beakers are partially
Then sodium hexametaphosphate solution is filtered with 0.45 μm of filter membrane, removes undissolved impurity, then take by sodium radio-phosphate,P-32 solution
The sodium hexametaphosphate solution of 30mL is in prepared 48g lime milk solutions, and continuing stirring 30min makes it fully react.Again
Sulfurous acid is added in the solution after reaction, adjusts pH=7.0, and be slowly stirred, generates calcium sulfite.Finally by generation
After calcium sulfite precipitation is filtered, centrifuged and alternately washed three times with redistilled water and absolute ethyl alcohol, under the conditions of 60 DEG C fully
It is dry.Pass through XRD（X-ray diffraction）Carry out crystal structure detection and SEM（Scanning electron microscope）After carrying out morphology observations, obtain
It is 600~800nm to have arrived particle diameter distribution, is evenly distributed, undefined structure, and pattern is granular calcium sulfite particle.
Embodiment 3：In 200mL beakers the six of lime milk solution and 3g/L that mass fraction is 10% are prepared with water respectively
Then sodium hexametaphosphate solution is filtered with 0.45 μm of filter membrane, removes undissolved impurity, then take by sodium metaphosphate solution
The sodium hexametaphosphate solution of 40mL is in prepared 80g lime milk solutions, and continuing stirring 30min makes it fully react.Again
Sulfurous acid is added in the solution after reaction, adjusts pH=7.0, and be slowly stirred, generates calcium sulfite.Finally by generation
After calcium sulfite precipitation is filtered, centrifuged and alternately washed three times with redistilled water and absolute ethyl alcohol, under the conditions of 60 DEG C fully
It is dry.Pass through XRD（X-ray diffraction）Carry out crystal structure detection and SEM（Scanning electron microscope）After carrying out morphology observations, obtain
It is 600~800nm to have arrived particle diameter distribution, is evenly distributed, undefined structure, and pattern is granular calcium sulfite particle.
Embodiment 4：The six of the lime milk solution and 1g/L for being respectively 5% with water preparation mass fraction in 200mL beakers are partially
Then sodium hexametaphosphate solution is filtered with 0.45 μm of filter membrane, removes undissolved impurity, then take by sodium radio-phosphate,P-32 solution
The sodium hexametaphosphate solution of 20mL is in prepared 20g lime milk solutions, and continuing stirring 30min makes it fully react.Again
Sulfurous acid is added in the solution after reaction, pH=7.0 is adjusted, after stove drying, it is molten to be subsequently added into 5g/L dodecyl sodium sulfates
Liquid is simultaneously sufficiently stirred 30min, and the addition of sodium dodecyl sulfate solution presses the concentration of dodecyl sodium sulfate in final solution
It is counted for 0.008mol/L, generates calcium sulfite.Finally by the filtering of the calcium sulfite of generation precipitation, centrifugation and with redistilled water and
Absolute ethyl alcohol alternately after washing three times, is fully dried under the conditions of 60 DEG C.Pass through XRD（X-ray diffraction）Carry out crystal structure inspection
Survey and SEM（Scanning electron microscope）After carrying out morphology observations, it is 600~800nm to have obtained particle diameter distribution, is evenly distributed, nothing
Stereotyped structure, pattern are granular calcium sulfite particle.
It is redistilled water that solution, which prepares water used, in the various embodiments described above of the present invention.
The calcium sulfite precipitation filtering of generation described in various embodiments of the present invention, centrifugation and with redistilled water and anhydrous second
It is once that alternately washed once with absolute ethyl alcohol that alcohol, which alternately washs first to washed once again with redistilled water,.
By the processing step of embodiment 1, calgon is not added in the process, obtains general calcium sulfite particle.Implement
Example 1 adds calgon, embodiment 4 and adds the calcium sulfite that calgon and dodecyl sodium sulfate are prepared simultaneously
The Zeta potential value of particle is as shown in following table one.
The Zeta potential parameter important as one is used to characterize the electrostatic interaction between particle, with particles agglomerate journey
The increase Zeta potential value of degree is gradually reduced, and potential value shows that particle is more easy to agglomerate closer to 0.CaSO3Particle was generating
Without SHMP in journey（Calgon）And SLS（Dodecyl sodium sulfate）When effect, Zeta potential is -3.75mV, is passed through
Its Zeta potential absolute value increases to -8.76mV after complexing agent SHMP effects, shows that the degree of scatter of particle obtains certain carry
It rises, after surfactant SLS effects, Zeta potential absolute value increases to -16.2 mV, illustrates new life at this time
CaSO3Particle has higher stability, and is easily dispersed in the solution.
Contrast experiment：The calcium sulfite particle prepared using the present invention removes sucrose mix juice with general calcium sulfite particle
Turbid experiment, the brix of the sucrose mix juice used is 18 ° of Bx, and turbidity 1250mg/L, turbidity removal effect is as shown in following table two.
As can be seen from the above table, newborn CaSO3Particle can effectively remove the colloidal particles to suspend in syrup, to reduce
The turbidity of syrup.Due to general CaSO3Particle shows spherical agglomeration on its pattern and particle size is larger, thus shows
Poor clarifying syrup effect.Newborn CaSO3Peace and quiet effect be gradually increased with the rising of its unformed degree, to syrup
With highest turbidity removal effect, reach 85%.Simultaneously as the effect of SLS so that the surface of particle is covered in hydrophobic official
It can roll into a ball, contribute to pigment, the suction-operated of the organic matters such as colloid.
Claims (8)
1. a kind of preparation method of the calcium sulfite particle of undefined structure, it is characterised in that：First quality point is prepared with water respectively
Number is 1g/L~10g/L sodium hexametaphosphate solutions for 1%~20% lime milk solution and mass concentration, is added by 1g milk of limes
0.01~0.04g calgon meters, sodium hexametaphosphate solution is added in lime milk solution, and continuing stirring keeps the two mixed
Conjunction is uniform, finally adjusts pH value of solution=6.8~7.2 with sulfurous acid, generates calcium sulfite, the calcium sulfite precipitation of generation is filtered,
It is fully dry after centrifuging and use water and absolute ethyl alcohol alternately to wash, obtain unformed calcium sulfite particle.
2. the preparation method of the calcium sulfite particle of undefined structure according to claim 1, it is characterised in that：Use sulfurous
Behind acid-conditioning solution pH=6.8~7.2, dodecyl sodium sulfate is added and is sufficiently stirred dissolving, generates calcium sulfite；Dodecane
The addition of base sodium sulfonate is based on a concentration of 0.005~0.010mol/L of dodecyl sodium sulfate in solution.
3. the preparation method of the calcium sulfite particle of undefined structure according to claim 1 or 2, it is characterised in that：Match
The sodium hexametaphosphate solution membrane filtration of system.
4. the preparation method of the calcium sulfite particle of undefined structure according to claim 3, it is characterised in that：Described
Filter membrane is 0.45 μm of filter membrane.
5. the preparation method of the calcium sulfite particle of undefined structure according to claim 1 or 2, it is characterised in that：It will
Sodium hexametaphosphate solution is added in lime milk solution, and continue stirring both make uniformly mixed mixing time be 25~
35min。
6. the preparation method of the calcium sulfite particle of undefined structure according to claim 1 or 2, it is characterised in that：It is dry
Dry temperature is 55~65 DEG C.
7. the preparation method of the calcium sulfite particle of undefined structure according to claim 1 or 2, it is characterised in that：Institute
The lime milk solution calcium oxide or calcium hydroxide stated are prepared.
8. the preparation method of the calcium sulfite particle of undefined structure according to claim 1 or 2, it is characterised in that：
It is 600~800nm to unformed calcium sulfite diameter of particle size.
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| CN201710570482.8A CN107188213B (en) | 2017-07-13 | 2017-07-13 | The preparation method of the calcium sulfite particle of undefined structure |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712484A (en) * | 2008-10-07 | 2010-05-26 | 刘武义 | Calcium sulfite particles and preparation method |
| CN103071382A (en) * | 2013-01-28 | 2013-05-01 | 山东星光生物科技有限公司 | Method for applying lime sludge of sugar refining waste to flue gas desulfurization |
| CN103232054A (en) * | 2013-05-08 | 2013-08-07 | 武汉钢铁(集团)公司 | Method for oxidizing CaSO3 in desulfurized fly ash in alkaline condition |
| CN105032149A (en) * | 2015-07-07 | 2015-11-11 | 沈阳化工大学 | Calcium carbonate/calcium hydrate-gypsum wet desulphurization and dedusting process for flue gas |
-
2017
- 2017-07-13 CN CN201710570482.8A patent/CN107188213B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712484A (en) * | 2008-10-07 | 2010-05-26 | 刘武义 | Calcium sulfite particles and preparation method |
| CN103071382A (en) * | 2013-01-28 | 2013-05-01 | 山东星光生物科技有限公司 | Method for applying lime sludge of sugar refining waste to flue gas desulfurization |
| CN103232054A (en) * | 2013-05-08 | 2013-08-07 | 武汉钢铁(集团)公司 | Method for oxidizing CaSO3 in desulfurized fly ash in alkaline condition |
| CN105032149A (en) * | 2015-07-07 | 2015-11-11 | 沈阳化工大学 | Calcium carbonate/calcium hydrate-gypsum wet desulphurization and dedusting process for flue gas |
Non-Patent Citations (1)
| Title |
|---|
| "超声波对亚硫酸钙晶粒形成及其形态的影响";赵小进等;《声学技术》;20101231;第29卷(第6期);第595-599页 * |
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