CN116947081A - Method for removing sulfides from natural calcium carbonate - Google Patents
Method for removing sulfides from natural calcium carbonate Download PDFInfo
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- CN116947081A CN116947081A CN202310951321.9A CN202310951321A CN116947081A CN 116947081 A CN116947081 A CN 116947081A CN 202310951321 A CN202310951321 A CN 202310951321A CN 116947081 A CN116947081 A CN 116947081A
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- calcium carbonate
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- treatment liquid
- natural calcium
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 327
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000003568 thioethers Chemical class 0.000 title claims abstract 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 132
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 239000004343 Calcium peroxide Substances 0.000 claims abstract description 27
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000019402 calcium peroxide Nutrition 0.000 claims abstract description 27
- 239000012530 fluid Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 66
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000606 toothpaste Substances 0.000 abstract description 22
- 229940034610 toothpaste Drugs 0.000 abstract description 22
- 230000000694 effects Effects 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- 150000004763 sulfides Chemical class 0.000 description 16
- 238000006477 desulfuration reaction Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000003595 mist Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910021532 Calcite Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940095991 ferrous disulfide Drugs 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910021654 trace metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Geology (AREA)
- Epidemiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Cosmetics (AREA)
Abstract
The application relates to the technical field of calcium carbonate, and particularly discloses a method for removing sulfides from natural calcium carbonate. A method for removing sulfides from natural calcium carbonate, comprising the steps of: step 1), pretreatment of calcium carbonate: mixing calcium carbonate with the treatment liquid to obtain pretreated calcium carbonate; step 2), carrying out microwave treatment on the pretreated calcium carbonate to obtain desulphurized calcium carbonate; the treatment fluid is a compound of calcium peroxide and hydrogen peroxide. The application has the advantage of removing sulfides in natural calcium carbonate to be suitable for the toothpaste industry.
Description
Technical Field
The application relates to the field of calcium carbonate, in particular to a method for removing sulfides by using natural calcium carbonate.
Background
In the domestic toothpaste market, the natural calcium carbonate powder is a common toothpaste abrasive, and the use of calcium carbonate as the toothpaste abrasive can obviously improve the friction cleaning performance of the toothpaste. According to the industry standard QB/T2317-2012, namely natural calcium carbonate for toothpaste of oral cleaning care products, the impurity index of the natural calcium carbonate powder is required to be free of sulfide, otherwise the natural calcium carbonate powder cannot be used for toothpaste; because the formula components of the toothpaste are complex, certain components possibly release hydrogen sulfide and the like from sulfides in the calcium carbonate powder, so that the toothpaste becomes tasty, discolored and deteriorated, but certain sulfates such as calcium sulfate, sodium sulfate and the like used as food additives can be used for the toothpaste.
The natural calcium carbonate in China has larger reserves and relatively lower cost, and the calcium carbonate is widely used in industries of toothpaste, cosmetics, rubber, plastics, cables, papermaking, paint and the like. The natural calcium carbonate for toothpaste is white fine powder mainly prepared from calcite ore through the processes of ore dressing, water washing, airing/sun drying, crushing and the like, and the main component of the calcite is calcium carbonate, the density is 2.6-2.94, the hardness is 3, the natural calcium carbonate has glass luster, the decomposition temperature is 898.6 ℃, the structure is compact, the natural calcium carbonate is insoluble in water, is dissolved in acid, has few impurities, has uniform granularity, and has good friction cleaning performance when used as a toothpaste grinding agent. However, with the rapid development of various industries and the increasing exploitation amount of natural calcite, the reserves of sulfide-free natural calcite suitable for toothpaste are smaller and smaller; at present, general natural calcium carbonate contains trace sulfide of several milligrams to tens of milligrams per kilogram, and is difficult to apply to toothpaste, so that the development of toothpaste industry is more and more restricted, and therefore, there is room for improvement.
Disclosure of Invention
In order to remove sulfides in natural calcium carbonate so as to be suitable for the toothpaste industry, the application provides a method for removing sulfides from natural calcium carbonate.
The method for removing sulfide from natural calcium carbonate provided by the application adopts the following technical scheme:
a method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate: mixing natural calcium carbonate with the treatment liquid to obtain pretreated calcium carbonate;
step 2), carrying out microwave treatment on the pretreated calcium carbonate to obtain desulphurized calcium carbonate;
the treatment fluid is a compound of calcium peroxide and hydrogen peroxide.
By adopting the technical scheme, trace metal sulfides (mainly ferrous sulfide and ferrous disulfide) in natural calcium carbonate are effectively removed through the cooperation of treatment fluid and microwave treatment, the metal sulfides are composed of polar molecules, the polar molecules generate dipole steering polarization under the action of a microwave field, and the high-speed steering arrangement aggravates the collision of molecular movement and leads to the rupture of sulfur-containing chemical bonds; at the same time, the microwave action promotes the temperature of the system to rise, thereby causing the treatment liquid on the surface of the calcium carbonate powder to decompose and generating a large amount of active oxygen with oxidation effect. In microwaves, on the one hand, the trace amount of FeS or FeS in calcite 2 The Fe-S bond is broken by the action of microwaves, a large amount of generated-S is continuously diffused to the surface, and on the other hand, broken-S is rapidly oxidized to form SO under the action of active oxygen generated by the decomposition of the treatment fluid 2 Releasing from the powder; SO (SO) 2 The active CaO produced by decomposition of calcium peroxide is encountered to form CaSO 3 While CaSO 3 Under the oxidation of active oxygen, caSO is finally formed 4 Thereby the sulfide in the calcium carbonate powder is thoroughly removed.
Preferably, the step 1) includes:
step 1-1), cleaning natural calcium carbonate, and crushing to obtain calcium carbonate powder;
step 1-2), adding calcium peroxide into hydrogen peroxide, and uniformly dispersing to obtain a treatment liquid;
step 1-3), mixing the treatment liquid with calcium carbonate powder to obtain pretreated calcium carbonate.
By adopting the technical scheme, the natural calcium carbonate is crushed, so that the natural calcium carbonate is better and uniformly contacted with the treatment fluid, the effect of removing sulfide under the microwave condition is better, sulfide can be removed more thoroughly, and the quality of the prepared calcium carbonate is better.
Preferably, in the step 1-1), the calcium carbonate powder is 500-1200 meshes.
By adopting the technical scheme, the calcium carbonate powder is more easily mixed with the treatment fluid by specifically selecting the calcium carbonate powder to be 500-1200 meshes, so that the desulfurization effect is better.
Preferably, in the step 1-2), the concentration of the hydrogen peroxide is 1% -10%.
Through adopting above-mentioned technical scheme, through the concentration of specifically selecting hydrogen peroxide solution for the effect of treatment fluid oxidation under the microwave condition is better, and the effect of calcium carbonate desulfurization is better.
Preferably, in the treatment solution in the step 1-2), the concentration of the calcium peroxide in the hydrogen peroxide is 5% -20%.
Through adopting above-mentioned technical scheme, through the concentration of concrete selection calcium peroxide in hydrogen peroxide for the treatment fluid is better to the treatment effect of calcium carbonate, realizes better desulfurization effect.
Preferably, in the step 1-3), the mass ratio of the treatment solution to the calcium carbonate powder is 1:100-200.
By adopting the technical scheme, the desulfurization effect of the calcium carbonate can be well realized, the waste of raw materials is reduced, and the method has higher economic value.
Preferably, in the fewer steps 1-1), clean water is adopted for cleaning the calcium carbonate, and crushing and grinding are carried out after drying to obtain the calcium carbonate powder.
Through adopting above-mentioned technical scheme, through clear water washing, can go out impurity better, and be difficult for leading to calcium carbonate to take place chemical reaction and appear the performance variation, the calcium carbonate quality of making is better.
Preferably, in the step 2), the microwave output power is 10-50KW, and the treatment time is 10-30min.
Through adopting above-mentioned technical scheme, through specifically selecting microwave output and process time for desulfurization effect is better, can realize thoroughly desulfurization effect better, and the calcium carbonate quality of making is better.
In summary, the application has the following beneficial effects:
1. due toAccording to the application, the treatment fluid is matched with microwave treatment, so that trace metal sulfides (mainly ferrous sulfide and ferrous disulfide) in natural calcium carbonate are effectively removed, the metal sulfides are composed of polar molecules, dipole steering polarization is generated by the polar molecules under the action of a microwave field, and the molecular movement collision is aggravated due to high-speed steering arrangement, so that sulfur-containing chemical bonds are broken; at the same time, the microwave action promotes the temperature of the system to rise, thereby causing the treatment liquid on the surface of the calcium carbonate powder to decompose and generating a large amount of active oxygen with oxidation effect. In microwaves, on the one hand, the trace amount of FeS or FeS in calcite 2 The Fe-S bond is broken by the action of microwaves, a large amount of generated-S is continuously diffused to the surface, and on the other hand, broken-S is rapidly oxidized to form SO under the action of active oxygen generated by the decomposition of the treatment fluid 2 Releasing from the powder; SO (SO) 2 The active CaO produced by decomposition of calcium peroxide is encountered to form CaSO 3 While CaSO 3 Under the oxidation of active oxygen, caSO is finally formed 4 Thereby the sulfide in the calcium carbonate powder is thoroughly removed.
2. In the application, the concentration of the calcium peroxide in the hydrogen peroxide is preferably selected, so that the treatment effect of the treatment fluid on the calcium carbonate is better, and a better desulfurization effect is realized.
3. The application preferably ensures better desulfurization effect and better complete desulfurization effect by specifically selecting the microwave output power and the treatment time, and the prepared calcium carbonate has better quality.
Detailed Description
The present application will be described in further detail with reference to examples.
Example 1
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground into 500-mesh calcium carbonate powder by a grinder.
And 1-2), adding the calcium peroxide into the hydrogen peroxide with the concentration of 1%, and uniformly dispersing to ensure that the concentration of the calcium peroxide in the hydrogen peroxide is 5%, thereby obtaining the treatment liquid.
Step 1-3), weighing 100kg of calcium carbonate powder, conveying the calcium carbonate powder into a vortex mill through a double-screw loss-in-weight feeder, weighing 1kg of treatment liquid, spraying the treatment liquid into the vortex mill through a high-speed centrifugal atomizer, and mixing the treatment liquid in mist form with the calcium carbonate powder at a high speed in the vortex mill, so that the treatment liquid is sprayed to the calcium carbonate powder and adheres to the surface of the calcium carbonate powder, thereby obtaining the pretreated calcium carbonate.
And 2) placing the pretreated calcium carbonate into microwave equipment for microwave heating, wherein the microwave output power is 10KW, the treatment time is 10min, and naturally cooling to obtain the desulfurized calcium carbonate.
Example 2
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground into 800-mesh calcium carbonate powder by a grinder.
And 1-2), adding the calcium peroxide into 5% hydrogen peroxide, and uniformly dispersing to ensure that the concentration of the calcium peroxide in the hydrogen peroxide is 10%, thereby obtaining the treatment liquid.
Step 1-3), weighing 150kg of calcium carbonate powder, conveying the calcium carbonate powder into a vortex mill through a double-screw loss-in-weight feeder, weighing 1kg of treatment liquid, spraying the treatment liquid into the vortex mill through a high-speed centrifugal atomizer, and mixing the treatment liquid in mist form with the calcium carbonate powder at a high speed in the vortex mill, so that the treatment liquid is sprayed to the calcium carbonate powder and adheres to the surface of the calcium carbonate powder, thereby obtaining the pretreated calcium carbonate.
And 2) placing the pretreated calcium carbonate into microwave equipment for microwave heating, wherein the microwave output power is 30KW, the treatment time is 20min, and naturally cooling to obtain the desulfurized calcium carbonate.
Example 3
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground by a grinder into 1200-mesh calcium carbonate powder.
And 1-2), adding the calcium peroxide into 10% hydrogen peroxide, and uniformly dispersing to ensure that the concentration of the calcium peroxide in the hydrogen peroxide is 20%, thereby obtaining the treatment liquid.
Step 1-3), weighing 200kg of calcium carbonate powder, conveying the calcium carbonate powder into a vortex mill through a double-screw loss-in-weight feeder, weighing 1kg of treatment liquid, spraying the treatment liquid into the vortex mill through a high-speed centrifugal atomizer, and mixing the treatment liquid in mist form with the calcium carbonate powder at a high speed in the vortex mill, so that the treatment liquid is sprayed to the calcium carbonate powder and adheres to the surface of the calcium carbonate powder, thereby obtaining the pretreated calcium carbonate.
And 2) placing the pretreated calcium carbonate into microwave equipment for microwave heating, wherein the microwave output power is 50KW, the treatment time is 30min, and naturally cooling to obtain the desulfurized calcium carbonate.
Example 4
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground into 1000-mesh calcium carbonate powder by a grinder.
And 1-2), adding the calcium peroxide into the hydrogen peroxide with the concentration of 6%, and uniformly dispersing to ensure that the concentration of the calcium peroxide in the hydrogen peroxide is 8%, thereby obtaining the treatment liquid.
Step 1-3), 160kg of calcium carbonate powder is weighed, the calcium carbonate powder is sent to a vortex mill through a double-screw loss-in-weight feeder, 1kg of treatment liquid is weighed, the treatment liquid is sprayed to the vortex mill through a high-speed centrifugal atomizer, and the treatment liquid and the calcium carbonate powder which are in mist form in the vortex mill are mixed at a high speed, so that the treatment liquid is sprayed to the calcium carbonate powder and is attached to the surface of the calcium carbonate powder, and the pretreated calcium carbonate is obtained.
And 2) placing the pretreated calcium carbonate into microwave equipment for microwave heating, wherein the microwave output power is 20KW, the treatment time is 15min, and naturally cooling to obtain the desulfurized calcium carbonate.
Comparative example 1
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground into 1000-mesh calcium carbonate powder by a grinder.
And 1-2), adding the calcium peroxide into the hydrogen peroxide with the concentration of 6%, and uniformly dispersing to ensure that the concentration of the calcium peroxide in the hydrogen peroxide is 3%, thereby obtaining the treatment liquid.
Step 1-3), 160kg of calcium carbonate powder is weighed, the calcium carbonate powder is sent to a vortex mill through a double-screw loss-in-weight feeder, 1kg of treatment liquid is weighed, the treatment liquid is sprayed to the vortex mill through a high-speed centrifugal atomizer, and the treatment liquid and the calcium carbonate powder which are in mist form in the vortex mill are mixed at a high speed, so that the treatment liquid is sprayed to the calcium carbonate powder and is attached to the surface of the calcium carbonate powder, and the pretreated calcium carbonate is obtained.
And 2) placing the pretreated calcium carbonate into microwave equipment for microwave heating, wherein the microwave output power is 20KW, the treatment time is 15min, and naturally cooling to obtain the desulfurized calcium carbonate.
Comparative example 2
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground into 1000-mesh calcium carbonate powder by a grinder.
And 2) placing the pretreated calcium carbonate into microwave equipment for microwave heating, wherein the microwave output power is 20KW, the treatment time is 15min, and naturally cooling to obtain the desulfurized calcium carbonate.
Comparative example 3
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground into 1000-mesh calcium carbonate powder by a grinder.
And 1-2), adding the calcium peroxide into the hydrogen peroxide with the concentration of 6%, and uniformly dispersing to ensure that the concentration of the calcium peroxide in the hydrogen peroxide is 8%, thereby obtaining the treatment liquid.
Step 1-3), 160kg of calcium carbonate powder is weighed, the calcium carbonate powder is sent to a vortex mill through a double-screw loss-in-weight feeder, 1kg of treatment liquid is weighed, the treatment liquid is sprayed to the vortex mill through a high-speed centrifugal atomizer, and the treatment liquid and the calcium carbonate powder which are in mist form in the vortex mill are mixed at a high speed, so that the treatment liquid is sprayed to the calcium carbonate powder and is attached to the surface of the calcium carbonate powder, and the pretreated calcium carbonate is obtained.
And 2) putting the pretreated calcium carbonate into an oven for drying, wherein the temperature of the oven is 110 ℃, the drying time is 15min, and naturally cooling to obtain the desulfurized calcium carbonate.
Comparative example 4
A method for removing sulfides from natural calcium carbonate, comprising the following steps:
step 1), pretreatment of natural calcium carbonate, which specifically comprises the following steps:
step 1-1), natural calcium carbonate is washed by clear water, naturally dried, crushed by a crusher and ground into 1000-mesh calcium carbonate powder by a grinder.
And 1-2), adding the calcium peroxide into the hydrogen peroxide with the concentration of 6%, and uniformly dispersing to ensure that the concentration of the calcium peroxide in the hydrogen peroxide is 8%, thereby obtaining the treatment liquid.
Step 1-3), 160kg of calcium carbonate powder is weighed, the calcium carbonate powder is sent to a vortex mill through a double-screw loss-in-weight feeder, 1kg of treatment liquid is weighed, the treatment liquid is sprayed to the vortex mill through a high-speed centrifugal atomizer, and the treatment liquid and the calcium carbonate powder which are in mist form in the vortex mill are mixed at a high speed, so that the treatment liquid is sprayed to the calcium carbonate powder and is attached to the surface of the calcium carbonate powder, and the pretreated calcium carbonate is obtained.
And 2) placing the pretreated calcium carbonate into microwave equipment for microwave heating, wherein the microwave output power is 2KW, the treatment time is 15min, and naturally cooling to obtain the desulfurized calcium carbonate.
Experiment 1
The sulfide content of the calcium carbonate prepared in each example and comparative example was measured according to the measurement method of 4.9 sulfide in QB/T2317-2012 Natural calcium carbonate for oral cleaning Care toothpast.
The detection method comprises the following steps: 1g (0.1 g) of a calcium carbonate sample is accurately weighed, placed in a Xu Shi carbonic acid tester, a bottle stopper is plugged, 10mL of distilled water is added from a small funnel above, the air outlet is sealed by a piece of lead acetate test paper, 10mL of 1+1 hydrochloric acid (the volume ratio of the concentrated hydrochloric acid to the water is 1:1) is added from the small funnel, the temperature is heated to 90 ℃, heating is stopped after 1min, cooling is performed, and the lead acetate test paper is taken down to be compared with a standard color plate of 0 mg/kg.
If white, the sulfide detection result is indicated as "none". If gray, the sulfide detection result is indicated as "present".
The specific test data for experiment 1 are detailed in table 1.
TABLE 1
| Test paper color | |
| Example 1 | White color |
| Example 2 | White color |
| Example 3 | White color |
| Example 4 | White color |
| Comparative example 1 | Gray color |
| Comparative example 2 | Gray color |
| Comparative example 3 | Gray color |
| Comparative example 4 | Gray color |
According to the comparison of the data of each example in Table 1 and the data of comparative example 1, the concentration of calcium peroxide in the treatment solution in comparative example 1 is too low, so that the oxidation effect is insufficient, and the desulfurization effect is poor, and the test result is gray, namely, the fact that the calcium carbonate prepared in comparative example 1 also contains sulfide is proved, and the oxidation effect is better in each example because the concentration of calcium peroxide in the hydrogen peroxide is proper, so that the desulfurization effect is better realized, and the test result is white, so that the calcium carbonate can be well removed from the calcium carbonate, and the calcium carbonate can be suitable for toothpaste production.
According to the comparison of the data of each example in Table 1 and the data of comparative example 2, the step of treating calcium carbonate in comparative example 2 without adding a treatment liquid, wherein the calcium carbonate is only subjected to microwave treatment, and the test result is gray, it is seen that the effect of removing sulfide in the calcium carbonate cannot be achieved by treating the calcium carbonate by microwave alone, and the prepared calcium carbonate is not suitable for toothpaste because of containing sulfide.
As can be seen from the comparison of the data of each example in table 1 with the data of comparative example 3, in comparative example 3, the drying and heating were not performed by the microwave treatment, and in comparative example 3, the calcium carbonate was treated by the treatment liquid, but the technical effect of removing sulfide from the calcium carbonate was difficult to be achieved by the treatment liquid alone without the cooperation of the microwave treatment.
Therefore, only when the special treatment liquid is matched with the special microwave treatment process, the oxidation effect can be well realized, so that sulfide in the calcium carbonate can be thoroughly removed, and the calcium carbonate can be well applied to toothpaste production.
As can be obtained by comparing the data of each example in table 1 with the data of comparative example 4, the microwave output power in the microwave treatment step adopted in comparative example 4 is 2KW, and the effect of exciting the oxidation performance of the treating agent is more general due to the lower microwave output power, so that the effect of removing sulfide in calcium carbonate is poor, the experimental result is "gray", and the prepared calcium carbonate is difficult to be suitable for toothpaste production.
In conclusion, when the calcium carbonate is treated by adopting a special treatment liquid under a special microwave condition, sulfide in the obtained calcium carbonate can be well removed to reach the standard of no sulfide, so that the calcium carbonate can be applied to toothpaste production, and the natural calcium carbonate with higher sulfide content can be widely applied.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. A method for removing sulfide from natural calcium carbonate, which is characterized by comprising the following steps: the method comprises the following steps:
step 1), pretreatment of natural calcium carbonate: mixing natural calcium carbonate with the treatment liquid to obtain pretreated calcium carbonate;
step 2), carrying out microwave treatment on the pretreated calcium carbonate to obtain desulphurized calcium carbonate;
the treatment fluid is a compound of calcium peroxide and hydrogen peroxide.
2. A method for removing sulfides from natural calcium carbonate according to claim 1, characterized by: the step 1) comprises the following steps:
step 1-1), cleaning natural calcium carbonate, and crushing to obtain calcium carbonate powder;
step 1-2), adding calcium peroxide into hydrogen peroxide, and uniformly dispersing to obtain a treatment liquid;
step 1-3), mixing the treatment liquid with calcium carbonate powder to obtain pretreated calcium carbonate.
3. A method for removing sulfides from natural calcium carbonate according to claim 2, characterized by: in the step 1-1), the calcium carbonate powder is 500-1200 meshes.
4. A method for removing sulfides from natural calcium carbonate according to claim 2, characterized by: in the step 1-2), the concentration of the hydrogen peroxide is 1% -10%.
5. The method for removing sulfide from natural calcium carbonate according to claim 4, wherein: in the treatment liquid in the step 1-2), the concentration of the calcium peroxide in the hydrogen peroxide is 5% -20%.
6. A method for removing sulfides from natural calcium carbonate according to claim 2, characterized by: in the step 1-3), the mass ratio of the treatment fluid to the calcium carbonate powder is 1:100-200.
7. A method for removing sulfides from natural calcium carbonate according to claim 2, characterized by: in the less step 1-1), clean water is adopted for cleaning the calcium carbonate, and crushing and grinding are carried out after drying, so as to obtain the calcium carbonate powder.
8. A method for removing sulfides from natural calcium carbonate according to claim 1, characterized by: in the step 2), the microwave output power is 10-50KW, and the treatment time is 10-30min.
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