CN107445188B - A kind of preparation method of rod-like precipitates calcium carbonate - Google Patents
A kind of preparation method of rod-like precipitates calcium carbonate Download PDFInfo
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- CN107445188B CN107445188B CN201710842190.5A CN201710842190A CN107445188B CN 107445188 B CN107445188 B CN 107445188B CN 201710842190 A CN201710842190 A CN 201710842190A CN 107445188 B CN107445188 B CN 107445188B
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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 147
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 62
- 239000002244 precipitate Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 21
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 21
- 239000004571 lime Substances 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000009423 ventilation Methods 0.000 claims abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 40
- 235000019738 Limestone Nutrition 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 20
- 235000012255 calcium oxide Nutrition 0.000 claims description 20
- 239000006028 limestone Substances 0.000 claims description 20
- 230000029087 digestion Effects 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 230000020477 pH reduction Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 30
- 239000013078 crystal Substances 0.000 abstract description 28
- 239000000654 additive Substances 0.000 abstract description 26
- 239000000126 substance Substances 0.000 abstract description 25
- 235000010216 calcium carbonate Nutrition 0.000 description 49
- 239000007789 gas Substances 0.000 description 27
- 239000000920 calcium hydroxide Substances 0.000 description 19
- 235000011116 calcium hydroxide Nutrition 0.000 description 19
- 239000000123 paper Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 13
- 229960004424 carbon dioxide Drugs 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 150000003438 strontium compounds Chemical class 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 241000276489 Merlangius merlangus Species 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JETSKDPKURDVNI-UHFFFAOYSA-N [C].[Ca] Chemical compound [C].[Ca] JETSKDPKURDVNI-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012495 reaction gas 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
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- 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
-
- 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
-
- 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
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of preparation methods of rod-like precipitates calcium carbonate, comprising the following steps: (1) prepares lime white；(2) carbonation reaction: by lime white merging carbonation reaction tower, opening stirring, and control temperature of reaction system is 40-80 DEG C, and the concentration that carbon dioxide in gas mixture is passed through in reaction 0-30min early period is 5-15vol%, flow 2-4m3/ h, the concentration that carbon dioxide in gas mixture is passed through in the carbonation reaction later period is 25-40vol%, flow 4-6m3/ h stops ventilation when pH value of reaction system reaches 7.5, terminates carbonation reaction, obtains winnofil suspension；(3) it dehydrates: winnofil suspension being dehydrated, rod-like precipitates calcium carbonate is dried to obtain.Preparation method of the present invention, addition chemical additives and/or crystal seed are not needed during the preparation process, rod-like precipitates calcium carbonate can be prepared by the control of technique, it solves the problems, such as using at high cost and poor product quality caused by chemical additives, the problems such as crystal seed preparation is difficult in crystal seed method, and process flow is long.
Description
Technical field
The invention belongs to technical field of inorganic material, are related to winnofil, more precisely, are related to lime stone for original
The preparation method of the rod-like precipitates calcium carbonate of material.
Background technique
Calcium carbonate is a kind of important inorganic filler, is widely used in the fields such as plastics, rubber, papermaking and coating.According to
Calcium carbonate can be divided into powdered whiting and winnofil by the difference of calcium carbonate production method.Powdered whiting is through machinery
Method directly crush natural marble or lime stone be made.Winnofil is crystallized through chemical precipitation and is prepared.According to difference
Reaction condition, can get the winnofil of different morphologies, such as rice-shaped, fusiform, class be cubic, chain, sheet, spherical
With it is rodlike etc..There are three types of the crystal phases of calcium carbonate: calcite, aragonite and vaterite.Rod-like precipitates calcium carbonate is generally aragonite crystal phase.
Because grain aspect is bigger, rod-like precipitates carbon calcium has some special application performances.The most relative to application
Extensive spindle winnofil, when rod-like precipitates calcium carbonate is used as filler, retention with higher improves paper
Bulk and printing adaptability.Because rod-like precipitates calcium carbonate is easy to generate bridging effect, filling paper strength drop with paper-making fibre
Low rate is smaller.Rod-like precipitates calcium carbonate (aragonite structure) has higher index of refraction than other calcite calcium carbonates, is used as papermaking
The higher hiding rare of paper and printing colour developing optical density can be assigned when coating.Rodlike calcium carbonate applies also for filling plastic, with
Other calcium carbonate of similar specific surface are compared, and rod-like precipitates calcium carbonate can assign the better processing fluidity of product, thermostabilization
Property, lustrous surface, stretching/bending elastic modulus and impact strength.
When as coating for paper, rod-like precipitates calcium carbonate can form uniform gap in coating, accelerate the ink of paper
Infiltration rate is conducive to high speed printing, paper sheet thickness and glossiness also can be improved, and is expected to replace the higher kaolin of price.Specially
Sharp CN 105484099A discloses a kind of aragonitic light calcium composition and its application method for coating for paper, preferred particle
Size distribution be 0.5~2.3um, the aragonitic light calcium of draw ratio 8~13, it is alternative or reduce paper in kaolin, improve
Art paper and art post paperboard surface strength and glossiness reduce coating for paper cost in the case where not influencing paper quality.Specially
Sharp WO 2009/009553A1 discloses a kind of aragonitic winnofil for Paper Coating material, and aragonite content is not less than
30%, and partial size more than or equal to 2um calcium carbonate content less than 4%, the calcium carbonate content less than or equal to 0.25um less than 10%,
The transparency of paper is effectively improved for Paper Coating, gloss prints gloss and brightness.
Carbonation method is most important and most mature winnofil industrial process, i.e., in lime white (calcium hydroxide
Slurry) in be passed through carbon dioxide containing gas carry out precipitated crystal reaction.Rod-like precipitates calcium carbonate is prepared using carbonation method, usually
It needs that chemical additives and/or crystal seed are added in crystallization reaction mixture.Chemical additives mainly based on inorganic compound,
Using more including magnesium, strontium compound and phosphoric acid/salt etc..
Carbonation method prepares rodlike (aragonitic) winnofil, and magnesium chloride is effective chemical additives, and magnesium salts valence
Lattice are lower.But generally existing magnesium chloride dosage excessive problem when making chemical additives with magnesium chloride, is difficult to remove in the product
As impurity.If making chemical additives with acicular magnesium hydroxide and magnesium carbonate, chemical additives itself are difficult to obtain.
The common chemical additives of rodlike (aragonitic) winnofil are prepared containing strontium compound and carbonation method, often
High aragonite content product can be obtained.But the mechanism of action of chemical additives containing strontium compound is complicated, to carbonation reaction process conditions
It is required that it is high, different carbonating technique is needed containing strontium compound using different.Price containing strontium compound is higher, examines for cost
Consider, usually prepares high aragonite content winnofil to make chemical additives containing strontium compound, then crystal seed batch is made with this and is prepared
Rod-like precipitates calcium carbonate.
Phosphoric acid/salt is also that carbonation method prepares the common chemical additives of rod-like precipitates calcium carbonate.It is other to be used to carbonate
Method prepares the single crystal form controlling agent of rodlike calcium carbonate, and there are also aluminum contained compounds.Most of additives are difficult to graining when being used alone
The effect of type control or effect are poor, therefore are common methods using two or more chemical additives compound use.
In addition to using chemical additives, carbonation method prepares rod-like precipitates calcium carbonate and also often adds crystal seed, i.e., carbonating is anti-
A certain amount of aragonitic/rodlike substance is introduced in lime white before answering make crystal seed prepare rodlike calcium carbonate.Using addition crystal seed
Method prepares rod-like precipitates calcium carbonate, can effectively improve rodlike calcium carbonate content in product, controls its crystal habit, while can solve
Crystal habit or aragonite content certainly using cost problem caused by more chemical additives, but to crystal seed require high.It is final to produce
Aragonite phase/rodlike calcium carbonate content in object is often below crystal seed.
In addition to using chemical additives and crystal seed, carbonating technique is also that carbonation method prepares the research of rod-like precipitates calcium carbonate
Emphasis, such as lime slaking temperature, lime slaking ash/water ratio, lime white solid content, carbonation reaction initial temperature, reaction gas
Gas concentration lwevel etc..It is mostly in the past on the basis of adding chemical additives or crystal seed to the research of carbonating process conditions
It carries out.So far, any additive or crystal seed are not used, and only by adjustment, preparation process prepares rod-like precipitates calcium carbonate
Method there is not been reported.Almost all of correlative study person not think to add chemical additives/crystal seed be difficult to prepare it is rodlike
Winnofil.
Generally speaking, rod-like precipitates calcium carbonate can be prepared by adding chemical additives/crystal seed method.But just industry is raw
For production, the dosage of chemical additives is excessive or selling at exorbitant prices can all cause product cost to rise, and high aragonite content carbonic acid
The preparation of calcium crystal seed is also not easy very much.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of rod-like precipitates calcium carbonate, prepare aragonite crystal phase to overcome
Calcium carbonate needs to be added chemical additives and/or crystal seed, the disadvantage that energy consumption is high, at high cost.
To achieve the above object, the present invention provides a kind of preparation methods of rod-like precipitates calcium carbonate, comprising the following steps:
(1) lime white the digestion of limestone calcination and quick lime: is prepared；
(2) carbonation reaction: by the lime white merging carbonation reaction tower of the step (1), stirring is opened, control is anti-
Answering system temperature is 40-80 DEG C, and the concentration that carbon dioxide in gas mixture is passed through in reaction 0-30min early period is 5-15vol%,
Flow is 2-4m3/ h, the concentration that carbon dioxide in gas mixture is passed through in the carbonation reaction later period is 25-40vol%, and flow is
4-6m3/ h stops ventilation when pH value of reaction system reaches 7.5, terminates carbonation reaction, obtains winnofil suspension；
(3) it dehydrates: the step (2) being obtained into winnofil suspension and is dehydrated, rod-like precipitates are dried to obtain
Calcium carbonate.
Preferably, in above-mentioned technical proposal, quick lime is obtained after being calcined lime stone in the step (1), will be given birth to
Lime and water are that 1:4-10 is mixed and sufficiently digestion obtains lime white, lime white sieving, and is adjusted lime white and contained admittedly in mass ratio
It measures to 10-20%.
Preferably, in above-mentioned technical proposal, the coolant-temperature gage of the digestion is 20-30 DEG C.
Preferably, in above-mentioned technical proposal, the lime white sieving was 80 meshes.
Preferably, in above-mentioned technical proposal, before being calcined to lime stone, by limestone crushing to lumpiness 2-3cm.
Preferably, in above-mentioned technical proposal, the limestone calcination is in 1000-1450 DEG C of temperature lower calcination 200-
400min obtains quick lime.
Preferably, in above-mentioned technical proposal, the limestone calcination is in 1100-1300 DEG C of temperature lower calcination 300-
400min obtains quick lime.
Preferably, in above-mentioned technical proposal, the mixing speed of carbonation reaction early period is 100- in the step (2)
300r/min。
Preferably, in above-mentioned technical proposal, the mixing speed of carbonation reaction middle and later periods is 300- in the step (2)
600r/min。
Preferably, in above-mentioned technical proposal, it is 100-120 DEG C of condition that the dehydration and drying in the step (3), which is in temperature,
Lower dry 3-7h.
Compared with prior art, the invention has the following beneficial effects: the preparation method of rod-like precipitates calcium carbonate of the present invention,
Addition chemical additives and/or crystal seed are not needed during the preparation process, and rod-like precipitates carbon only can be prepared by the control of technique
Sour calcium can solve the problems, such as that the prior art uses at high cost and poor product quality caused by chemical additives and crystal seed method
The problems such as crystal seed preparation is difficult, and process flow is long.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum that product is prepared according to the preparation method of different rodlike winnofils；Wherein
A is the X ray diffracting spectrum of 1 product of embodiment in figure；B is the X ray diffracting spectrum of 2 product of embodiment；C is the production of embodiment 3
The X ray diffracting spectrum of object；D is the X ray diffracting spectrum of 4 product of embodiment；E is the X-ray diffractogram of 5 product of embodiment
Spectrum；F is the X ray diffracting spectrum of 1 product of comparative example；
Fig. 2 is that the SEM photograph of product is prepared in the preparation method embodiment 1 of rod-like precipitates calcium carbonate according to the present invention
Piece.
Fig. 3 is that the SEM photograph of product is prepared in the preparation method embodiment 2 of rod-like precipitates calcium carbonate according to the present invention
Piece.
Fig. 4 is that the SEM photograph of product is prepared in the preparation method embodiment 3 of rod-like precipitates calcium carbonate according to the present invention
Piece.
Fig. 5 is that the SEM photograph of product is prepared in the preparation method embodiment 4 of rod-like precipitates calcium carbonate according to the present invention
Piece.
Fig. 6 is that the SEM photograph of product is prepared in the preparation method embodiment 5 of rod-like precipitates calcium carbonate according to the present invention
Piece.
Fig. 7 is that the SEM photograph of product is prepared in the preparation method comparative example 1 of rod-like precipitates calcium carbonate according to the present invention
Piece.
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention will be described in detail, it is to be understood that guarantor of the invention
Shield range is not limited by the specific implementation.
Unless otherwise explicitly stated, otherwise in entire disclosure and claims, term " includes " or its change
Changing such as "comprising" or " including " etc. will be understood to comprise stated element or component, and not exclude other members
Part or other component parts.
Embodiment 1
The preparation method of rod-like precipitates calcium carbonate, the specific method is as follows: lime stone is crushed to 2-3cm through jaw crusher
Lumpiness calcines 400min at 1100 DEG C and obtains quick lime, 2kg quick lime is added at one time 25 by the buck mass ratio of 1:4
In DEG C digestion water, after stirring 20min, through 80 mesh vibrating screen filtering and removing slag, adjusting milk of lime solid content is for obtained milk of lime
13.0%.20kg milk of lime is taken, controlled at 55-60 DEG C, and is sent into carbonators, stirring is opened, reaches to system temperature
50 DEG C, adjusting stirring rate is 200r/min, is passed through carbonated mixed gas and starts to react, and controls carburizing reagent 0-20
The concentration of carbon dioxide in gas mixture is 10% in minute, flow 2m3/ h, adjustment stirring rate is when reaction was to 20 minutes
500r/min, gas concentration lwevel 30%, flow 4m3/ h, carbonating to reaction mixture pH are that 7.5 i.e. stopping is passed through gas
Body terminates carbonation reaction, obtains winnofil suspension, up to product after 5h dry under the conditions of dehydration, 110 DEG C.
Products therefrom specific surface area is 7.11m2/ g, aragonite content 74.88%, XRD spectrum are shown in Fig. 1 (a), electromicroscopic photograph
See Fig. 2.
Embodiment 2
The preparation method of rod-like precipitates calcium carbonate, the specific method is as follows: lime stone is crushed to 2 through jaw crusher~
3cm lumpiness calcines 350min at 1150 DEG C and obtains quick lime, is added at one time 2kg quick lime by the buck mass ratio of 1:6
In 25 DEG C of digestion water, after stirring 15min, through 80 mesh vibrating screen filtering and removing slag, adjust milk of lime solid content is obtained milk of lime
15.3%.20kg milk of lime is taken, controlled at 60-65 DEG C, and is sent into carbonators, stirring is opened, reaches to system temperature
55 DEG C, adjusting stirring rate is 100r/min, is passed through carbonated mixed gas and starts to react, and is mixed in control 0-20 minutes
The concentration for closing carbon dioxide in gas is 15%, flow 3m3/ h, adjustment stirring rate is 300r/ when reaction was to 20 minutes
Min, gas concentration lwevel 33%, flow 4m3/ h, carbonating to reaction mixture pH are that 7.5 i.e. stopping is passed through gas, eventually
Blocking acidification reaction obtains winnofil suspension, up to product after 5h dry under the conditions of dehydration, 110 DEG C.
Products therefrom specific surface area is 7.56m2/ g, aragonite content 83.35%, XRD spectrum are shown in Fig. 1 (b), electromicroscopic photograph
See Fig. 3.
Embodiment 3
The preparation method of rod-like precipitates calcium carbonate, the specific method is as follows: lime stone is crushed to 2 through jaw crusher~
3cm lumpiness calcines 300min at 1350 DEG C and obtains quick lime, is added at one time 2kg quick lime by the buck mass ratio of 1:7
In 25 DEG C of digestion water, after stirring 20min, through 80 mesh vibrating screen filtering and removing slag, adjust milk of lime solid content is obtained milk of lime
19.5%.20kg milk of lime is taken, controlled at 70~75 DEG C, and is sent into carbonators, stirring is opened, reaches to system temperature
65 DEG C, adjusting stirring rate is 300r/min, is passed through carbonated mixed gas and starts to react, in control 0~30 minute
The concentration of carbon dioxide in gas mixture is 10%, flow 4m3/ h, adjustment stirring rate is 600r/ when reaction was to 30 minutes
Min, gas concentration lwevel 20%, flow 4m3/ h, carbonating to reaction mixture pH are that 7.5 i.e. stopping is passed through gas, eventually
Blocking acidification reaction obtains winnofil suspension, up to product after 5h dry under the conditions of dehydration, 110 DEG C.
Products therefrom specific surface area is 6.84m2/ g, aragonite content 85.10%, XRD spectrum are shown in Fig. 1 (c), electromicroscopic photograph
See Fig. 4.
Embodiment 4
The preparation method of rod-like precipitates calcium carbonate, the specific method is as follows: lime stone is crushed to 2 through jaw crusher~
3cm lumpiness calcines 300min at 1200 DEG C and obtains quick lime, is added at one time 2kg quick lime by the buck mass ratio of 1:5
In 25 DEG C of digestion water, after stirring 20min, through 80 mesh vibrating screen filtering and removing slag, adjust milk of lime solid content is obtained milk of lime
12.1%.20kg milk of lime is taken, controlled at 50~55 DEG C, and is sent into carbonators, stirring is opened, reaches to system temperature
45 DEG C, adjusting stirring rate is 200r/min, is passed through carbonated mixed gas and starts to react, in control 0~30 minute
The concentration of carbon dioxide in gas mixture is 10%, flow 3m3/ h, adjustment stirring rate is 300r/ when reaction was to 20 minutes
Min, gas concentration lwevel 25%, flow 4m3/ h, carbonating to reaction mixture pH are that 7.5 i.e. stopping is passed through gas, eventually
Blocking acidification reaction obtains winnofil suspension, up to product after 5h dry under the conditions of dehydration, 110 DEG C.
Products therefrom specific surface area is 6.95m2/ g, aragonite content 79.42%, XRD spectrum are shown in Fig. 1 (d), electromicroscopic photograph
See Fig. 4.
Embodiment 5
The preparation method of rod-like precipitates calcium carbonate, the specific method is as follows: lime stone is crushed to 2 through jaw crusher~
3cm lumpiness calcines 200min at 1400 DEG C and obtains quick lime, disposably adds 2kg quick lime by the buck mass ratio of 1:10
Enter in 25 DEG C of digestion water, after stirring 20min, obtained milk of lime adjusts milk of lime solid content through 80 mesh vibrating screen filtering and removing slag
It is 11.0%.20kg milk of lime is taken, controlled at 75~80 DEG C, and is sent into carbonators, stirring is opened, is reached to system temperature
To 70 DEG C, adjusting stirring rate is 200r/min, is passed through carbonated mixed gas and starts to react, and is controlled 0~20 minute
The concentration of interior carbon dioxide in gas mixture is 8%, flow 3m3/ h, adjustment stirring rate is 600r/ when reaction was to 20 minutes
Min, gas concentration lwevel 28%, flow 5m3/ h, carbonating to reaction mixture pH are that 7.5 i.e. stopping is passed through gas, eventually
Blocking acidification reaction obtains winnofil suspension, up to product after 5h dry under the conditions of dehydration, 110 DEG C.
Products therefrom specific surface area is 7.12m2/ g, aragonite content 80.33%, XRD spectrum are shown in Fig. 1 (e), electromicroscopic photograph
See Fig. 6.
Comparative example 1
After limestone crushing, 200min is calcined at 950 DEG C and obtains quick lime, it is by the buck mass ratio of 1:5 that 2kg is raw
Lime is added at one time the milk of lime digested in 25 DEG C of digestion water through 80 mesh vibrating screen filtering and removing slag, adjusts milk of lime and contains admittedly
Amount is 12.5%.20kg milk of lime is taken, controlled at 55~60 DEG C, and is sent into carbonators, stirring is opened, to system temperature
Reach 50 DEG C, adjusting stirring rate is 500r/min, is passed through carbonated mixed gas and starts to react, two in mixed gas
The concentration of carbonoxide is 30%, flow 5m3/ h, carbonating to reaction mixture pH are that 7.5 i.e. stopping is passed through gas, terminate carbon
Acidification reaction obtains winnofil suspension, up to product after being dehydrated, being dried.Products therefrom specific surface area is 7.79m2/
G, no aragonite, XRD spectrum are shown in that Fig. 1 (f), electromicroscopic photograph are shown in Fig. 6.
Product shape comparison
Analysis comparison is carried out to the product of different embodiment and comparative examples, the aragonite content of rod-like precipitates calcium carbonate is penetrated by X
Line diffractometer (XRD) tests post analysis, and pattern is characterized by scanning electron microscope (SEM), and specific surface area is by BET specific surface area point
Analyzer characterization.The basic characterization information of 1-5 of the embodiment of the present invention and 1 product of comparative example is shown in Table 1.
The different embodiment and comparative example product shape contrast tables of table 1
| Group | Aragonite content | Pattern | Specific surface area (m2/g) |
| Embodiment 1 | 74.88% | It is rodlike | 7.11 |
| Embodiment 2 | 83.35% | It is rodlike | 7.56 |
| Embodiment 3 | 85.10% | It is rodlike | 6.84 |
| Embodiment 4 | 79.42% | It is rodlike | 6.95 |
| Embodiment 5 | 80.33% | It is rodlike | 7.12 |
| Comparative example 1 | 0 | Fusiform | 7.79 |
As shown in table 1, rodlike winnofil can be prepared using preparation method of the invention, aragonite content reaches
74.88-85.35%, specific surface area 6.84-7.12m2/g.And the calcium carbonate that comparative example is prepared is then at fusiform, also
There is no aragonite, specific surface area 7.79m2/g.Illustrate the preparation method using rod-like precipitates calcium carbonate of the present invention, in preparation process
In do not need addition chemical additives and/or crystal seed, rod-like precipitates calcium carbonate only can be prepared by the control of technique.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of preparation method of rod-like precipitates calcium carbonate, which comprises the following steps:
(1) lime white the digestion of limestone calcination and quick lime: is prepared；
(2) carbonation reaction: by the lime white merging carbonation reaction tower of the step (1), stirring is opened, reactant is controlled
Be temperature be 40-80 DEG C, react 0-30min early period in be passed through carbon dioxide in gas mixture concentration be 5-15vol%, flow
For 2-4m3/ h, the concentration that carbon dioxide in gas mixture is passed through in the carbonation reaction later period is 25-40vol%, flow 4-
6m3/ h stops ventilation when pH value of reaction system reaches 7.5, terminates carbonation reaction, obtains winnofil suspension；
(3) it dehydrates: the step (2) being obtained into winnofil suspension and is dehydrated, rod-like precipitates carbonic acid is dried to obtain
Calcium.
2. the preparation method of rod-like precipitates calcium carbonate according to claim 1, which is characterized in that will in the step (1)
Lime stone obtains quick lime after being calcined, and is in mass ratio that 1:4-10 is mixed and sufficiently digestion obtains lime by quick lime and water
Slurry, lime white sieving, and lime white solid content is adjusted to 10-20%.
3. the preparation method of rod-like precipitates calcium carbonate according to claim 2, which is characterized in that the water temperature of the digestion
Degree is 20-30 DEG C.
4. the preparation method of rod-like precipitates calcium carbonate according to claim 2, which is characterized in that the lime white, which is sieved, is
Cross 80 meshes.
5. the preparation method of rod-like precipitates calcium carbonate according to claim 1, which is characterized in that calcined to lime stone
Before, by limestone crushing to lumpiness 2-3cm.
6. the preparation method of rod-like precipitates calcium carbonate according to claim 1, which is characterized in that the limestone calcination is
Quick lime is obtained in 1000-1450 DEG C of temperature lower calcination 200-400min.
7. the preparation method of rod-like precipitates calcium carbonate according to claim 1, which is characterized in that the limestone calcination is
Quick lime is obtained in 1100-1300 DEG C of temperature lower calcination 300-400min.
8. the preparation method of rod-like precipitates calcium carbonate according to claim 1, which is characterized in that carbon in the step (2)
The mixing speed of acidification reaction early period is 100-300r/min.
9. the preparation method of rod-like precipitates calcium carbonate according to claim 1, which is characterized in that carbon in the step (2)
The mixing speed of acidification reaction middle and later periods is 300-600r/min.
10. the preparation method of rod-like precipitates calcium carbonate according to claim 1, which is characterized in that in the step (3)
Dehydration and drying is 3-7h dry under the conditions of temperature is 100-120 DEG C.
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| TWI791339B (en) * | 2021-11-26 | 2023-02-01 | 財團法人工業技術研究院 | Method for preparing rod-shaped calcium carbonate |
| CN117303423B (en) * | 2022-06-20 | 2025-02-18 | 中国科学院过程工程研究所 | Rod-shaped calcium carbonate and preparation method and application thereof |
| CN115092948B (en) * | 2022-06-27 | 2024-03-15 | 山西石器时代新材料科技有限公司 | Fine rod-shaped aragonite calcium carbonate prepared by utilizing flue gas and preparation method thereof |
| CN118439641B (en) * | 2024-03-27 | 2024-12-03 | 衢州五星纳米材料有限公司 | Precipitated calcium carbonate production and recovery process |
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| CN101525147A (en) * | 2008-12-04 | 2009-09-09 | 兰州理工大学 | Preparation method of nano calcium carbonate |
| CN102834356A (en) * | 2010-04-01 | 2012-12-19 | Omya发展股份公司 | Process for obtaining precipitated calcium carbonate |
| CN106832660A (en) * | 2017-01-09 | 2017-06-13 | 广西华纳新材料科技有限公司 | A kind of method that rod-like precipitates calcium carbonate improves hard PVC section bar performance |
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| EP1785397A4 (en) * | 2004-06-08 | 2011-12-07 | Fujifilm Corp | Method for producing carbonate |
| FI120032B (en) * | 2004-07-13 | 2009-06-15 | Fp Pigments Oy | Method and apparatus for making a calcium carbonate product, the product and its use |
| CN105417569A (en) * | 2015-12-28 | 2016-03-23 | 常熟市宏宇钙化物有限公司 | Preparation method of rodlike nano-calcium carbonate |
| CN106517285B (en) * | 2016-11-21 | 2017-11-14 | 广西华纳新材料科技有限公司 | A kind of preparation method of rod-like nano calcium carbonate |
| CN106430272B (en) * | 2016-11-21 | 2017-10-31 | 广西华纳新材料科技有限公司 | A kind of preparation method of bar-shaped aragonite calcium carbonate |
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| CN101525147A (en) * | 2008-12-04 | 2009-09-09 | 兰州理工大学 | Preparation method of nano calcium carbonate |
| CN102834356A (en) * | 2010-04-01 | 2012-12-19 | Omya发展股份公司 | Process for obtaining precipitated calcium carbonate |
| CN106832660A (en) * | 2017-01-09 | 2017-06-13 | 广西华纳新材料科技有限公司 | A kind of method that rod-like precipitates calcium carbonate improves hard PVC section bar performance |
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