CN107915247A - A kind of method with coal ash for manufacturing for precipitated calcium carbonate - Google Patents
A kind of method with coal ash for manufacturing for precipitated calcium carbonate Download PDFInfo
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- CN107915247A CN107915247A CN201711347776.0A CN201711347776A CN107915247A CN 107915247 A CN107915247 A CN 107915247A CN 201711347776 A CN201711347776 A CN 201711347776A CN 107915247 A CN107915247 A CN 107915247A
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- Prior art keywords
- calcium carbonate
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- precipitated calcium
- manufacturing
- coal ash
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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 127
- 229940088417 precipitated calcium carbonate Drugs 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000010883 coal ash Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000010881 fly ash Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- -1 iron ion Chemical class 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003763 carbonization Methods 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 17
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 17
- 239000004571 lime Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000007605 air drying Methods 0.000 claims abstract description 10
- 239000013522 chelant Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000002525 ultrasonication Methods 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000013049 sediment Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000003643 water by type Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 11
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 15
- 238000005034 decoration Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 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
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of method with coal ash for manufacturing for precipitated calcium carbonate, comprise the following steps：(1) flyash pre-processes：Flyash and deionized water are put into reactor, add hydrogen peroxide and concentrated hydrochloric acid, filtering, add ferrous metal chelating agent chelant iron ion in filtrate, filtering, addition sodium carbonate liquor is precipitated in filtrate, taking precipitate is dried, and obtains calcium carbonate powder crude product；(2) roast；(3) it is carbonized：Lime powder and deionized water are put into carbonization reactor, the packed sack for having porous silica titanium catalyst is put into deionized water, carbon dioxide is passed through under ultrasonication to be carbonized, react 45min, obtain calcium carbonate crystal, after calcium carbonate crystal is carried out heated-air drying processing, precipitated calcium carbonate finished product is obtained.Coal ash for manufacturing in the present invention to derive from a wealth of sources, cheap is for precipitated calcium carbonate, and the purity of the precipitated calcium carbonate prepared is high, can be widely applied to medicine, building decoration field.
Description
【Technical field】
The invention belongs to the recycling field of flyash, more particularly to a kind of side with coal ash for manufacturing for precipitated calcium carbonate
Method.
【Background technology】
Precipitated calcium carbonate is a kind of extremely wide inorganic filler of purposes, and the output of current whole nation precipitated calcium carbonate is
Reach 40 ten thousand tons/year.With the rapid development of the national economy, its demand still locates ascendant trend, especially construction industry in recent years
By national requirements by plastic-steel door window, drainage pipeline to mould Dai Gang, while the popularization of paper industry alkaline bleach liquor sizing technology and
Popularization and the increase of foreign export amount etc., more expand the application market of precipitated calcium carbonate.In terms of national market, precipitated calcium carbonate
It is even more increasingly still in the state that supply falls short of demand, the especially demand of some special required precipitated calcium carbonates of quality material
Increase.Analysis shows, particularly rubber, plastics, ink, papermaking processing manufacturing industry level are higher, to the demand of precipitated calcium carbonate
Larger and quality requirement is high.
Flyash, is the fine ash that catching is got off from the flue gas after coal combustion, and flyash is the main of coal-burning power plant's discharge
Solid waste.Power plants flyash main oxides composition for silica, ferrous oxide, iron oxide, calcium oxide and
Titanium dioxide etc..Flyash is all using directly being discarded or be directly prepared into concrete at present, following process and is utilized
Industrialization degree is relatively low, and product economic value added is smaller.Therefore, a kind of method with coal ash for manufacturing for precipitated calcium carbonate is studied,
There is huge reference value for the recycling for lifting flyash.
【The content of the invention】
Present invention aims at provide a kind of method with coal ash for manufacturing for precipitated calcium carbonate, the present invention first to flyash into
Row pretreatment, the silica in flyash, ferrous oxide, iron oxide, calcium oxide and titanium dioxide are removed；Then by fine coal
Ash is roasted, and generates calcium oxide；Finally it is carbonized under the catalytic action of porous silica titanium catalyst, obtains lightweight carbon
Sour calcium.Coal ash for manufacturing in the present invention to derive from a wealth of sources, cheap is for precipitated calcium carbonate, and the precipitated calcium carbonate prepared is pure
Degree is high, can be widely applied to medicine, building decoration field.
To reach above-mentioned purpose, the technical solution adopted in the present invention is：It is a kind of with coal ash for manufacturing for precipitated calcium carbonate
Method, comprises the following steps：
(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor
In, 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids are added, filtering, adds 3 parts of ferrous metal chelating agent chelant iron ions, mistake in filtrate
Filter, the sodium carbonate liquor that 50 parts of mass fractions are 15% is added in filtrate and is precipitated, taking precipitate is dried, and obtains carbon
Sour calcium powder crude product；
(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, with the speed of 50~65 DEG C/min be rapidly heated to
700~1000 DEG C, 2h is roasted, obtains lime powder；
(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor
In, the packed sack for having porous silica titanium catalyst is put into deionized water, ultrasonication power for 1200~
1800W, temperature are passed through carbon dioxide under conditions of being 40~55 DEG C and are carbonized, and reaction system is kept during carbonization
Pressure be 2.5~4.5MPa, react 45min after, obtained sediment is calcium carbonate crystal, by calcium carbonate crystal carry out heat
After wind drying process, precipitated calcium carbonate finished product is obtained.
In the present invention, as further explanation, the porous silica titanium catalyst described in step (3) is by following methods system
It is standby：Count in parts by weight, 100 parts of ethanol solutions, 1 part of surfactant and 2 parts of ferric sulfate are put into reactor, start stirring
Device, is stirred in the speed of 300~600r/min, while adds 10 parts of butyl titanates with the speed of 2mL/min, continues
2~3h is reacted, after vacuum distillation, is precipitated with absolute ethyl alcohol, collects sediment, and 25min is rinsed with pure water, is protected
It is 25~40L/ (m to hold backwash rate2S), the sediment after flushing is placed on after Muffle furnace roasted, obtained doped with iron
The porous silica titanium catalyst of ion.
In the present invention, as further explanation, the mass fraction of the ethanol solution is 60~73%.
In the present invention, as further explanation, the ferrous metal chelating agent described in step (1) is the condition in assisted microwave synthesis
Lower use.
In the present invention, it is as further explanation, the parameter of the heated-air drying processing described in step (3)：Temperature is 110
~120 DEG C, drying time be 5~8h.
In the present invention, as further explanation, the water content of the precipitated calcium carbonate finished product described in step (3) for 0.5~
1%.
The function introduction of part material is as follows：
Hydrogen peroxide, is used to aoxidize ferrous oxide in the present invention, makes ferrous ions into iron ion.
Concentrated hydrochloric acid, is used as being dissolved in the water to form hydrochloric acid solution in the present invention, in order to dissolve iron oxide, calcium oxide,
Achieve the purpose that to remove titanium dioxide, silica.
Sodium carbonate liquor, is used in the present invention and calcium ion generates precipitation of calcium carbonate.
Carbon dioxide, is used as in the present invention and calcium hydroxide reaction generates precipitation of calcium carbonate.
Ethanol solution, is used as the reactant for preparing porous silica titanium catalyst, for dissolving metatitanic acid four in the present invention
Butyl ester.
Ferric sulfate, in the present invention in be used as the main reactant for preparing porous silica titanium catalyst, for providing iron
Ion.
Butyl titanate, is used as being used as the key reaction for preparing porous silica titanium catalyst in preparing in the present invention
Thing, as titanium source.
The invention has the advantages that：
1. the technological means of flyash of the present invention pretreatment can efficiently remove silica in flyash,
Ferrous oxide, iron oxide, calcium oxide and titanium dioxide, improve the content of calcium carbonate in flyash, and then high for follow-up lifting
The preparation of purity precipitated calcium carbonate hides the foreshadowing.The present invention first aoxidizes ferrous oxide using hydrogen peroxide, makes ferrous ion oxygen
It is melted into iron ion；Then solution is generated, and then is removed silica, titanium dioxide with hydrochloric acid and iron oxide, calcium oxide reaction
The effect of titanium；Then ferrous metal chelating agent chelant iron ion is used, so as to reach the effect of iron ions；Finally by molten
Sodium carbonate liquor is added in liquid system, calcium ion is formed precipitation, generates the calcium carbonate powder crude product of preliminary purification.
2. technological means of the present invention employed in carbonisation can shorten the same of time for preparing precipitated calcium carbonate
When, improve the purity of precipitated calcium carbonate.The present invention first makes calcium oxide and water generate calcium hydroxide precipitation in carbonisation；So
Add the porous silica titanium catalyst doped with iron ion afterwards, by under the catalytic action of iron ion, make calcium hydroxide and
Carbon dioxide contacts rapidly, then aids in the treatment conditions with ultrasonic wave, calcium hydroxide is constantly vibrated and is disperseed, and further increases
With the contact area of carbon dioxide, and then generate high-purity precipitated calcium carbonate.Each technological means of the present invention is mutual
Coordinate, mutually promote, is indispensable, the total effect reached is significantly larger than the simple of the effect acquired by single technological means
Adduction.
3. it is titanium doped to have started porous silica doped with iron ion for the porous silica C catalyst prepared by the present invention
The new tool of metal ion.The present invention uses sol-gel process, using ferric sulfate as Doped ions presoma, in the environment of ethanol
Under be stirred, while be slowly added to the titanium source of butyl titanate, after alcohol precipitation, roasting, obtain doped with the more of iron ion
Porous titanium dioxide catalyst.
【Embodiment】
Embodiment 1：
1. early-stage preparations
The preparation of porous silica titanium catalyst：Count in parts by weight, 100 parts of mass fractions are molten for 60% ethanol
Liquid, 1 part of surfactant and 2 parts of ferric sulfate are put into reactor, are started agitating device, are stirred in the speed of 300r/min
Mix, while 10 parts of butyl titanates are added with the speed of 2mL/min, the reaction was continued 2h after vacuum distillation, uses absolute ethyl alcohol
Precipitated, collect sediment, and 25min is rinsed with pure water, holding backwash rate is 25L/ (m2S), by after flushing
Sediment is placed on after Muffle furnace roasted, and obtains the porous silica titanium catalyst doped with iron ion.
Above-mentioned prepared material is used in following preparation methods.
2. a kind of method with coal ash for manufacturing for precipitated calcium carbonate, comprises the following steps：
(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor
In, 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids are added, filtering, adds 3 parts of ferrous metal chelating agent chelant iron ions, first in filtrate
After carrying out at microwave, filtering, the sodium carbonate liquor that 50 parts of mass fractions are 15% is added in filtrate and is precipitated, taking precipitate
It is dried, obtains calcium carbonate powder crude product；
(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, is rapidly heated with the speed of 50 DEG C/min to 700 DEG C,
2h is roasted, obtains lime powder；
(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor
In, the packed sack for having porous silica titanium catalyst is put into deionized water, is 1200W, temperature in ultrasonication power
Spend and be carbonized to be passed through carbon dioxide under conditions of 40 DEG C, the pressure that reaction system is kept during carbonization is
2.5MPa, react 45min after, obtained sediment is calcium carbonate crystal, by calcium carbonate crystal at 110 DEG C heated-air drying
5h, obtains the precipitated calcium carbonate finished product that water content is 1%.
After testing, the purity of precipitated calcium carbonate is 99.93%.
Embodiment 2：
1. early-stage preparations
The preparation of porous silica titanium catalyst：Count in parts by weight, 100 parts of mass fractions are molten for 63% ethanol
Liquid, 1 part of surfactant and 2 parts of ferric sulfate are put into reactor, are started agitating device, are stirred in the speed of 400r/min
Mix, while 10 parts of butyl titanates are added with the speed of 2mL/min, the reaction was continued 2.5h, after vacuum distillation, with anhydrous second
Alcohol is precipitated, and collects sediment, and rinses 25min with pure water, and holding backwash rate is 30L/ (m2S), by after flushing
Sediment be placed on after Muffle furnace roasted, obtain the porous silica titanium catalyst doped with iron ion.
Above-mentioned prepared material is used in following preparation methods.
2. a kind of method with coal ash for manufacturing for precipitated calcium carbonate, comprises the following steps：
(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor
In, 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids are added, filtering, adds 3 parts of ferrous metal chelating agent chelant iron ions, first in filtrate
After carrying out at microwave, filtering, the sodium carbonate liquor that 50 parts of mass fractions are 15% is added in filtrate and is precipitated, taking precipitate
It is dried, obtains calcium carbonate powder crude product；
(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, is rapidly heated with the speed of 55 DEG C/min to 800 DEG C,
2h is roasted, obtains lime powder；
(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor
In, the packed sack for having porous silica titanium catalyst is put into deionized water, is 1400W, temperature in ultrasonication power
Spend and be carbonized to be passed through carbon dioxide under conditions of 45 DEG C, the pressure that reaction system is kept during carbonization is
3.0MPa, react 45min after, obtained sediment is calcium carbonate crystal, by calcium carbonate crystal at 113 DEG C heated-air drying
6.5h, obtains the precipitated calcium carbonate finished product that water content is 0.7%.
After testing, the purity of precipitated calcium carbonate is 99.92%.
Embodiment 3：
1. early-stage preparations
The preparation of porous silica titanium catalyst：Count in parts by weight, 100 parts of mass fractions are molten for 68% ethanol
Liquid, 1 part of surfactant and 2 parts of ferric sulfate are put into reactor, are started agitating device, are stirred in the speed of 500r/min
Mix, while 10 parts of butyl titanates are added with the speed of 2mL/min, the reaction was continued 2.5h, after vacuum distillation, with anhydrous second
Alcohol is precipitated, and collects sediment, and rinses 25min with pure water, and holding backwash rate is 33L/ (m2S), by after flushing
Sediment be placed on after Muffle furnace roasted, obtain the porous silica titanium catalyst doped with iron ion.
Above-mentioned prepared material is used in following preparation methods.
2. a kind of method with coal ash for manufacturing for precipitated calcium carbonate, comprises the following steps：
(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor
In, 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids are added, filtering, adds 3 parts of ferrous metal chelating agent chelant iron ions, first in filtrate
After carrying out at microwave, filtering, the sodium carbonate liquor that 50 parts of mass fractions are 15% is added in filtrate and is precipitated, taking precipitate
It is dried, obtains calcium carbonate powder crude product；
(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, is rapidly heated with the speed of 57 DEG C/min to 850 DEG C,
2h is roasted, obtains lime powder；
(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor
In, the packed sack for having porous silica titanium catalyst is put into deionized water, is 1500W, temperature in ultrasonication power
Spend and be carbonized to be passed through carbon dioxide under conditions of 50 DEG C, the pressure that reaction system is kept during carbonization is
3.4MPa, react 45min after, obtained sediment is calcium carbonate crystal, by calcium carbonate crystal at 112 DEG C heated-air drying
6h, obtains the precipitated calcium carbonate finished product that water content is 0.8%.
After testing, the purity of precipitated calcium carbonate is 99.95%.
Embodiment 4：
1. early-stage preparations
The preparation of porous silica titanium catalyst：Count in parts by weight, 100 parts of mass fractions are molten for 70% ethanol
Liquid, 1 part of surfactant and 2 parts of ferric sulfate are put into reactor, are started agitating device, are stirred in the speed of 550r/min
Mix, while 10 parts of butyl titanates are added with the speed of 2mL/min, the reaction was continued 3h after vacuum distillation, uses absolute ethyl alcohol
Precipitated, collect sediment, and 25min is rinsed with pure water, holding backwash rate is 28L/ (m2S), by after flushing
Sediment is placed on after Muffle furnace roasted, and obtains the porous silica titanium catalyst doped with iron ion.
Above-mentioned prepared material is used in following preparation methods.
2. a kind of method with coal ash for manufacturing for precipitated calcium carbonate, comprises the following steps：
(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor
In, 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids are added, filtering, adds 3 parts of ferrous metal chelating agent chelant iron ions, first in filtrate
After carrying out at microwave, filtering, the sodium carbonate liquor that 50 parts of mass fractions are 15% is added in filtrate and is precipitated, taking precipitate
It is dried, obtains calcium carbonate powder crude product；
(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, is rapidly heated with the speed of 61 DEG C/min to 900 DEG C,
2h is roasted, obtains lime powder；
(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor
In, the packed sack for having porous silica titanium catalyst is put into deionized water, is 1600W, temperature in ultrasonication power
Spend and be carbonized to be passed through carbon dioxide under conditions of 52 DEG C, the pressure that reaction system is kept during carbonization is
2.9MPa, react 45min after, obtained sediment is calcium carbonate crystal, by calcium carbonate crystal at 114 DEG C heated-air drying
7h, obtains the precipitated calcium carbonate finished product that water content is 0.5%.
After testing, the purity of precipitated calcium carbonate is 99.92%.
Embodiment 5：
1. early-stage preparations
The preparation of porous silica titanium catalyst：Count in parts by weight, 100 parts of mass fractions are molten for 68% ethanol
Liquid, 1 part of surfactant and 2 parts of ferric sulfate are put into reactor, are started agitating device, are stirred in the speed of 450r/min
Mix, while 10 parts of butyl titanates are added with the speed of 2mL/min, the reaction was continued 3h after vacuum distillation, uses absolute ethyl alcohol
Precipitated, collect sediment, and 25min is rinsed with pure water, holding backwash rate is 35L/ (m2S), by after flushing
Sediment is placed on after Muffle furnace roasted, and obtains the porous silica titanium catalyst doped with iron ion.
Above-mentioned prepared material is used in following preparation methods.
2. a kind of method with coal ash for manufacturing for precipitated calcium carbonate, comprises the following steps：
(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor
In, 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids are added, filtering, adds 3 parts of ferrous metal chelating agent chelant iron ions, first in filtrate
After carrying out at microwave, filtering, the sodium carbonate liquor that 50 parts of mass fractions are 15% is added in filtrate and is precipitated, taking precipitate
It is dried, obtains calcium carbonate powder crude product；
(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, is rapidly heated with the speed of 64 DEG C/min to 920 DEG C,
2h is roasted, obtains lime powder；
(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor
In, the packed sack for having porous silica titanium catalyst is put into deionized water, is 1700W, temperature in ultrasonication power
Spend and be carbonized to be passed through carbon dioxide under conditions of 51 DEG C, the pressure that reaction system is kept during carbonization is
4.1MPa, react 45min after, obtained sediment is calcium carbonate crystal, by calcium carbonate crystal at 113 DEG C heated-air drying
7h, obtains the precipitated calcium carbonate finished product that water content is 0.9%.
After testing, the purity of precipitated calcium carbonate is 99.90%.
Embodiment 6：
1. early-stage preparations
The preparation of porous silica titanium catalyst：Count in parts by weight, 100 parts of mass fractions are molten for 73% ethanol
Liquid, 1 part of surfactant and 2 parts of ferric sulfate are put into reactor, are started agitating device, are stirred in the speed of 600r/min
Mix, while 10 parts of butyl titanates are added with the speed of 2mL/min, the reaction was continued 3h after vacuum distillation, uses absolute ethyl alcohol
Precipitated, collect sediment, and 25min is rinsed with pure water, holding backwash rate is 40L/ (m2S), by after flushing
Sediment is placed on after Muffle furnace roasted, and obtains the porous silica titanium catalyst doped with iron ion.
Above-mentioned prepared material is used in following preparation methods.
2. a kind of method with coal ash for manufacturing for precipitated calcium carbonate, comprises the following steps：
(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor
In, 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids are added, filtering, adds 3 parts of ferrous metal chelating agent chelant iron ions, first in filtrate
After carrying out at microwave, filtering, the sodium carbonate liquor that 50 parts of mass fractions are 15% is added in filtrate and is precipitated, taking precipitate
It is dried, obtains calcium carbonate powder crude product；
(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, is rapidly heated with the speed of 65 DEG C/min to 1000
DEG C, 2h is roasted, obtains lime powder；
(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor
In, the packed sack for having porous silica titanium catalyst is put into deionized water, is 1800W, temperature in ultrasonication power
Spend and be carbonized to be passed through carbon dioxide under conditions of 55 DEG C, the pressure that reaction system is kept during carbonization is
4.5MPa, react 45min after, obtained sediment is calcium carbonate crystal, by calcium carbonate crystal at 120 DEG C heated-air drying
8h, obtains the precipitated calcium carbonate finished product that water content is 0.5%.
After testing, the purity of precipitated calcium carbonate is 99.93%.
Described above is the detailed description for the present invention preferably possible embodiments, but embodiment is not limited to this hair
Bright patent claim, equal change or the modification change completed under the technical spirit suggested by all present invention, should all belong to
Cover the scope of the claims in the present invention.
Claims (6)
- A kind of 1. method with coal ash for manufacturing for precipitated calcium carbonate, it is characterised in that：Comprise the following steps：(1) flyash pre-processes：Count in parts by weight, 200 parts of flyash and 500 parts of deionized waters are put into reactor, are added Enter 1 part of hydrogen peroxide and 15 parts of concentrated hydrochloric acids, filter, 3 parts of ferrous metal chelating agent chelant iron ions are added in filtrate, filter, Add the sodium carbonate liquor that 50 parts of mass fractions are 15% in filtrate to be precipitated, taking precipitate is dried, and obtains calcium carbonate Powder crude product；(2) roast：Calcium carbonate powder crude product is put into Muffle furnace, be rapidly heated to 700 with the speed of 50~65 DEG C/min~ 1000 DEG C, 2h is roasted, obtains lime powder；(3) it is carbonized：Count in parts by weight, 100 parts of lime powders and 5000 parts of deionized waters are put into carbonization reactor, will The packed sack for having porous silica titanium catalyst is put into deionized water, is 1200~1800W, temperature in ultrasonication power Spend and be carbonized to be passed through carbon dioxide under conditions of 40~55 DEG C, the pressure that reaction system is kept during carbonization is 2.5~4.5MPa, after reacting 45min, obtained sediment is calcium carbonate crystal, and calcium carbonate crystal is carried out at heated-air drying After reason, precipitated calcium carbonate finished product is obtained.
- A kind of 2. method with coal ash for manufacturing for precipitated calcium carbonate according to claim 1, it is characterised in that：Step (3) The porous silica titanium catalyst is prepared by following methods：Count in parts by weight, 100 parts of ethanol solutions, 1 part of surface are lived Property agent and 2 parts of ferric sulfate be put into reactor, start agitating device, be stirred in the speed of 300~600r/min, at the same with The speed of 2mL/min adds 10 parts of butyl titanates, the reaction was continued 2~3h, after vacuum distillation, is sunk with absolute ethyl alcohol Form sediment, collect sediment, and 25min is rinsed with pure water, holding backwash rate is 25~40L/ (m2S), will be heavy after flushing Starch is placed on after Muffle furnace roasted, and obtains the porous silica titanium catalyst doped with iron ion.
- A kind of 3. method with coal ash for manufacturing for precipitated calcium carbonate according to claim 2, it is characterised in that：The second The mass fraction of alcoholic solution is 60~73%.
- A kind of 4. method with coal ash for manufacturing for precipitated calcium carbonate according to claim 1, it is characterised in that：Step (1) The ferrous metal chelating agent is used under conditions of assisted microwave synthesis.
- A kind of 5. method with coal ash for manufacturing for precipitated calcium carbonate according to claim 1, it is characterised in that：Step (3) The parameter of described heated-air drying processing is：Temperature is 110~120 DEG C, drying time is 5~8h.
- A kind of 6. method with coal ash for manufacturing for precipitated calcium carbonate according to claim 1, it is characterised in that：Step (3) The water content of the precipitated calcium carbonate finished product is 0.5~1%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392101A (en) * | 2002-07-29 | 2003-01-22 | 上海天福机电化工技术研究所 | Process for producing nano calcium carbonate by ultrasonic cavitation technology |
| CN102466620A (en) * | 2010-11-01 | 2012-05-23 | 袁俊海 | Method for measuring influence of addition amount of heavy metal chelator to iron ion clearance |
| CN104114721A (en) * | 2011-12-21 | 2014-10-22 | 康莱克斯材料有限公司 | Recovery method for a continuous calcium extraction and PCC production |
-
2017
- 2017-12-15 CN CN201711347776.0A patent/CN107915247A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392101A (en) * | 2002-07-29 | 2003-01-22 | 上海天福机电化工技术研究所 | Process for producing nano calcium carbonate by ultrasonic cavitation technology |
| CN102466620A (en) * | 2010-11-01 | 2012-05-23 | 袁俊海 | Method for measuring influence of addition amount of heavy metal chelator to iron ion clearance |
| CN104114721A (en) * | 2011-12-21 | 2014-10-22 | 康莱克斯材料有限公司 | Recovery method for a continuous calcium extraction and PCC production |
Non-Patent Citations (1)
| Title |
|---|
| 郝妮等: ""粉煤灰制备碳酸钙和硅酸钙填料在造纸中的应用"", 《江苏造纸》 * |
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Application publication date: 20180417 |