CN100338306C

CN100338306C - Method of making calcium carbonate for inner filling paper

Info

Publication number: CN100338306C
Application number: CNB991056809A
Authority: CN
Inventors: 俞圭在
Original assignee: Individual
Current assignee: Individual
Priority date: 1999-03-04
Filing date: 1999-03-04
Publication date: 2007-09-19
Anticipated expiration: 2019-03-04
Also published as: CN1266124A

Abstract

The present invention relates to a preparation method for calcium carbonate used for spindle-shaped inner filling paper with the short electric-display particle diameter of 0.2 to 0.3 mu m and the long electric-display particle diameter of 1.0+/-0.2 mu m. Carbon dioxide is led into lime milk processed by a sand mixer so as to prepare suspending liquid containing calcene of 0.04 mu m, and the other lime milk which is processed by the sand mixer and contains 0.01 to 0.20 mol/Ca (OH) 2 mol NH4Cl added in advance is added to the suspension liquid at the speed of 10 to 30 mol/CaCO3 mol; carbon dioxide gas is led into the mixture, and then the calcium carbonate used for inner filling paper can be prepared.

Description

The manufacture method of calcium carbonate for inner filling paper

As the synthetic calcium carbonate that produces by milk of lime and carbon dioxide gas precursor reactant, it is representational that to have electricity to show particle diameter be that cube calcene and the minor axis of 0.01-0.10 μ m is 0.2-0.5 μ m, major diameter is the spindle precipitated calcium carbonate of 1-20 μ m, is used in rubber, plastics, coating, printing ink, fluid sealant and paper industry respectively.

In paper-making industry as in fill out the paper filler, use relatively cheaply, be 0.2-0.3 μ m that major diameter is that the spindle calcium carbonate of 1-4 μ m is the precipitated calcium carbonate of main body with the high minor axis of whiteness.

Because thereby the opacity low, papermaking of the meticulous qualification rate of calcene particle in the calcium carbonate is also poor, the abrasion degree of its plastic silk screen of powdered whiting of only lime stone being pulverized classification is bad, so fusiform precipitated calcium carbonate is mainly used as only filler.

But because former precipitated calcium carbonate size distribution heterogeneity, the filler qualification rate in the time of can not satisfying papermaking, silk screen abrasion degree and in fill out paper whiteness, opacity, industry strong request granularity is the spindle calcium carbonate of homogeneous more.

In fill out the spindle calcium carbonate that paper uses and be called as precipitated calcium carbonate, but its manufacture method, different with the powdered whiting of only lime stone being pulverized classification, belong to the synthetic calcium carbonate of making by milk of lime and carbon dioxide gas precursor reactant, different with the fine calcene that shows particle diameter 0.04 μ m based on electricity, its minor axis is 0.2-0.5 μ m, and major diameter is 1-20 μ m, so the bigger particle of apparent specific volume is called precipitated calcium carbonate.

It is created conditions and differs widely.

1) calcene is in the milk of lime of 3-10%, 10-20 ℃ low concentration, low temperature, with the carbon dioxide of 20-40 volume % with 40-100l/minkg Ca (OH) ₂Speed importing faster, just imported after the carbon dioxide, produce the cube particle of a large amount of (or most) 0.04 μ m, the Ca (OH) in this cube particle articulated system quickly ₂Produce overbasic calcium carbonate, grow into the pin column after, in case after obtaining the gel state (zol-gel state) of very high granularity, continue carbonating again the Ca (OH) that is comprised in this pin columnar-shaped particle ₂Carbonating, in the end the pin columnar-shaped particle is split into CaCO the stage ₃, the apparent particle diameter of electricity that generates single homogeneous is the cube particle of 0.04 μ m.

In this reaction, the Ca (OH) before carbonating begins ₂With reacted Ca (OH) among high alkalinity calcium carbonate when becoming gel state ₂, particle diameter is all different with character, if the Ca (OH) before the former promptly reacts ₂Remaining same as before, then can not obtain the cube particle of 0.04 μ m of final homogeneous.

2) precipitated calcium carbonate is opposite with calcene, only generate the particle that a small amount of (or minority) becomes the 0.04 μ m of " kind " after just having imported carbon dioxide, because need be with it as protokaryon order growth, thus usually in the milk of lime of 10-15%, 30-50 ℃ higher concentration, high-temperature with 30-50l/minkg Ca (OH) ₂Speed the carbon dioxide of 20-40 volume % is imported more slowly thereby to make minor axis be that 0.2-0.3 μ m, major diameter are the spindle calcium carbonate of 1-4 μ m.

But existing precipitated calcium carbonate is as shown in Figure 2, other particles of growing up from the side of major diameter 1-4 μ m particle, and that is the macroparticle of the 1-20 μ m that adsorbing mutually, says closely, becomes the aggregate based on the particle that varies in size of spindle.

Therefore with its as in when filling out paper and using with filler, can not avoid filler qualification rate, an abrasion degree and in fill out the situation of the opacity difference of paper.

In order to reach the homogenization of this spindle particle, carried out all trials, but perhaps because consider that economy, present situation are the goods that do not have desired quality.

The present inventor follows the trail of with electron microscope at any time to course of reaction, the result of prudent research is, the particle chain lock that it is protokaryon with cubical crystallization of the oblique side of 0.04 μ m substantially that major diameter surpasses the lightweight particle of 1 μ m, its chain lock shape particle crystal stock that is parallel to each other is arranged regularly, at reaction end, the spindle particle is finished to form in two ends, unless recognize the reaction of in tighter homogeneous system, carrying out milk of lime and carbon dioxide, to the growth of different direction, generate the inevitable of the different shape aggregate that produces by sorption.

In order to overcome this shortcoming, repeated all experiments, if find correctly to observe particularly following 3, can be manufactured on the spindle calcium carbonate for inner filling paper of industrial also homogeneous fairly simplely.

1) wet type of milk of lime grinds

Behind the aquation quick lime, at least 1 month with its Ca of interior milk of lime (OH) ₂The mutual aggegation of particle become the above big aggegation piece of 1 μ m, if it is ground with wet types such as puddle mixers, can understand easy dispersion and obtain original electricity to show particle diameter be the primary particle of 0.1 μ m, think that using SM milk of lime is at first the 1st condition that reaches institute's phase purpose.

2) by adding the kind reaction that former nuclear particle produces

When milk of lime and carbon dioxide gas precursor reactant, few as far as possible calcium carbonate of making the 0.04 μ m that becomes nuclear that generates after the reaction just substitutes initial Ca (OH) ₂Carbonating slowly, former nuclear particle separate out CaCO along crystallography C direction of principal axis ₃, the particle parallel crystal stock of growing up, and adopt in the turbid liquid through the former nuclear particle of adjusting the 0.04 μ m that makes in addition in advance, 10～30mol/CaCO added ₃Behind the SM milk of lime of mol, mode that the what is called of beginning carbonation reaction " is planted reaction ".

The Ca that in calcene, adds (OH) ₂Amount less than 10mol/CaCO ₃Mol and when surpassing 30mol all causes the size distribution heterogeneity, can not obtain filling out the paper rerum natura in desired.

As creating conditions of the calcene of 0.04 μ m of this former nuclear particle, except that puddle mixer is handled, can adopt common in 3-10%, 10-20 ℃ milk of lime with 40-100l/minkg Ca (OH) ₂Speed method that 20-40 volume % carbon dioxide is imported.

And adding NH ₄The carbonating condition of Cl SM milk of lime, be not resemble before in 10-15%, 30-50 ℃ milk of lime with 30-50l/minkg Ca (OH) ₂Speed import the carbon dioxide of 20-40 volume %, but by in 3-10%, 10-30 ℃ SM milk of lime with 20-80l/minkgCa (OH) ₂Speed import the carbon dioxide of 20-40 volume %, at first obtaining particle diameter is 0.2-0.3 μ m, major diameter is the spindle calcium carbonate for inner filling paper of 1 ± 0.2 μ m.

3) add NH ₄Cl

If in advance NH ₄Cl adds in the milk of lime, does not then grow to different shape direction in carbonation, therefore can obtain the spindle particle of final homogeneous particle diameter.

Can think that this is owing to there is NH ₄The Cl of Cl ^-1(Cl ion) becomes CaCl ₂, NH ₄ ⁺Become (NH ₄) ₂CO ₃The liquid phase reactor effect, the CaCO that separates out ₃At any time the phenomenon that generates on the surface of former nuclear particle is being added NH ₄When importing carbon dioxide in the SM milk of lime of Cl, CaCO takes place to promote ₃Phenomenon along the C direction of principal axis growth of examining.

Therefore by CaCl ₂(NH ₄) ₂CO ₃Separate out CaCO ₃After, revert to original NH ₄Cl, as if NH ₄The action effect of Cl catalyst is until final.

But NH ₄The adding rate of Cl is at 0.01-0.20mol/CaCO ₃Mol is necessary, is difficult to prevent the mutual aggegation of spindle particle during not enough 0.01mol, and unusual the growth sharply increases when surpassing 0.20mol.

The present invention is by all satisfying above 3, produce desired when making papermaking filler qualification rate, silk screen abrasion degree and in fill out the spindle calcium carbonate of the splendid size distribution homogeneous of whiteness, the opacity of paper.

And precipitated calcium carbonate of the present invention except that in fill out paper with, behind the dry classification, promptly be used in rubber, plastics, coating, printing ink, fluid sealant and also can effectively utilize.

Embodiment and comparative example are shown below.

Embodiment 1

1) Ca (OH) ₂Carry out wet type with puddle mixer and grind, make grinding standard specification granularity reach 5 μ m 0% (zero), be adjusted to after 5%, 15 ℃, with 60l/minkg Ca (OH) ₂Speed import the carbon dioxide of 30 volume %, be that 6.8 o'clock carbonatings finish at pH, obtain the cube calcium carbonate of 0.04 μ m.

2) identical SM milk of lime is adjusted into 8%, 20 ℃ after, with 0.1mol/Ca (OH) ₂The amount of mol is added 8%, 20 ℃ NH ₄Behind the Cl, with respect to above-mentioned 1) the CaCO of 0.04 μ m ₃Turbid liquid is pressed 15mol/CaCO ₃The amount of mol adds,

3) with 50l/minkg Ca (OH) ₂Speed import the carbon dioxide of 30 volume %, be 6.8 as terminal point with pH, be 65% to fill out the paper filler in making thereby dewater to solid constituent with centrifugal separator.

For the difference of clear and definite and embodiment 1, be summarized in table 1 expression embodiment 2-4, comparative example 1-5.The value identical with embodiment 1 represented on empty hurdle in the table.

Fig. 1 and Fig. 2 represent the particle configuration of goods of the present invention and former goods respectively.

The invention provides to make and comprise in rice paper general and fill out paper usefulness, filler qualification rate height when making papermaking, The optical characteristics such as the abrasion degree reduction of plastic silk screen, whiteness, opacity, the excellent paper of filling out in costly The filler of less expensive is therefore owing to as powder whiteness, covering power height, easily disperse, so also as rubber The filler of glue, plastics, coating, ink, fluid sealant etc. uses, and is very big to the relevant industries contribution.

[table 1]

	0.04μmCaCO ₃Create conditions						Creating conditions of precipitated calcium carbonate								The product of generation particle diameter
	0.04μmCaCO ₃Create conditions						Creating conditions of precipitated calcium carbonate									Milk of lime			Carbon dioxide		Particle diameter	NH ₄Cl			Ca(OH) ₂			Carbon dioxide
	SM processes	Concentration	Temperature	Concentration	Flow	The aobvious particle diameter of electricity	Adding rate	Concentration	Temperature	Adding rate	Concentration	Temperature	Concentration	Flow		Milk of lime			Carbon dioxide		Particle diameter	NH ₄Cl			Ca(OH) ₂			Carbon dioxide		The aobvious particle diameter of electricity
	SM processes	Concentration	Temperature	Concentration	Flow	The aobvious particle diameter of electricity	Adding rate	Concentration	Temperature	Adding rate	Concentration	Temperature	Concentration	Flow	Granularity μ m	％	℃	％	l/min kg Ca(OH) ₂	μm	mol/ Ca(OH) ₂mol	％	℃	mol/CaCO ₃ mol	％	℃	％	l/min kg Ca(OH) ₂	μm	The aobvious particle diameter of electricity
	Invention scope	5 μ m following 0%	3-10	10-20	20-40	40-100	0.04	0.01-0.20	3-10	10-30	10-30	3-10	10-30	20-40	Granularity μ m	％	℃	％	l/min kg Ca(OH) ₂	μm	mol/ Ca(OH) ₂mol	％	℃	mol/CaCO ₃ mol	％	℃	％	l/min kg Ca(OH) ₂	μm	20-80	Minor axis 0.2-0.3 major diameter 1 ± 0.2
Embodiment 1234	Invention scope	5 μ m following 0%	3-10	10-20	20-40	40-100	0.04	0.01-0.20	3-10	10-30	10-30	3-10	10-30	20-40	0	5	15	30	60	0.04	0.10	8	20	15	8	20	30	50	Minor axis 0.2 major diameter 1.0	20-80	Minor axis 0.2-0.3 major diameter 1 ± 0.2
							0.15								0	5	15	30	60	0.04	0.10	8	20	15	8	20	30	50	Minor axis 0.2 major diameter 1.0	Minor axis 0.2 major diameter 1.0
							0.15																	11					Minor axis 0.2 major diameter 1.0	Minor axis 0.2 major diameter 1.0
										25														11					Minor axis 0.2 major diameter 1.0	Minor axis 0.2 major diameter 1.0
										25					Comparative example 12345	Unreasonable *														Minor axis 0.2 major diameter 1.0	Minor axis 0.2 major diameter 15.8
						0								Minor axis 0.3 major diameter 12.5		Unreasonable *															Minor axis 0.2 major diameter 15.8
						0								Minor axis 0.3 major diameter 12.5											0					Minor axis 0.5 major diameter 15.0
									50					Minor axis 0.3 major diameter 19.5											0					Minor axis 0.5 major diameter 15.0
									50					Minor axis 0.3 major diameter 19.5								0.3								Minor axis 0.3 major diameter 10.0
* non-processor, more than the granularity 80 μ m																						0.3								Minor axis 0.3 major diameter 10.0

[table 2]

	Filler				In fill out paper rerum natura *
	Filler				In fill out paper rerum natura *					General rerum natura				Quantitative g/m²	Filler qualification rate %	Whiteness %	Opacity %	Scattering coefficient S cm²/g
	BET specific area m²/g	Covering power cm²/g	Oil absorption ml/100g	The abrasion degree Off_イル _エApplication formula mg						General rerum natura
	BET specific area m²/g	Covering power cm²/g	Oil absorption ml/100g	The abrasion degree Off_イル _エApplication formula mg	The present invention's product (spindle) of embodiment 1	14.5	32	86	180 fens 15mg	50.0	63.2	92.5	88.3						530
Existing commercially available product (spindle)	9.2	21	43	180 fens 110mg	The present invention's product (spindle) of embodiment 1	14.5	32	86	180 fens 15mg	50.0	63.2	92.5	88.3	49.9	27.5	89.4	84.1	501	530
Existing commercially available product (spindle)	9.2	21	43	180 fens 110mg	Commercially available powdered whiting (amorphous)	9.1	13	20	Cut off in 100 timesharing	50.0	25.2	88.0	76.3	49.9	27.5	89.4	84.1	501	420
Filling paper not	-	-	-	-	Commercially available powdered whiting (amorphous)	9.1	13	20	Cut off in 100 timesharing	50.0	25.2	88.0	76.3	49.2	0	84.7	71.2	270	420
Filling paper not	-	-	-	-	* fill out paper test Rp in and cooperate prescription (weight portion) filler: the quantitative 50g/m of target²LBKP 50 pulp beating degree: 250ml NBKP 50 copies paper concentration: during making beating 1.2%, after the making beating 0.15%										0	84.7	71.2	270

Claims

1. the manufacture method of calcium carbonate for inner filling paper is made of following steps, to handle with puddle mixer milk of lime-below be called that SM milk of lime-and the 0.04 μ m calcene made adds 10-30mol/CaCO ₃Mol has added 0.01-0.20mol/Ca (OH) in advance ₂Mol NH ₄The SM milk of lime of Cl obtains the size distribution homogeneous thereby import carbon dioxide, is 0.2-0.3 μ m according to the average grain diameter minor axis of electron microscope, and major diameter is the spindle calcium carbonate of 1.0 ± 0.2 μ m.

2. the manufacture method of the described calcium carbonate for inner filling paper of claim 1 is with 40-1001/minkg Ca (OH) in 3-10 weight %, 10-20 ℃ SM milk of lime ₂Thereby the speed carbon dioxide that imports 20-40 volume % produce the calcene of 0.04 μ m.

3. the manufacture method of the described calcium carbonate for inner filling paper of claim 1 is having added NH in advance ₄3-10 weight %, the 10-30 of Cl ℃ SM milk of lime adds in the calcium carbonate turbid liquid, with 20-801/minkg Ca (OH) ₂Speed import the method for carbon dioxide.