CN100503743C

CN100503743C - Method for producing ferric oxide black pigment from titanium pigment waste slag copperas

Info

Publication number: CN100503743C
Application number: CNB2007101304288A
Authority: CN
Inventors: 黄平峰
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-07-18
Filing date: 2007-07-18
Publication date: 2009-06-24
Anticipated expiration: 2027-07-18
Also published as: CN101077945A

Abstract

The process of producing iron oxide black with titanium white slag and green vitriol includes the following steps: dissolving titanium white slag and green vitriol in water, vapor heating to 60-100 deg.c, adding calcium carbonate powder slowly, regulating pH value to 3-5, maintaining for over 30 min, clarifying or filtering to obtain light green transparent ferrous sulfate solution, neutralizing the ferrous sulfate solution with sodium hydroxide or liquid ammonia to pH 7-10, oxidizing with air to obtain iron oxide black slurry, water washing the iron oxide black slurry, pressure filtering, drying, and crushing to obtain iron oxide black product. The process can lower the titanium content in water solution of ferrous sulfate to below 0.05 % and raise the quality of iron oxide black product, and has the advantages of simplicity and low production cost.

Description

Method with producing ferric oxide black pigment from titanium pigment waste slag copperas

Technical field

The present invention relates to a kind of production method of pigment, be specifically related to a kind of method with producing ferric oxide black pigment from titanium pigment waste slag copperas.

Background technology

Produce titanium dioxide with ilmenite for the raw material sulphuric acid method, one ton of titanium dioxide of every production will produce 3.5-4 ton green vitriol, the major ingredient of green vitriol is an iron vitriol, green vitriol can be used for producing ferric oxide series pigment, but the titanium white waste residue green vitriol that produces owing to the production titanium dioxide can contain some impurity, so influenced the quality of producing pigment, for example when producing black iron oxide pigment, owing to contain free sulfuric acid and titanyl sulfate in the titanium white waste residue green vitriol, free sulfuric acid content is about 0.5-1.0%, and titanium content is (with TiO ₂Expression) content is about 0.5-1.5%, and these impurity can have a significant impact indexs such as the iron level of product, tones, can increase production cost and remove these impurity.

Summary of the invention

The technical problem to be solved in the present invention provides a kind of can improving the quality of products, and the method with producing ferric oxide black pigment from titanium pigment waste slag copperas that technology is simple, production cost is low.

The technical scheme that addresses the above problem is: soluble in water titanium white waste residue green vitriol, use steam heating, controlled temperature is at 60-100 ℃, add calcium carbonate powders while stirring, regulating the pH value is 3-5, insulation is no less than 30 minutes, and turbid solution clarification or filtration are obtained the transparent copperas solution of light green; With caustic soda or liquefied ammonia neutralisation of sulphuric acid ferrous iron solution to pH value is 7-10; Obtain the iron oxide black slip with atmospheric oxidation again, the iron oxide black slip is washed successively, press filtration, drying, pulverized, obtains iron black product.

When the titanium white waste residue green vitriol aqueous solution being purified, can make titanium content in the ferrous sulfate aqueous solution (with TiO with the inventive method ₂Expression), thereby improved the quality of black iron oxide pigment product greatly smaller or equal to 0.05%.

The inventive method has the measured advantage of iron oxide black product matter that technology is simple, production cost is low, make.

Embodiment

The inventive method mainly comprises purification, neutralization, three processes of oxidation, and specific implementation method is:

1 purifies:

In the dissolving tank that band stirs, add a certain amount of water, add titanium white waste residue green vitriol again and stir, the concentration of control ferrous sulfate (is pressed FeSO ₄7H ₂The O meter) in the 350-600g/l scope, and make its dissolving by steam, temperature is warmed up to 60-100 ℃, add lime carbonate while stirring, described lime carbonate can be water-ground limestone and/or light calcium carbonate, water-ground limestone wherein such as limestone powder, dry powder, calcite in powder etc., or other main chemical is CaCO ₃Material, when reaching 3-5, the pH value is terminal point, continue insulation and be no less than 30 minutes, guarantee the abundant hydrolysis of titanyl sulfate, this suspension is put into the settling pond clarification, or adopt to filter machinery (as pressure filter, band filter etc.) and filter, promptly obtain meeting the copperas solution of the clarification green transparent that black iron oxide pigment produces.

The titanium content of this copperas solution is (with TiO ₂Meter) less than 0.05%.

The reaction principle of said process is:

TiOSO ₄+2H ₂O＝H ₂TiO ₃↓+H ₂SO ₄

H ₂SO ₄+ CaCO ₃=CaSO ₄+ CO ₂Individual+H ₂O

2 neutralizations

Adding neutralization bucket through the copperas solution that purifies, be diluted with water to 200-350g/l, adding caustic soda or liquefied ammonia are neutralized to the pH value and are 7-10;

3 oxidations

Be transported to the oxidation bucket with above-mentioned through neutral solution, with 90-95 ℃ of steam controlled temperature, bubbling air oxidation; The iron oxide black slip that oxidation obtains after finishing passes through washing, press filtration, drying more successively, pulverizes, is packaged to be iron black product.

Be the specific embodiment of scavenging process below, A#～C# is a copperas solution correlation data of not doing any purifying treatment, 1#～9# be with lime carbonate carry out under different condition that the above-mentioned the first step purifies that copperas solution handles data;

Concentration in the form (g/L) is meant that the concentration that titanium white waste residue green vitriol is put into the ferrous sulfate that the stirring and dissolving groove that adds water controlled (presses FeSO ₄7H ₂The O meter), the pH value is meant and adds the pH value that lime carbonate is controlled that titanium content is meant that the titanium content that purifies the back copperas solution is (with TiO ₂Meter)

Table 1

Numbering	Concentration (g/L)	Temperature (℃)	The pH value	Titanium content (%)
Numbering	Concentration (g/L)	Temperature (℃)	The pH value	Titanium content (%)	A	405	60℃	0.5	0.95
B	466	80℃	0.5	0.87	A	405	60℃	0.5	0.95
B	466	80℃	0.5	0.87	C	538	100℃	0.5	1.04
1	355	60℃	3	0.05	C	538	100℃	0.5	1.04
1	355	60℃	3	0.05	2	368	80℃	3	0.04
3	402	100℃	3	0.03	2	368	80℃	3	0.04
3	402	100℃	3	0.03	4	420	60℃	4	0.05
5	432	80℃	4	0.03	4	420	60℃	4	0.05
5	432	80℃	4	0.03	6	446	100℃	4	0.02
7	492	60℃	5	0.03	6	446	100℃	4	0.02
7	492	60℃	5	0.03	8	525	80℃	5	0.02
9	580	100℃	5	0.01	8	525	80℃	5	0.02

Above-mentioned treated 12 batches ferrous sulfate aqueous solution is carried out the neutralization of aforementioned the 2nd step more respectively, obtain 12 batches iron oxide black product (the pH value with process in it is 8, and oxidizing temperature is 93 ℃) after the oxidation of the 3rd step;

Now the quality of 12 batches of iron oxide black products is done a contrast and carried out mass analysis, analytical data sees the following form:

Table 2

Numbering	Fe ₃O ₄Content (%)	Lightness (L*)	Red value (a*) mutually	Huang is worth (b*) mutually
Numbering	Fe ₃O ₄Content (%)	Lightness (L*)	Red value (a*) mutually	Huang is worth (b*) mutually	A	92.6	59.24	-1.18	-5.86
B	92.3	59.48	-1.21	-5.94	A	92.6	59.24	-1.18	-5.86

C	92.8	58.86	-1.14	-5.52
C	92.8	58.86	-1.14	-5.52	1	95.5	62.08	-1.48	-8.21
2	95.8	62.26	-1.45	-8.36	1	95.5	62.08	-1.48	-8.21
2	95.8	62.26	-1.45	-8.36	3	95.8	62.21	-1.46	-8.32
4	95.7	62.12	-1.49	-8.28	3	95.8	62.21	-1.46	-8.32
4	95.7	62.12	-1.49	-8.28	5	96.1	62.55	-1.52	-8.46
6	95.9	62.47	-1.51	-8.42	5	96.1	62.55	-1.52	-8.46
6	95.9	62.47	-1.51	-8.42	7	95.8	62.52	-1.52	-8.48
8	96.2	62.58	-1.48	-8.62	7	95.8	62.52	-1.52	-8.48
8	96.2	62.58	-1.48	-8.62	9	96.1	62.47	-1.48	-8.58

In last table:

1, to the Fe in the iron oxide black product ₃O ₄Content adopts chemical analysis;

2, color data is to use the color difference meter analysis after iron oxide black is made reduced tint with titanium dioxide, color data CIE1976L*a*b* chrominance space data representation:

3, lightness (L*): numerical value is big more, and lightness is good more, and quality product is also good more;

4, red value (a*) mutually: on the occasion of being red phase, negative value is green phase;

5, Huang is worth (b*) mutually: on the occasion of being yellow phase, negative value is blue phase, and negative value is big more, and Lan Xiangyue is good.

Above-mentioned data declaration, after titanium white waste residue green vitriol being purified as scavenging agent with lime carbonate, titanium content (representing with TiO2) in the ferrous sulfate aqueous solution is dropped to be not more than 0.05%, thereby black iron oxide pigment iron level height, the indigo plant of using this ferrous sulfate aqueous solution to produce are worth height mutually, have improved product quality.

The common pH value of N-process of producing iron oxide black with titanium white waste residue green vitriol is 7-10, oxidizing temperature is 90-95 ℃, above-mentioned table 2 is to be 8 in the pH value, oxidizing temperature is the numerical value that obtains under 93 ℃ of conditions, the product that obtains under other identical neutralization, oxidizing condition also all embodies the result identical with table 2: use the iron-holder of the iron oxide black product that the ferrous sulfate aqueous solution that purified through lime carbonate produces and blue value, tone mutually to be better than usefulness and do not do the iron oxide black product that the ferrous sulfate aqueous solution of any purifying treatment is produced.

Claims

1, uses the method for producing ferric oxide black pigment from titanium pigment waste slag copperas, it is characterized in that: soluble in water titanium white waste residue green vitriol, use steam heating, controlled temperature is at 60-100 ℃, add calcium carbonate powders while stirring, regulating the pH value is 3-5, and insulation is no less than 30 minutes, and turbid solution clarification or filtration are obtained the transparent copperas solution of light green; With caustic soda or liquefied ammonia neutralisation of sulphuric acid ferrous iron solution to pH value is 7-10; Obtain the iron oxide black slip with atmospheric oxidation again, the iron oxide black slip is washed successively, press filtration, drying, pulverized, obtains iron black product.

2, the method with producing ferric oxide black pigment from titanium pigment waste slag copperas according to claim 1 is characterized in that: when soluble in water, the concentration of control ferrous sulfate is in the 350-600g/l scope titanium white waste residue green vitriol, and described ferrous sulfate is by FeSO ₄7H ₂The O meter.

3, the method with producing ferric oxide black pigment from titanium pigment waste slag copperas according to claim 1 and 2 is characterized in that: the copperas solution thin up that will obtain after will purifying with Paris white adds caustic soda or liquefied ammonia neutralizes again to 200-350g/l.

4, the method with producing ferric oxide black pigment from titanium pigment waste slag copperas according to claim 1 and 2 is characterized in that: the temperature that described process neutral copperas solution is carried out atmospheric oxidation is controlled at 90-95 ℃.

5, the method with producing ferric oxide black pigment from titanium pigment waste slag copperas according to claim 3 is characterized in that: the temperature that described process neutral copperas solution is carried out atmospheric oxidation is controlled at 90-95 ℃.

6, the method with producing ferric oxide black pigment from titanium pigment waste slag copperas according to claim 1 and 2, it is characterized in that: described lime carbonate is water-ground limestone and/or light calcium carbonate.