CN102745741A - Chlor-alkali and hydrochloric acid method integrated method for production of titanium-rich materials - Google Patents
Chlor-alkali and hydrochloric acid method integrated method for production of titanium-rich materials Download PDFInfo
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- CN102745741A CN102745741A CN2012102473960A CN201210247396A CN102745741A CN 102745741 A CN102745741 A CN 102745741A CN 2012102473960 A CN2012102473960 A CN 2012102473960A CN 201210247396 A CN201210247396 A CN 201210247396A CN 102745741 A CN102745741 A CN 102745741A
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Abstract
The invention relates to a chlor-alkali and hydrochloric acid method integrated method for production of titanium-rich materials in the field of titanium dioxide manufacturing. The method includes the steps: A, grinding ilmenite into powder, making the powder into slurry, and feeding hydrogen chloride; B, enabling the hydrogen chloride to react with ferric oxide to generate iron chloride and ferrous chloride; C, filtering, and washing and drying filter residue to obtain titanium-rich materials; D, adding sodium carbonate into filtrate to obtain precipitates including iron hydroxide and ferrous carbonate, namely siderite; E, re-filtering, and supplying the obtained siderite to steel works for iron making; and F, subjecting the filtered sodium chloride solution to reverse osmosis concentration, recycling the obtained purified water, and using the concentrated sodium chloride solution as raw materials for chloralkali plants. Hydrogen chloride which is a byproduct of the chloralkali plants is used for production of titanium-rich materials by means of the hydrochloric acid method, the byproduct sodium chloride in the filtrate in production of the titanium-rich materials is used as raw materials for the chloralkali plants, and the siderite is a raw material for iron making. Therefore, production cost is reduced, quality of the titanium-rich materials is improved, zero emission of 'three wastes' (waste water, waste gas and waste residues) is realized, and true green production is realized for the benefit of human.
Description
Technical field
The present invention relates to the manufacturing field of white pigment white titanium pigment, specifically be meant the method for the rich titanium material of a kind of chlor-alkali and salt acid system combination producing.
Background technology
White titanium pigment formal name used at school titanium oxide (TiO
2), be acknowledged as at present the most superior white pigment of performance in the world.It is nontoxic and have best opacity, best whiteness and a luminance brightness; Be widely used in industry such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, pottery, makeup, food and medicine; Be called as " industrial monosodium glutamate "; Its consumption per head also is a strong evidence of weighing this state's market potential as the important indicator of weighing a national economic development level.As the basic industry of China's economy, white titanium pigment is fundamentally affecting the development of industry-by-industry neural, often is described as " weather glass " of the national economic development.
The method of manufacture of white titanium pigment has two kinds, sulfuric acid process and chlorination.
The production operation program of sulfate process titanium dioxide production technique is very complicated, and its basic chemical reaction includes a series of simple chemical reaction, as by acidolysis, hydrolysis and the calcining etc. of iron ore concentrate as raw material.Sulfuric acid process mainly is to be raw material with ilmenite and sulfuric acid, resolves into TiOSO with sulfuric acid
4Solution removes by filter the insoluble impurities in the titanium liquid, removes FeSO through vacuum crystallization, solid-liquid separation then
47H
2O, thermal hydrolysis after concentrating makes metatitanic acid again, and soluble sulphate is removed in washing, bleaching and filter is done, and is converted into titanium oxide through the calcined dehydration desulfurization.Sulfuric acid process, one ton of white titanium pigment of every production produces 4-5 ton green vitriol, produces the spent acid of 8-10 ton 20% concentration, and these refuses all impact environment.Sulfuric acid process can only be produced low-grade titanium white product.
The chloride process titanium dioxide production technique is with containing rich titanium material, is containing under the situation that reducing material exists, and chlorine is fed carry out continuously in 800-1000 ℃ the chlorination reactor reaction gained TiCl
4Through rectification and purification, and then carry out gaseous oxidation, after speed is cold, obtain white titanium pigment through gas solid separation; It can high efficiency serialization, automated operation; Good product quality, directly " three wastes " of discharging will replace the sulfate process titanium dioxide production technique than sulfuric acid process much less.
The national industry structural adjustment instructs catalogue (basis in 2011) to encourage the 7th section of the 11 article regulation in the class; Encourage 30,000 tons/year of single line production capacities and above and to be not less than 90% rich titanium material (artificial rutile, natural rutile, titanium slag) with content of titanium dioxide be the chloride process titanium dioxide powder production project of raw material, and 11th item in the 4th clearly limits newly-built sulfate process titanium dioxide project in restricted.
Because the chloride process titanium dioxide manufacturing technique requirent produces (content of titanium dioxide is not less than 90% rich titanium material) with rich titanium material, supply falls short of demand in the world market for rich titanium material, and domestic still do not have a mass-producing manufacturing enterprise.
The rich titanium material of salt acid system production technology is an a kind of rich titanium material production technology newly developed in recent years; The technology of this technical finesse waste water is sour spray roasting; Make the iron(ic)chloride in the waste water, the oxide compound that iron protochloride is converted into iron, the chlorine root is converted into hydrochloric acid and is recycled, and this method is wanted a large amount of energy consumptions when concentrating waste water; And because calcium chloride, magnesium chloride decomposition temperature are higher; Cause contain a large amount of cl ionss in the oxidation scum and can't be used for ironmaking, add that the hydrogenchloride under the high temperature is very big to equipment corrosion, sulfide and phosphide are also sneaked into the hydrochloric acid recovery system in roasting process; Increased the impurity composition of hydrochloric acid, these effects limit applying of the rich titanium material manufacturing technique of salt acid system.
On the other hand, existing chlor-alkali enterprise also can produce a large amount of chlorine, i.e. chlorine or hydrogenchloride when producing caustic soda.Relied on the approach of PVC balance chlorine to cause whole industry loss in recent years, balance chlorine has been the cardinal task of current chlor-alkali enterprise.
To sum up, promote the production of chloride process titanium dioxide powder, enough rich titanium material must be arranged.The rich titanium material of salt acid system is produced, and not high to the ilmenite grade requirement, the products obtained therefrom quality is high, and production cost is low, is best manufacturing technology.And the production of the rich titanium material of salt acid system must solve the iron(ic)chloride waste water handling problem; Chlor-alkali enterprise is the important basic chemical industry industry of China, and the status is of crucial importance, and chlor-alkali enterprise also will solve the chlorine equilibrium problem.
Summary of the invention
In order to solve the problem of above-mentioned existence, the present invention provides the method for a kind of chlor-alkali and the rich titanium material of salt acid system combination producing.
The technical scheme that the present invention uses is following:
The method of the rich titanium material of a kind of chlor-alkali and salt acid system combination producing, it may further comprise the steps:
A, ilmenite powder is worn into powder, add pure water and process slurry, feed hydrogenchloride;
B, hydrogenchloride and red stone carry out the acidolysis chemical reaction, generate iron trichloride and iron protochloride;
C, filtration, filter residue makes rich titanium material after washing, drying;
D, in filtrating, add soda ash, throw out is ironic hydroxide and iron protocarbonate, i.e. spathic iron ore;
E, filtration once more, the spathic iron ore that obtains is supplied with Iron And Steel Plant's ironmaking;
F, sodium chloride solution carry out reverse osmosis concentration, and the gained pure water above-mentioned steps A that is used for capable of circulation processes slurry again, and the sodium chloride solution after concentrating becomes the raw material of chlor-alkali plant.
Said steps A is used crusher and ball mill two-stage mechanical disintegration, and powder particle size 70um sieving rate is greater than 70%, and the slurry solid-to-liquid ratio is 1: 4, and said hydrogenchloride is the chlor-alkali plant sub product.
Among the said step B, the molar concentration rate of hydrogenchloride and red stone is 2-3: 1, and the acidolysis chemical time is 4-6 hour.
Among said step C or the E, the applying pressure filtration unit filters.
Among the said step D in the spathic iron ore of gained chloride ion content less than 0.5%.
In the said step F, reverse osmosis membrane salt rejection is greater than 95%, and sodium chloride content is less than 5 grams per liters in the pure water, and sodium chloride content is greater than 300 grams per liters in the sodium chloride solution after concentrating.
Among the above-mentioned steps B, also generate micro-magnesium chloride, calcium chloride, Manganous chloride tetrahydrate, aluminum chloride; Among above-mentioned steps D or the E, also contain micro-magnesiumcarbonate, lime carbonate, manganous carbonate, white lake in the spathic iron ore.
The invention has the beneficial effects as follows:
(1) the rich titanium material of chlor-alkali and salt acid system combination producing, two factory's zero emission realize green manufacturing.The sub product hydrogenchloride that is chlor-alkali production is used for the production of the rich titanium material of salt acid system; The sub product sodium-chlor that rich titanium material is produced is as the raw material of chlor-alkali enterprise manufacturing caustic soda, and spathic iron ore is the raw material of ironmaking.
(2) adopt the salt acid system to produce rich titanium material, significantly reduce the consumption of acid, improve rich titanium material quality, save cost more than 3000 yuan/ton.
(3) solved the chlorine equilibrium problem of chlor-alkali plant,, saved cost for the enterprise production caustic soda and (contain balance chlorine and subsidize the expense on the PVC) more than 1500 yuan/ton again for chlor-alkali enterprise provides the sodium-chlor raw material.
(4) the present invention is strong to the grade height flexibility of ilmenite, both available homemade Guangxi, Hainan, Flos Bombacis Malabarici ore deposit, also available import ore deposit.
(5) chlorine of the present invention circulates in chlor-alkali and rich titanium material production process, does not outwards export, and efficiently solves the chlorine equilibrium problem of chlor-alkali enterprise, has also solved the waste water handling problem that the rich titanium material of salt acid system is produced, and kills two birds with one stone.
(6) using soda ash to handle filtrating more has following four aspects to give prominence to advantage:
A. can disposable metalliferous minerals such as iron, aluminium, magnesium, calcium, manganese all be precipitated away, and chloride ion-containing not in the throw out, the raw material that makes throw out can be used as ironmaking uses.
B. after adding soda ash, waste water is converted into the neutral sodium chloride solution, can purify at normal temperatures and pressures concentrated, to not corrosion of equipment.
C. sodium chloride solution, promptly salt solution can use the method for r-o-to concentrate, and this is most economical in the world at present sophisticated waste water concentrating unit.
As long as the salt solution after d. handling is concentrated to the raw material use that certain concentration just can be used as chlor-alkali enterprise, need not crystallization, oven dry, thus save mass energy, do not cause waste yet.
Description of drawings
Fig. 1 is chlor-alkali of the present invention and the rich titanium material of salt acid system combination producing skeleton diagram;
Embodiment
Through following embodiment the present invention is described in further detail.As shown in Figure 1, the method for the rich titanium material of a kind of chlor-alkali and salt acid system combination producing, it may further comprise the steps:
A, ilmenite powder is worn into powder, add water and process slurry, feed chlor-alkali sub product hydrogenchloride; B, hydrogenchloride and red stone reaction generate iron trichloride and iron protochloride, and micro-magnesium chloride, calcium chloride, Manganous chloride tetrahydrate, aluminum chloride; C, employing filtering under pressure device filter, and filter residue makes rich titanium material after washing, drying; D, in filtrating, add soda ash, stir, throw out is ironic hydroxide and iron protocarbonate, and promptly spathic iron ore also contains micro-magnesiumcarbonate, lime carbonate, manganous carbonate, white lake; E, filtration once more, the spathic iron ore that obtains is supplied with Iron And Steel Plant's ironmaking; F, the sodium chloride solution reverse osmosis concentration that leaches, gained pure water usefulness more capable of circulation, the sodium chloride solution after concentrating becomes the raw material of chlor-alkali plant.
Among the above-mentioned steps B, generate iron trichloride: FeCl
3, iron protochloride: FeCl
2, and micro-magnesium chloride: MgCl
2, calcium chloride: CaCl
2, Manganous chloride tetrahydrate: MnCl
2, aluminum chloride AlCl
3
Among the above-mentioned steps D, in filtrating, add soda ash: Na
2CO
3, following chemical reaction takes place:
2FeCl
3+3Na
2CO
3+3H2O→2Fe(OH)
3↓+6NaCl+3CO
2↑
FeCl
2+Na
2CO
3→FeCO
3↓+2NaCl
MgCl
2+Na
2CO
3→MgCO
3↓+2NaCl
CaCl
2+Na
2CO
3→CaCO
3↓+2NaCl
MnCl
2+Na
2CO
3→MnCO
3↓+2NaCl
2AlCl
3+3Na
2CO
3+3H2O→2Al(OH)
3↓+6NaCl+2CO
2↑
Can know that from above-mentioned chemical reaction the solution metal ion all is converted into throw out, former mixing solutions is converted into the purified solution that only contains the sodium-chlor solute, and after filtering once more through step e, the filter residue that obtains is with Fe (OH)
3And FeCO
3Be the spathic iron ore of major ingredient, filtrating is comparatively purified sodium chloride solution.
Table 1 is to produce 100000 tons of rich titanium material (95%TiO per year
2) the input and output measuring and calculating
Table 1 is produced 100000 tons of rich titanium material (95%TiO per year
2) the input and output measuring and calculating
Can find out from last table, adopt 100,000 tons of rich titanium material (95%TiO of annual output of the present invention
2) rate of gross profit can reach 48%, and be environmental protection, green production, meet national industrial policies, be well worth doing.
Claims (6)
1. the method for the rich titanium material of chlor-alkali and salt acid system combination producing, it is characterized in that: it may further comprise the steps:
A, ilmenite powder is worn into powder, add pure water and process slurry, feed hydrogenchloride;
B, hydrogenchloride and red stone carry out the acidolysis chemical reaction, generate iron trichloride and iron protochloride;
C, filtration, filter residue makes rich titanium material after washing, drying;
D, in filtrating, add soda ash, throw out is ironic hydroxide and iron protocarbonate, i.e. spathic iron ore;
E, filtration once more, the spathic iron ore that obtains is supplied with Iron And Steel Plant's ironmaking;
F, sodium chloride solution carry out reverse osmosis concentration, and the gained pure water above-mentioned steps A that is used for capable of circulation processes slurry again, and the sodium chloride solution after concentrating becomes the raw material of chlor-alkali plant.
2. the method for the rich titanium material of a kind of chlor-alkali according to claim 1 and salt acid system combination producing; It is characterized in that: said steps A is used crusher and ball mill two-stage mechanical disintegration; Powder particle size 70um sieving rate is greater than 70%; The slurry solid-to-liquid ratio is 1: 4, and said hydrogenchloride is the chlor-alkali plant sub product.
3. the method for the rich titanium material of a kind of chlor-alkali according to claim 1 and salt acid system combination producing, it is characterized in that: among the said step B, the molar concentration rate of hydrogenchloride and red stone is 2-3: 1, the acidolysis chemical time is 4-6 hour.
4. the method for the rich titanium material of a kind of chlor-alkali according to claim 1 and salt acid system combination producing, it is characterized in that: among said step C or the E, the applying pressure filtration unit filters.
5. the method for the rich titanium material of a kind of chlor-alkali according to claim 1 and salt acid system combination producing is characterized in that: among the said step D in the spathic iron ore of gained chloride ion content less than 0.5%.
6. the method for the rich titanium material of a kind of chlor-alkali according to claim 1 and salt acid system combination producing; It is characterized in that: in the said step F; Reverse osmosis membrane salt rejection is greater than 95%; Sodium chloride content is less than 5 grams per liters in the pure water, and sodium chloride content is greater than 300 grams per liters in the sodium chloride solution after concentrating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285379A (en) * | 2020-03-17 | 2020-06-16 | 塔里木大学 | Vermiculite processing clean comprehensive utilization system and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4019898A (en) * | 1976-04-30 | 1977-04-26 | Benilite Corporation Of America | Beneficiation of ilmenite ore |
| CN102009995A (en) * | 2010-10-25 | 2011-04-13 | 汪晋强 | Method for preparing carbonate from waste slag obtained by producing lithopone |
| CN102352437A (en) * | 2011-09-15 | 2012-02-15 | 沙立林 | Method for treating hydrochloric acid leachate of ferrotitanium materials |
-
2012
- 2012-07-13 CN CN2012102473960A patent/CN102745741A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4019898A (en) * | 1976-04-30 | 1977-04-26 | Benilite Corporation Of America | Beneficiation of ilmenite ore |
| CN102009995A (en) * | 2010-10-25 | 2011-04-13 | 汪晋强 | Method for preparing carbonate from waste slag obtained by producing lithopone |
| CN102352437A (en) * | 2011-09-15 | 2012-02-15 | 沙立林 | Method for treating hydrochloric acid leachate of ferrotitanium materials |
Non-Patent Citations (1)
| Title |
|---|
| 韦亮平: "机械活化攀枝花钛铁矿精矿中主要矿物的结构与性质变化规律研究", 《中国优秀硕士学位论文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285379A (en) * | 2020-03-17 | 2020-06-16 | 塔里木大学 | Vermiculite processing clean comprehensive utilization system and method |
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Application publication date: 20121024 |