The method for improving titanium slag acidolysis rate
Technical field
The invention belongs to Titanium White Production By Sulfuric Acid Process fields, and in particular to the method for improving titanium slag acidolysis rate.
Background technique
The production method of titanium dioxide is mainly two kinds i.e. sulfuric acid process and chloridising, 90% or more titanium white production of the current country
Method is sulfuric acid process.Sulfate process titanium dioxide deadly defect is environmental issue, such as spent acid, ferrous sulfate and sulfur-containing tail gas.If with titanium
Iron ore produces titanium dioxide, and average titanium white per ton wants ferrous sulfate by-product 2.5t~4.0t, spent acid 5t~8t that concentration is about 20%,
Acid sulphur-containing exhaust gas 15000m3~2000m3.In fact, disposal of waste gas, water and industrial residue just becomes the work from being born from sulfate process titanium dioxide
Skill stubborn problem, each sulfate process titanium dioxide manufacturing enterprise is all utilizing some fruitful techniques and technology in the world at present
With reduction " three wastes ", wherein being typically represented as titanium slag instead of ilmenite concentrate.But continuous acidolysis investment is larger, operation and maintenance cost
It is higher therefore domestic at present mainly based on interval acidolysis.
Titanium slag replaces ilmenite concentrate to be the fundamental way for reducing or eliminating by-product green vitriol, it, which at least has the advantage that, subtracts
Few sulphur consumption 20%~30%;Greatly reduce and even is eliminated by-product green vitriol;Improve unit equipment production capacity about 30%;Reduce fixed throw
Money 7%.With constantly improve with strictly for national environmental protection policy, it is the general trend of events that it is raw material that domestic sulfuric acid method titanium pigment factory, which uses titanium slag instead,
Become.But the process of titanium slag acidolysis has that acidolysis rate is relatively low compared to ilmenite concentrate acidolysis, the interval acidolysis of ilmenite concentrate at present
The preferable level of rate can reach 96%~97%, and the preferable level of the interval acidolysis rate of titanium slag is 93~94%, thus acidolysis rate
Still there is biggish room for promotion.
The means for improving titanium slag acidolysis at present, which generally pass through, adjusts acid sludge ratio, reaction acid concentration etc., but after being limited to acidolysis
The temperature control requirement etc. that titanium liquid norm controlling requires and reaction causes, the increase rate of acidolysis rate is limited, still reaches to less than titanium
Concentrate acidolysis rate level or higher acidolysis rate are horizontal.
Summary of the invention
Present invention solves the technical problem that be the prior art improve acidolysis rate ability it is limited, titanium slag interval acid hydrolyzation acidolysis
Rate is to be improved.
Technical proposal that the invention solves the above-mentioned problems is to provide the method for improving titanium slag acidolysis rate, and step includes by titanium
Slag, 98% concentrated sulfuric acid, acidolysis auxiliary agent premix under agitation obtains premix, and reactor is added in premix, be passed through water or
Steam initiation reaction carries out acidolysis, acidolysis main reaction terminate after through curing, leach, acidolysis titanium liquid be obtained by filtration, the acidolysis helps
Agent is small molecular alcohol substance.
Further, by titanium slag, 98% concentrated sulfuric acid it is pre- it is mixed after, acidolysis auxiliary agent is added under agitation and is mixed to get
Reactor is added in premix by premix, is passed through water or steam initiation reaction and is carried out acidolysis, acidolysis main reaction terminate after through ripe
Change, leach, acidolysis titanium liquid is obtained by filtration, the acidolysis auxiliary agent is small molecular alcohol substance.
Wherein, acidolysis auxiliary agent is at least one of dehydrated alcohol, anhydrous methanol.
Wherein, the adding proportion of acidolysis auxiliary agent is the 0.05%~1% of titanium slag quality.
Wherein, the incorporation time of acidolysis auxiliary agent is 10~30min, and premix system temperature is controlled at≤30 DEG C.
Wherein, cooling control premix system temperature≤30 DEG C of collet are utilized.
Wherein, the mass ratio of 98% concentrated sulfuric acid and titanium slag is 1.7~1.8:1.
Beneficial effects of the present invention:
The present invention adds small molecular alcohol substance as acidolysis auxiliary agent in titanium slag sulfuric acid process acid hemolysis process, can effectively improve
Titanium slag acidolysis rate, batch process acidolysis rate is 95%~96%, to improve whole process titanium dioxide yield, reduces production cost,
Improve the profitability of titanium slag application;Operation of the present invention is simple, is easy to implement, promoting and applying titanium slag has very important work
With.
Specific embodiment
The present invention provides the method for improving titanium slag acidolysis rate, and step includes stirring titanium slag, 98% concentrated sulfuric acid, acidolysis auxiliary agent
Premix obtains premix under the conditions of mixing, and reactor is added in premix, is passed through water or steam initiation reaction carries out acidolysis, acidolysis master
After reaction through curing, leach, be obtained by filtration acidolysis titanium liquid, the acidolysis auxiliary agent is small molecular alcohol substance.
The reaction that acid hemolysis process mainly occurs has:
FeTiO3+3H2SO4→Ti(SO4)2+FeSO4+3H2O
FeTiO3+2H2SO4→TiOSO4+FeSO4+2H2O
The use of small molecular alcohol substance can reduce the activation energy of titanium slag acidolysis reaction, and reaction forward is promoted to carry out, from
And achieve the purpose that improve acidolysis rate.
Further, by titanium slag, 98% concentrated sulfuric acid it is pre- it is mixed after, acidolysis auxiliary agent is added under agitation and is mixed to get
Reactor is added in premix by premix, is passed through water or steam initiation reaction and is carried out acidolysis, acidolysis main reaction terminate after through ripe
Change, leach, acidolysis titanium liquid is obtained by filtration, the acidolysis auxiliary agent is small molecular alcohol substance.
Acidolysis auxiliary agent, can be uneven to avoid mixing in titanium slag, the pre- mixed addition later of 98% concentrated sulfuric acid, and is added in advance
Acidolysis auxiliary agent may cause volatilization and increase, and cause loss of material.
Wherein, acidolysis auxiliary agent is at least one of dehydrated alcohol, anhydrous methanol.
Wherein, the adding proportion of acidolysis auxiliary agent is the 0.05%~1% of titanium slag quality.It is found by many experiments, acidolysis
The additive amount of auxiliary agent need to be controlled in suitable range, and additive amount is too small not to have the effect for improving acidolysis rate, and additive amount is too big, right
In interval acidolysis, since volume expansion multiple is excessive, the probability for risking the danger such as pot or fryer increases, and exhaust emissions amount will
It can sharply increase, acidolysis auxiliary agent increased costs.It therefore cannot be in order to improve acidolysis rate, without the factor of consideration volume expansion.
Wherein, the incorporation time of acidolysis auxiliary agent is 10~30min, and premix system temperature is controlled at≤30 DEG C.Control is mixed
Zoarium system temperature be in order to avoid titanium slag acidolysis reaction in advance premix slot in react, thus premix slot in scab,
It is easy to cause premix slot that safety accident occurs, and the slurry after premix can not be transported in acidolysis pot and effectively be reacted, drops
Low acidolysis rate, and the volatilization of temperature height then acidolysis auxiliary agent increases, and reduces acidolysis rate.
Wherein, cooling control premix system temperature≤30 DEG C of collet are utilized.
Wherein, the mass ratio of 98% concentrated sulfuric acid and titanium slag is 1.7~1.8:1.
Comparative example 1
Under stirring conditions, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, according to titanium slag acidolysis process: anti-
Answer acid concentration 92%, 130 DEG C of initiation temperature, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time
1.5h carries out acidolysis, calculates acidolysis rate and volume expansion situation after obtaining acidolysis titanium liquid by sheet frame expression separation.
Embodiment 2
Under stirring conditions, take 98% concentrated sulfuric acid 173.5g, titanium slag 100g premix, add 1% dehydrated alcohol it is pre-
Mixed 20min obtains premix, using cooling control premix system temperature≤30 DEG C of collet, then according to titanium slag acidolysis process:
Reaction acid concentration 92%, 130 DEG C of initiation temperature, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time
1.5h carries out acidolysis, calculates acidolysis rate and volume expansion situation after obtaining acidolysis titanium liquid by sheet frame expression separation.
Embodiment 3
Under stirring conditions, take 98% concentrated sulfuric acid 173.5g, titanium slag 100g premix, add 1% anhydrous methanol it is pre-
Mixed 20min obtains premix, using cooling control premix system temperature≤30 DEG C of collet, then according to titanium slag acidolysis process:
Reaction acid concentration 92%, 130 DEG C of initiation temperature, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time
1.5h carries out acidolysis, calculates acidolysis rate and volume expansion situation after obtaining acidolysis titanium liquid by sheet frame expression separation.
Embodiment 4
Under stirring conditions, it takes 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, adds 0.1% dehydrated alcohol
Premix 20min obtains premix, using cooling control premix system temperature≤30 DEG C of collet, then according to titanium slag acidolysis work
Skill: reaction acid concentration 92%, 68 DEG C of extraction temperature, leaches by 130 DEG C of initiation temperature, curing time 1.5h, 170 DEG C of curing temperature
Time 1.5h carries out acidolysis, calculates acidolysis rate and volume expansion situation after obtaining acidolysis titanium liquid by sheet frame expression separation.
Embodiment 5
Under stirring conditions, it takes 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, adds 0.1% anhydrous methanol
Premix 20min obtains premix, using cooling control premix system temperature≤30 DEG C of collet, then according to titanium slag acidolysis work
Skill: reaction acid concentration 92%, 68 DEG C of extraction temperature, leaches by 130 DEG C of initiation temperature, curing time 1.5h, 170 DEG C of curing temperature
Time 1.5h carries out acidolysis, calculates acidolysis rate and volume expansion situation after obtaining acidolysis titanium liquid by sheet frame expression separation.
The indexs of correlation of above-mentioned comparative example and embodiment is summarized as shown in table 1, wherein volume expansion refer to material by
Gas is generated in chemical reaction, so that the phenomenon that system volume expansion.
Table 1
As can be seen from the above table, in the identical situation of other acidolysis process, acid hemolysis process adds anhydrous methanol or anhydrous
Ethyl alcohol compares the case where being not added with acidolysis auxiliary agent, and acidolysis rate is improved to some extent, and shows present invention addition acidolysis auxiliary agent
Method facilitate the raising of acidolysis rate.In addition, the addition of acidolysis auxiliary agent, reduces main reaction temperature, acidolysis behaviour can effectively reduce
The risk of work reduces sulfur content in acid hydrolysis tail gas.
Acidolysis rate calculation formula are as follows: Ti content/(Ti content in Ti content+residue in titanium liquid) in titanium liquid, acidolysis rate it is big
It is small to influence subsequent titanium dioxide yield.Titanium slag is in and expands market energetically the stage at present, and improving acidolysis rate is this work
One of emphasis.If by 74% titanium slag, 4500 yuan/t of unit price, acidolysis rate 94%, whole process titanium dioxide yield 86%, then titanium is used
Slag yield, which improves 1%, 1t titanium white, can save 396 yuan.If country's sulfate process titanium dioxide yield is according to 2,800,000 t/a at present, all of
Titanium slag is produced, and due to improving titanium slag acidolysis rate 1%, is cast aside a small amount of investment, then can be created 11.09 hundred million yuan of benefit.