CN103028224A - Method for treating titanium tetrachloride-containing waste liquid - Google Patents
Method for treating titanium tetrachloride-containing waste liquid Download PDFInfo
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- CN103028224A CN103028224A CN 201110303200 CN201110303200A CN103028224A CN 103028224 A CN103028224 A CN 103028224A CN 201110303200 CN201110303200 CN 201110303200 CN 201110303200 A CN201110303200 A CN 201110303200A CN 103028224 A CN103028224 A CN 103028224A
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Abstract
The invention discloses a method for treating a titanium-containing waste liquid, which belongs to the field of treatment of industrial waste liquids. The method comprises the following process steps of: preparing white lime (Ca(OH)2) and water into lime milk according to a certain proportion in a lime milk storage tank; putting a certain amount of the prepared lime milk into a reactor; and directly adding a certain amount of titanium-containing waste liquid into the reactor, controlling the adding speed of the titanium-containing waste liquid, keeping the reaction temperature below or equal to 90 DEG C, and finally reacting to form solid waste residues TiO2/CaCl2.nH2O. White lime is taken as an alkali neutralizing agent, and the titanium-containing waste liquid directly undergoes a hydrolysis neutralizing reaction with lime milk without a hydrolysis reaction, so that the amount of water needed in the conventional method is saved, and solid waste residues are taken as a final treatment product and are convenient to transport; and moreover, conventional measures such as burning and landfilling can be adopted in a subsequent treatment way, so that the treatment cost is saved.
Description
Technical field
The invention belongs to the industrial wastes process field, relate to a kind of processing method of titaniferous waste liquid, relate more specifically to the processing method of the titaniferous waste liquid that produces in a kind of polyolefin catalyst production process.
Background technology
In polyolefin industry, use now maximum Ziegler-Natta catalysts and be the efficient magnesium chloride supported catalyst take magnesium chloride as carrier, it mainly is take magnesium chloride as carrier, titanium tetrachloride is active component, and interior external electron donor forms.As everyone knows, in the Ziegler-Natta catalyst preparation process, need to use a large amount of and excessive titanium tetrachloride, so in process of production except the output catalyst prod, also can produce a large amount of titaniferous mother liquors, it contains unreacted titanium tetrachloride, one or more hydrocarbon solvents, (halo) alkoxytitanium and electron donor etc.
Existing technique, the method for distillation commonly used is recycled the titanium tetrachloride in the titaniferous mother liquor and solvent.Under the air-distillation condition, because the notable difference of boiling point, the hydrocarbon solvent that boiling point is minimum can easily separate with other components in destilling tower.But next continue to promote vapo(u)rizing temperature, the accessory substances such as lower boiling titanium tetrachloride and high boiling alkoxytitanium but are difficult to separate fully.This is that cracking and decomposition can occur the other accessory substance because along with the steaming of titanium tetrachloride, the proportion of alkoxytitanium increases gradually, and these all can cause solution viscosity to continue to increase, and then are created in the risk of the fouling of destilling tower tower reactor and obstruction.So under this condition, it is impossible that titanium tetrachloride is steamed fully, because can cause like this serious scale and the obstruction of destilling tower tower reactor, the still raffinate can not be discharged smoothly.So only can carry out the preliminary recovery of titanium tetrachloride at distilling period, usually through just steaming, also contain the part titanium tetrachloride in the bottoms and be not recovered.
Usually for the processing of the bottoms after the first steaming, commonly based on hydrolysis and the utilization of liquid phase
NaOHNeutralizing hydrolysis produces
HClTreatment process.Yet, process through this mode, can consume a large amount of water, and finally can produce the aqueous slurry that contains in a large number titanium oxygen compound and organic pollution, and these waste water need to be processed in quality purifying device for water, processing cost is higher, and owing to contain simultaneously a large amount of chlorions in these slurries, has also increased follow-up wastewater treatment difficulty.
Summary of the invention
Technical problem solved by the invention: the invention provides a kind of method of processing the titaniferous waste liquid, directly react by adopting milk of lime and the titaniferous waste liquid that flows out from the destilling tower bottom, generate a kind of solid slag, utilize to solve in the prior art
NaOHIn and the hydrolyzate of titaniferous waste liquid and produce a large amount of waste water that contains titanium oxygen compound and organic pollution, increased the problem of subsequent wastewater treatment difficulty.
The technical solution used in the present invention:
The invention provides a kind of processing method of titaniferous waste liquid, comprise following steps:
(1) a certain amount of milk of lime is placed in the reactor;
(2) a certain amount of titaniferous waste liquid is directly added in the above-mentioned reactor, the adding speed of control titaniferous waste liquid, so that reaction temperature is no more than 90 ℃, end reaction forms solid slag
Described milk of lime employing white lime (
) add water and in the milk of lime storage tank, dispose, wherein the ratio of white lime and water is controlled at 1:1 ~ 1:2 according to mass ratio.
Described titaniferous waste liquid mainly comprises titanium tetrachloride, (halo) alkoxytitanium and other accessory substance, for example derives from solid or the liquid organic compound of the electron suppling compound of charging during the titanate step of ingredient of solid catalyst.
Described (halo) alkoxytitanium can be used general formula
Expression, wherein X is halogen, is preferably chlorine, R is alkyl, is preferably the low alkyl group with 1 ~ 10 carbon atom, such as ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl etc., m=0 ~ 3, n=1 ~ 4,2≤m+n≤4.
Described electron donor such as aromatics and/or aliphatic series (two) ester, (two) ether and their derivative etc.
The ratio of described milk of lime and titaniferous waste liquid according to white lime in the milk of lime (
) with the mass ratio of titaniferous waste liquid be 1:0.5~1:2 control.
Described reactor adopts the water leg cooling so that reaction temperature≤90 ℃.
Described reactor is mixing screw or kneader, but be not only limited to above reactor types, because the final reaction product forms pressed powder, so stir in order to react and to have reacted blowing convenient, should select mixing screw, kneader etc. can produce to solid-state or semisolid material the reactor types of strong shearing, immixture, should not select general stirring reactor.
Inventive point of the present invention is: select milk of lime to replace sodium hydrate aqueous solution used in the existing popular response, with the neutralization reaction that directly is hydrolyzed without the titaniferous waste liquid that is hydrolyzed, key point is to control the mass ratio of white lime and water in the milk of lime, and the mass ratio of white lime and titaniferous waste liquid, according to the ratio that provides among the present invention neutralization reaction that is hydrolyzed, can obtain final reacting product is solid slag.
The essential distinction of the present invention and prior art is: existing hydrolysis process, can produce the aqueous slurry that contains in a large number titanium oxygen compound and organic pollution, and be difficult for carrying out subsequent treatment.The present invention proposes to adopt milk of lime as hydrolysis and alkali nertralizer, directly the titaniferous waste liquid is processed, and finally produces solid slag, and product can further be disposed according to solid waste.
The invention has the beneficial effects as follows: the titaniferous spent lye is without hydrolysis process, directly and the milk of lime neutralization reaction that is hydrolyzed, saved in the conventional method required a large amount of water yields in the titaniferous waste liquid hydrolytic process; Reduce simultaneously final refuse treating capacity, reduced waste discharge; Final processing product is solid slag, can further dispose according to solid waste.Relative waste liquid, solid slag is convenient to transportation, and the subsequent treatment mode can adopt the conventional meanses such as burning, landfill to process, and has saved processing cost.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
The specific embodiment
Embodiment 1:
100g white lime is mixed in the milk of lime storage tank with 100g water, be configured to milk of lime, then first milk of lime is joined in the kneader, and then 100g titaniferous waste liquid is joined in the kneader, and abundant mixing.Reactor adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 80 ℃ during reaction.After reaction is finished, finally form the solid slag of 300g, can further dispose.
Embodiment 2: 100g white lime is mixed in the milk of lime storage tank with 100g water, be configured to milk of lime, then first milk of lime is joined in the mixing screw, and then 50g titaniferous waste liquid is joined in the mixing screw, and fully mix even.Mixing screw adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 80 ℃ during reaction.After reaction is finished, finally form the solid slag of 250g, can further dispose.
Implement 3: 100g white lime is mixed in the milk of lime storage tank with 100g water, be configured to milk of lime, then first milk of lime is joined in the kneader, and then 150g titaniferous waste liquid is joined in the kneader, and abundant mixing.Kneader adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 90 ℃ during reaction.After reaction is finished, finally form the solid slag of 350g, can further dispose.
Embodiment 4: 100g white lime mixed in the milk of lime storage tank with 100g water, is configured to milk of lime, then first milk of lime is joined in the kneader, and then 200g titaniferous waste liquid is joined in the kneader, and abundant mixing.Kneader adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 90 ℃ during reaction.After reaction is finished, finally form the solid slag of 400g, can further dispose.
Embodiment 5: 100g white lime mixed in the milk of lime storage tank with 200g water, is configured to milk of lime, then first milk of lime is joined in the mixing screw, and then 50g titaniferous waste liquid is joined in the mixing screw, and abundant mixing.Mixing screw adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 80 ℃ during reaction.After reaction is finished, finally form the solid slag of 350g, can further dispose.
Embodiment 6: 100g white lime mixed in the milk of lime storage tank with 200g water, is configured to milk of lime, then first milk of lime is joined in the kneader, and then 100g titaniferous waste liquid is joined in the kneader, and abundant mixing.Kneader adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 90 ℃ during reaction.After reaction is finished, finally form the solid slag of 400g, can further dispose.
Embodiment 7: 100g white lime mixed in the milk of lime storage tank with 200g water, is configured to milk of lime, then first milk of lime is joined in the mixing screw, and then 150g titaniferous waste liquid is joined in the mixing screw, and abundant mixing.Mixing screw adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 80 ℃ during reaction.After reaction is finished, finally form the solid slag of 450 g, can further dispose.
Embodiment 8: 100g white lime mixed in the milk of lime storage tank with 200g water, is configured to milk of lime, then first milk of lime is joined in the mixing screw, and then 200g titaniferous waste liquid is joined in the mixing screw, and abundant mixing.Mixing screw adopts the water leg cooling, and the adding speed of control titaniferous waste liquid is so that temperature is no more than 90 ℃ during reaction.After reaction is finished, finally form the solid slag of 500g, can further dispose.
Claims (5)
1. method of processing the titaniferous waste liquid comprises following processing step:
(1) with white lime (
) in the milk of lime storage tank, be configured to milk of lime according to a certain percentage with water;
(2) the above-mentioned a certain amount of milk of lime that configures is placed in the reactor;
(3) a certain amount of titaniferous waste liquid is directly added in the above-mentioned reactor, the adding speed of control titaniferous waste liquid, so that reaction temperature is no more than 90 ℃, end reaction forms solid slag.
3. a kind of method of processing the titaniferous waste liquid according to claim 2 is characterized in that the ratio of described milk of lime and titaniferous waste liquid, is 1:0.5~1:2 wt control according to the mass ratio of the white lime that contains in the milk of lime and titaniferous waste liquid.
4. a kind of method of processing the titaniferous waste liquid according to claim 3, it is characterized in that selecting in the neutralization reaction reactor is mixing screw or kneader.
5. a kind of method of processing the titaniferous waste liquid according to claim 3 is characterized in that described reactor adopts the water leg cooling so that reaction temperature≤90 ℃.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103449495A (en) * | 2013-08-30 | 2013-12-18 | 遵宝钛业有限公司 | Method for preparing calcium chloride by hydrochloric acid recovered from production of titanium tetrachloride |
CN104445701A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for processing titanium-containing organic matter-containing waste acid water from polyolefin catalyst |
CN111908610A (en) * | 2020-07-14 | 2020-11-10 | 河北美卡诺生物科技有限公司 | Novel carbon source for sewage denitrification |
-
2011
- 2011-10-09 CN CN 201110303200 patent/CN103028224A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103449495A (en) * | 2013-08-30 | 2013-12-18 | 遵宝钛业有限公司 | Method for preparing calcium chloride by hydrochloric acid recovered from production of titanium tetrachloride |
CN103449495B (en) * | 2013-08-30 | 2015-08-19 | 遵宝钛业有限公司 | A kind of utilization in titanium tetrachloride production reclaims the method that hydrochloric acid produces calcium chloride |
CN104445701A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for processing titanium-containing organic matter-containing waste acid water from polyolefin catalyst |
CN104445701B (en) * | 2013-09-16 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of polyolefin catalyst titaniferous is containing the treatment process of organism waste acid water |
CN111908610A (en) * | 2020-07-14 | 2020-11-10 | 河北美卡诺生物科技有限公司 | Novel carbon source for sewage denitrification |
CN111908610B (en) * | 2020-07-14 | 2022-03-22 | 河北美卡诺生物科技有限公司 | Carbon source for sewage denitrification |
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Application publication date: 20130410 |