CN104445701A - Method for processing titanium-containing organic matter-containing waste acid water from polyolefin catalyst - Google Patents
Method for processing titanium-containing organic matter-containing waste acid water from polyolefin catalyst Download PDFInfo
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- CN104445701A CN104445701A CN201310421760.5A CN201310421760A CN104445701A CN 104445701 A CN104445701 A CN 104445701A CN 201310421760 A CN201310421760 A CN 201310421760A CN 104445701 A CN104445701 A CN 104445701A
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- raffinate
- polyolefin catalyst
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to waste water processing technology, and concretely relates to a method for processing titanium-containing organic matter-containing waste acid water from a polyolefin catalyst. The processing method is characterized in that a diffusion dialyzer is used for separating hydrochloric acid in the titanium-containing organic matter-containing waste acid water from the polyolefin catalyst to obtain hydrochloric acid and raffinate, titanium in the raffinate is conversed to a titanium dioxide solid for recovery by neutralizing, and finally a Fenton oxidation method is used for removing the organic matter in the raffinate which is used for filtering the titanium dioxide solid. The processing method fully realizes the resource recovery and reduces the risk of environment pollution.
Description
Technical field
The present invention relates to wastewater processing technology, being specially the treatment process of a kind of polyolefin catalyst titaniferous containing organism waste acid water, relating more specifically to a kind of method that titaniferous to producing in polyolefin catalyst preparation process recycles containing organism waste acid water.
Background technology
Polyolefin industry has very important effect in petroleum chemical industry.The product that polyolefin industry is produced is widely used in every field, for national economy makes major contribution.Ziegler-Natta catalyst is a kind of catalyzer be most widely used in polyolefin industry.The preparation of Ziegler-Natta catalyst first titanium tetrachloride is mixed for some time with the solid phase carrier of magnesium-containing compound, to obtain highly active Ziegler-Natta catalyst component.Then the salvage stores such as titanium tetrachloride and high boiling material utilizing varsol to wash not to be loaded into, obtains Ziegler-Natta catalyst mother liquor, wherein, high boiling material mainly comprises (halo) high boiling substances such as titan-alkoxide, ester class.Ziegler-Natta catalyst mother liquor reclaims the titanium tetrachloride be not loaded into through destructive distillation, high boiling material enters hydrolysis kettle and is hydrolyzed, and obtains polyolefin catalyst titaniferous containing organism waste acid water.Mainly to adopt containing the process of organism waste acid water for this kind of polyolefin catalyst titaniferous at present and first add sodium hydroxide and neutralize, the method for the titanium dioxide that reprocessing produces and waste water.But this method needs to consume a large amount of sodium hydroxide, cost is very high, and it is very high to neutralize chlorine ion concentration in the waste water that produces, is difficult to subsequent disposal.
Patent " a kind for the treatment of process of Dye acidic waste water and device " (application number 201310078739.X) describes a kind for the treatment of process of dyestuff waste acid water, pass through automatic control system, carry out distillation and concentration successively, neutralization, absorption, light electrolysis, coagulating sedimentation, activated carbon column absorption, condensing crystal, separation prepare sodium sulfate or sodium-chlor, the water distilled can reach industrial reuse water quality standard.Patent " a kind of method for recycling waste acid " (application number 201110372272.0) describes the organism utilized in activated carbon treatment sour water, the sour water after process is added original nut liquid, returns and apply mechanically.More than patent describes the treatment process containing organism sour water, for the process rare report of polyolefin catalyst titaniferous containing organism waste acid water.
Summary of the invention
For the shortcoming that prior art exists, the object of the present invention is to provide a kind of polyolefin catalyst titaniferous containing the treatment process of organism waste acid water.Polyolefin catalyst titaniferous of the present invention is containing the treatment process of organism waste acid water, first the method for diffusion dialysis is utilized to reclaim this polyolefin catalyst titaniferous containing the hydrochloric acid in organism waste acid water, then the method recovery titanium dioxide wherein of neutralization is utilized, finally recycle the method process organism wherein of Fenton oxidation, avoid the pollution that this kind of polyolefin catalyst titaniferous causes environment containing the discharge of organism waste acid water, and recyclable hydrochloric acid, reduces processing cost.
For reaching above object, the technical scheme that the present invention takes is:
A kind of polyolefin catalyst titaniferous is containing the treatment process of organism waste acid water, it is characterized in that, described polyolefin catalyst titaniferous is the product water that the high boiling material in the preparation process of Ziegler-Natta catalyst is hydrolyzed through hydrolysis kettle containing organism waste acid water, its water quality characteristic is: the mass concentration of hydrochloric acid is 20 ~ 26%, the mass concentration of titanium is 10 ~ 13%, TOC is 1000 ~ 3000mg/L, specifically comprises the steps:
Step 1, diffusion dialysis: polyolefin catalyst titaniferous is joined in the dialysing compartment of diffusion dialysis device containing organism waste acid water, tap water joins in the diffuser casing of diffusion dialysis device, be separated by with anionic membrane between dialysing compartment and diffuser casing, both countercurrent flows, after diffusion dialysis after a while, obtain raffinate in dialysing compartment outlet, obtain hydrochloric acid in diffuser casing outlet, the hydrochloric acid obtained reclaims;
Step 2, filtration treatment: in the raffinate that step 1 obtains, add alkali, by the pH regulator of raffinate to 7 ~ 9, and make the titanium in raffinate be converted into titanium dioxide solids, filter and reclaimed by the titanium dioxide solids obtained;
Step 3, Fenton oxidation process: the raffinate having filtered titanium dioxide solids is carried out Fenton oxidation process, be first adjusted to 3 ~ 4 with acid by its pH, then add ferrous sulfate and oxydol H
2o
2, stirring reaction 0.5 ~ 3h, after completion of the reaction, is adjusted to 7 ~ 9 with alkali by the pH of raffinate after reaction.
On the basis of such scheme, in step 1, polyolefin catalyst titaniferous is 1:1 ~ 1:1.5 containing the mass ratio of organism waste acid water and tap water.
On the basis of such scheme, for some time in step 1 is 2 ~ 5h.
On the basis of such scheme, the hydrochloric acid reclaimed in step 1 is 0.8:1.2 ~ 0.9:1.1 with the mass ratio of the raffinate obtained, and in the raffinate obtained, the mass concentration of hydrochloric acid is 2 ~ 5%, and the mass concentration of titanium is 8 ~ 10%, TOC is 950 ~ 2700mg/L.
On the basis of such scheme, the mass concentration of the hydrochloric acid that step 1 reclaims is 17 ~ 25%.
On the basis of such scheme, in the titanium dioxide solids that step 2 reclaims, the mass content of titanium dioxide is higher than 98%, and rest part is organism.
On the basis of such scheme, step 2 has been filtered in the raffinate of titanium dioxide solids, and its TOC is 900 ~ 2500mg/L.
On the basis of such scheme, the acid in step 3 is sulfuric acid or hydrochloric acid, ferrous sulfate and H
2o
2add-on should meet: H
2o
2be 10:1 ~ 20:1, H with the mass ratio of TOC in the raffinate having filtered titanium dioxide solids
2o
2and Fe
2+mass ratio be 5:1 ~ 10:1.
On the basis of such scheme, the alkali in step 2 and 3 is sodium hydroxide or potassium hydroxide.
On the basis of such scheme, the raffinate in step 3 after Fenton oxidation process, its TOC is less than 50mg/L.
Polyolefin catalyst titaniferous of the present invention is containing the treatment process of organism waste acid water, diffusion dialysis device is utilized to be separated containing the hydrochloric acid in organism waste acid water by polyolefin catalyst titaniferous, obtain hydrochloric acid and raffinate, greatly save the amount of the sodium hydroxide added needed for follow-up neutralization, by neutralization, the titanium in raffinate is converted into titanium dioxide solids again to reclaim, finally utilizes the method for Fenton oxidation to remove the organism filtered in the raffinate of titanium dioxide solids.
Compared with prior art, the invention has the beneficial effects as follows:
1) the present invention utilizes diffusion dialysis device to process polyolefin catalyst titaniferous containing organism waste acid water, by hydrochloric acid Separation and Recovery, adequately achieve resource reclaim, reduce the expense needed for follow-up neutralization, simultaneously in Fenton oxidation step, because the hydroxyl radical free radical meeting oxidize chloride ions that Fenton oxidation produces, the too high effect that can affect Fenton oxidation of chloride ion content, make Fenton oxidation remove organic effect to reduce, and the consumption of hydrogen peroxide and ferrous sulfate is increased, the method of diffusion dialysis is utilized first to be separated by hydrochloric acid, Fenton oxidation can be made to have better effect,
2) the present invention adopts the method for Fenton oxidation to process the raffinate having filtered titanium dioxide solids, effectively can remove polyolefin catalyst titaniferous containing the organism in organism waste acid water, reduce the risk of contaminate environment.
Accompanying drawing explanation
The present invention has following accompanying drawing:
Fig. 1 process flow sheet of the present invention,
Fig. 2 utilizes diffusion dialysis device process polyolefin catalyst titaniferous containing the schematic diagram of organism waste acid water.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
As shown in Figure 1, the invention provides the treatment process of a kind of polyolefin catalyst titaniferous containing organism waste acid water, described polyolefin catalyst titaniferous is the product water that the high boiling material in the preparation process of Ziegler-Natta catalyst is hydrolyzed through hydrolysis kettle containing organism waste acid water, its water quality characteristic is: the mass concentration of hydrochloric acid is 20 ~ 26%, the mass concentration of titanium is 10 ~ 13%, TOC is 1000 ~ 3000mg/L, specifically comprises the steps:
Step 1, diffusion dialysis: as shown in Figure 2, polyolefin catalyst titaniferous is joined in the dialysing compartment of diffusion dialysis device (commercially available prod) containing organism waste acid water, tap water joins in the diffuser casing of diffusion dialysis device, be separated by with anionic membrane between dialysing compartment and diffuser casing, both countercurrent flows, after diffusion dialysis after a while, obtain raffinate in dialysing compartment outlet, obtain hydrochloric acid in diffuser casing outlet, the hydrochloric acid obtained reclaims;
Step 2, filtration treatment: in the raffinate that step 1 obtains, add alkali, by the pH regulator of raffinate to 7 ~ 9, and make the titanium in raffinate be converted into titanium dioxide solids, filter and reclaimed by the titanium dioxide solids obtained;
Add the acting body of alkali now both ways: one is make the titanium in raffinate be converted into titanium dioxide solids completely, the titanium in raffinate is removed clean; Two is make the hydrochloric acid in raffinate be converted into water by neutralization reaction, thus is removed by the hydrochloric acid in raffinate.
Step 3, Fenton oxidation process: the raffinate having filtered titanium dioxide solids is carried out Fenton oxidation process, be first adjusted to 3 ~ 4 with acid by its pH, then add ferrous sulfate and hydrogen peroxide (H
2o
2), stirring reaction 0.5 ~ 3h, after completion of the reaction, is adjusted to 7 ~ 9 with alkali by the pH of raffinate after reaction.
On the basis of such scheme, in step 1, polyolefin catalyst titaniferous is 1:1 ~ 1:1.5 containing the mass ratio of organism waste acid water and tap water.
On the basis of such scheme, for some time in step 1 is 2 ~ 5h.
On the basis of such scheme, the hydrochloric acid reclaimed in step 1 is 0.8:1.2 ~ 0.9:1.1 with the mass ratio of the raffinate obtained.
On the basis of such scheme, in the raffinate described in step 1, the mass concentration of hydrochloric acid is 2 ~ 5%, and the mass concentration of titanium is 8 ~ 10%, TOC is 950 ~ 2700mg/L.
On the basis of such scheme, the mass concentration of the hydrochloric acid reclaimed in step 1 is 17 ~ 25%.
On the basis of such scheme, in the titanium dioxide solids reclaimed in step 2, the mass content of titanium dioxide is higher than 98%, and rest part is organism.
On the basis of such scheme, step 2 has been filtered in the raffinate of titanium dioxide solids, and TOC is 900 ~ 2500mg/L.
On the basis of such scheme, the acid in step 3 is sulfuric acid or hydrochloric acid.
On the basis of such scheme, ferrous sulfate and H in step 3
2o
2add-on should meet: H
2o
2be 10:1 ~ 20:1, H with the mass ratio of TOC in the raffinate having filtered titanium dioxide solids
2o
2and Fe
2+mass ratio be 5:1 ~ 10:1.
On the basis of such scheme, the alkali in step 2 and 3 is sodium hydroxide or potassium hydroxide.
On the basis of such scheme, the raffinate in step 3 after Fenton oxidation process, its TOC is less than 50mg/L.
Be below some embodiments.
Embodiment 1
The polypropylene catalyst titaniferous that the present embodiment uses is containing the hydrolysis of organism waste acid water from hydrolysis kettle in the preparation process of polypropylene industrial Ziegler-Natta catalyst, and wherein the mass concentration of hydrochloric acid is 26%, and the mass concentration of titanium is 13%, TOC is 3000mg/L.
The experimental procedure of the present embodiment:
1) polyolefin catalyst titaniferous is joined in the dialysing compartment of diffusion dialysis device containing organism waste acid water, tap water joins in the diffuser casing of diffusion dialysis device, wherein, the polyolefin catalyst titaniferous added is 1:1 containing the mass ratio of organism waste acid water and tap water, be separated by with anionic membrane between dialysing compartment and diffuser casing, both countercurrent flows, after the diffusion dialysis of 2h, raffinate is obtained in dialysing compartment outlet, hydrochloric acid is obtained in diffuser casing outlet, the hydrochloric acid obtained reclaims, the hydrochloric acid reclaimed is 0.9:1.1 with the mass ratio of the raffinate obtained, wherein, the mass concentration of the hydrochloric acid reclaimed is 25%, in the raffinate obtained, the mass concentration of hydrochloric acid is 3%, the mass content of titanium is 10%, TOC is 2700mg/L,
2) potassium hydroxide is added in the raffinate obtained to step 1), by the pH regulator to 8 at residual night, and make the titanium in raffinate be converted into titanium dioxide solids, filter and the titanium dioxide solids obtained is reclaimed, in the titanium dioxide solids wherein reclaimed, the mass content of titanium dioxide is 99%, and having filtered TOC in the raffinate of titanium dioxide solids is 2500mg/L;
3) by step 2) raffinate that filtered titanium dioxide solids carries out Fenton oxidation process, and first with hydrochloric acid, its pH is adjusted to 3, then adds ferrous sulfate and hydrogen peroxide, control H
2o
2be 20:1, H with the mass ratio of TOC in the raffinate having filtered titanium dioxide solids
2o
2and Fe
2+mass ratio be 5:1, stirring reaction 3h, after completion of the reaction, with potassium hydroxide, the pH of raffinate after reaction is adjusted to 8, the raffinate after Fenton oxidation process, its TOC is 25mg/L.
Embodiment 2
The polypropylene catalyst titaniferous that the present embodiment uses is containing the hydrolysis of organism waste acid water from hydrolysis kettle in the preparation process of polypropylene industrial Ziegler-Natta catalyst, and wherein the mass concentration of hydrochloric acid is 20%, and the mass concentration of titanium is 10%, TOC is 1000mg/L.
The experimental procedure of the present embodiment:
1) polyolefin catalyst titaniferous is joined in the dialysing compartment of diffusion dialysis device containing organism waste acid water, tap water joins in the diffuser casing of diffusion dialysis device, wherein, the polyolefin catalyst titaniferous added is 1:1.5 containing the mass ratio of organism waste acid water and tap water, be separated by with anionic membrane between dialysing compartment and diffuser casing, both countercurrent flows, after the diffusion dialysis of 5h, raffinate is obtained in dialysing compartment outlet, hydrochloric acid is obtained in diffuser casing outlet, the hydrochloric acid obtained reclaims, the hydrochloric acid reclaimed is 1:1.5 with the mass ratio of the raffinate obtained, wherein, the mass concentration of the hydrochloric acid reclaimed is 17%, in the raffinate obtained, the mass concentration of hydrochloric acid is 2%, the mass content of titanium is 8%, TOC is 950mg/L,
2) sodium hydroxide is added in the raffinate obtained to step 1), by the pH regulator to 9 at residual night, and make the titanium in raffinate be converted into titanium dioxide solids, filter and the titanium dioxide solids obtained is reclaimed, in the titanium dioxide solids wherein reclaimed, the mass content of titanium dioxide is 98%, and having filtered TOC in the raffinate of titanium dioxide solids is 900mg/L;
3) by step 2) raffinate that filtered titanium dioxide solids carries out Fenton oxidation process, and first with sulfuric acid, its pH is adjusted to 4, then adds ferrous sulfate and hydrogen peroxide, control H
2o
2be 10:1, H with the mass ratio of TOC in the raffinate having filtered titanium dioxide solids
2o
2and Fe
2+mass ratio be 10:1, stirring reaction 0.5h, after completion of the reaction, with potassium hydroxide, the pH of raffinate after reaction is adjusted to 9, the raffinate after Fenton oxidation process, its TOC is 45mg/L.
Embodiment 3
The polypropylene catalyst titaniferous that the present embodiment uses is containing the hydrolysis of organism waste acid water from hydrolysis kettle in the preparation process of polypropylene industrial Ziegler-Natta catalyst, and wherein the mass concentration of hydrochloric acid is 23%, and the mass concentration of titanium is 12%, TOC is 2000mg/L.
The experimental procedure of the present embodiment:
1) polyolefin catalyst titaniferous is joined in the dialysing compartment of diffusion dialysis device containing organism waste acid water, tap water joins in the diffuser casing of diffusion dialysis device, wherein, the polyolefin catalyst titaniferous added is 1:1.2 containing the mass ratio of organism waste acid water and tap water, be separated by with anionic membrane between dialysing compartment and diffuser casing, both countercurrent flows, after the diffusion dialysis of 3h, raffinate is obtained in dialysing compartment outlet, hydrochloric acid is obtained in diffuser casing outlet, the hydrochloric acid obtained reclaims, the hydrochloric acid reclaimed is 0.9:1.3 with the mass ratio of the raffinate obtained, wherein, the mass concentration of the hydrochloric acid reclaimed is 18%, in the raffinate obtained, the mass concentration of hydrochloric acid is 5%, the mass content of titanium is 9%, TOC is 1950mg/L,
2) sodium hydroxide is added in the raffinate obtained to step 1), by the pH regulator to 7 of raffinate, and make the titanium in raffinate be converted into titanium dioxide solids, filter and the titanium dioxide solids obtained is reclaimed, in the titanium dioxide solids wherein reclaimed, the mass content of titanium dioxide is 98.5%, and having filtered TOC in the raffinate of titanium dioxide solids is 1900mg/L;
3) by step 2) raffinate that filtered titanium dioxide solids carries out Fenton oxidation process, and first with sulfuric acid, its pH is adjusted to 3.5, then adds ferrous sulfate and hydrogen peroxide, control H
2o
2be 15:1, H with the mass ratio of TOC in the raffinate having filtered titanium dioxide solids
2o
2and Fe
2+mass ratio be 6:1, stirring reaction 2h, after completion of the reaction, with sodium hydroxide, the pH of raffinate after reaction is adjusted to 7, the raffinate after Fenton oxidation process, its TOC is 40mg/L.
Embodiment 4
The polypropylene catalyst titaniferous that the present embodiment uses is containing the hydrolysis of organism waste acid water from hydrolysis kettle in the preparation process of polyolefin industry Ziegler-Natta catalyst, and wherein the mass concentration of hydrochloric acid is 25%, and the mass concentration of titanium is 11%, TOC is 2500mg/L.
The experimental procedure of the present embodiment:
1) polyolefin catalyst titaniferous is joined in the dialysing compartment of diffusion dialysis device containing organism waste acid water, tap water joins in the diffuser casing of diffusion dialysis device, wherein, the polyolefin catalyst titaniferous added is 1:1.1 containing the mass ratio of organism waste acid water and tap water, be separated by with anionic membrane between dialysing compartment and diffuser casing, both countercurrent flows, after the diffusion dialysis of 4h, raffinate is obtained in dialysing compartment outlet, hydrochloric acid is obtained in diffuser casing outlet, the hydrochloric acid obtained reclaims, the hydrochloric acid reclaimed is 0.9:1.2 with the mass ratio of the raffinate obtained, wherein, the mass concentration of the hydrochloric acid reclaimed is 23%, in the raffinate obtained, the mass concentration of hydrochloric acid is 3.5%, the mass content of titanium is 9%, TOC is 2400mg/L,
2) potassium hydroxide is added in the raffinate obtained to step 1), by the pH regulator to 7 at residual night, and make the titanium in raffinate be converted into titanium dioxide solids, filter and the titanium dioxide solids obtained is reclaimed, in the titanium dioxide solids wherein reclaimed, the mass content of titanium dioxide is 99%, and having filtered TOC in the raffinate of titanium dioxide solids is 2300mg/L;
3) by step 2) raffinate that filtered titanium dioxide solids carries out Fenton oxidation process, and first with sulfuric acid, its pH is adjusted to 3.8, then adds ferrous sulfate and hydrogen peroxide, control H
2o
2be 12:1, H with the mass ratio of TOC in the raffinate having filtered titanium dioxide solids
2o
2and Fe
2+mass ratio be 8:1, stirring reaction 1.5h, after completion of the reaction, with sodium hydroxide, the pH of raffinate after reaction is adjusted to 7, the raffinate after Fenton oxidation process, its TOC is 30mg/L.
The content be not described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (10)
1. a polyolefin catalyst titaniferous is containing the treatment process of organism waste acid water, it is characterized in that, described polyolefin catalyst titaniferous is the product water that the high boiling material in the preparation process of Ge Le-Natta catalyst is hydrolyzed through hydrolysis kettle containing organism waste acid water, its water quality characteristic is: the mass concentration of hydrochloric acid is 20 ~ 26%, the mass concentration of titanium is 10 ~ 13%, TOC is 1000 ~ 3000mg/L, specifically comprises the steps:
Step 1, diffusion dialysis: polyolefin catalyst titaniferous is joined in the dialysing compartment of diffusion dialysis device containing organism waste acid water, tap water joins in the diffuser casing of diffusion dialysis device, be separated by with anionic membrane between dialysing compartment and diffuser casing, both countercurrent flows, after diffusion dialysis after a while, obtain raffinate in dialysing compartment outlet, obtain hydrochloric acid in diffuser casing outlet, the hydrochloric acid obtained reclaims;
Step 2, filtration treatment: in the raffinate that step 1 obtains, add alkali, by the pH regulator of raffinate to 7 ~ 9, and make the titanium in raffinate be converted into titanium dioxide solids, filter and reclaimed by the titanium dioxide solids obtained;
Step 3, Fenton oxidation process: the raffinate having filtered titanium dioxide solids is carried out Fenton oxidation process, be first adjusted to 3 ~ 4 with acid by its pH, then add ferrous sulfate and oxydol H
2o
2, stirring reaction 0.5 ~ 3h, after completion of the reaction, is adjusted to 7 ~ 9 with alkali by the pH of raffinate after reaction.
2. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, it is characterized in that, in step 1, polyolefin catalyst titaniferous is 1:1 ~ 1:1.5 containing the mass ratio of organism waste acid water and tap water.
3. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, and it is characterized in that, for some time in step 1 is 2 ~ 5h.
4. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, it is characterized in that, the hydrochloric acid reclaimed in step 1 is 0.8:1.2 ~ 0.9:1.1 with the mass ratio of the raffinate obtained, in the raffinate obtained, the mass concentration of hydrochloric acid is 2 ~ 5%, the mass concentration of titanium is 8 ~ 10%, TOC is 950 ~ 2700mg/L.
5. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, it is characterized in that, the mass concentration of the hydrochloric acid that step 1 reclaims is 17 ~ 25%.
6. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, it is characterized in that, in the titanium dioxide solids that step 2 reclaims, the mass content of titanium dioxide is higher than 98%, and rest part is organism.
7. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, and it is characterized in that, step 2 has been filtered in the raffinate of titanium dioxide solids, and its TOC is 900 ~ 2500mg/L.
8. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, and it is characterized in that, the acid in step 3 is sulfuric acid or hydrochloric acid, ferrous sulfate and H
2o
2add-on should meet: H
2o
2be 10:1 ~ 20:1, H with the mass ratio of TOC in the raffinate having filtered titanium dioxide solids
2o
2and Fe
2+mass ratio be 5:1 ~ 10:1.
9. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, and it is characterized in that, the alkali in step 2 and 3 is sodium hydroxide or potassium hydroxide.
10. polyolefin catalyst titaniferous as claimed in claim 1 is containing the treatment process of organism waste acid water, and it is characterized in that, the raffinate in step 3 after Fenton oxidation process, its TOC is less than 50mg/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807384A (en) * | 2019-04-10 | 2020-10-23 | 中国石油化工股份有限公司 | Polyolefin magnesium titanium catalyst production residue treatment process |
| CN112898113A (en) * | 2019-12-03 | 2021-06-04 | 中国石油天然气股份有限公司 | Method for recycling polyolefin catalyst waste liquid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111807384A (en) * | 2019-04-10 | 2020-10-23 | 中国石油化工股份有限公司 | Polyolefin magnesium titanium catalyst production residue treatment process |
| CN111807384B (en) * | 2019-04-10 | 2022-08-19 | 中国石油化工股份有限公司 | Polyolefin magnesium titanium catalyst production residue treatment process |
| CN112898113A (en) * | 2019-12-03 | 2021-06-04 | 中国石油天然气股份有限公司 | Method for recycling polyolefin catalyst waste liquid |
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| CN104445701B (en) | 2016-01-13 |
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