CN108101106B - The Sewage treatment of zirconium carbonate process units discharge utilizes method - Google Patents
The Sewage treatment of zirconium carbonate process units discharge utilizes method Download PDFInfo
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Abstract
The present invention is that a kind of Sewage treatment of zirconium carbonate process units discharge utilizes method.Belong to the compounds process for production thereof of zirconium.It is characterized in that the waste water from crude product zirconium carbonate device and product zirconium carbonate device is used for zirconium basic sulphate device, substitute deionized water, as the raw material zirconium basic sulphate slurrying water in zirconium basic sulphate slurry and raw material preparation water and crude product zirconium carbonate device, zirconium carbonate product deionized water consumption per ton is reduced to 6.8 tons or less, save 89.8% or more anhydrous sodium sulfate, 32.8% or more sodium carbonate is saved, adding up to reduces about 342 yuan/ton of product raw materials consumption.The zirconium carbonate washing water and filtrated stock of zirconium carbonate product device discharge, are largely recycled.Most of deionized water and its chemical recovery carried utilize, and considerably reducing reduces production cost, alleviates the load of water treatment facilities.
Description
Technical field
The present invention is that a kind of Sewage treatment of zirconium carbonate process units discharge utilizes method.Belong to the compound preparation side of zirconium
Method.
Background technique
Zirconium carbonate Zr2O(CO3).nH2O, also known as zirconium oxycarbonate ZrO2CO2·nH2O or zirconyl carbonate.It is a kind of heavy
It is resistance to be widely used in function ceramics, structural ceramics, cosmetics antiperspirant, cleaning catalyst for tail gases of automobiles, papermaking for the zirconium compounds wanted
Water crosslinking agent, paint, printing ink drier, while being also the relatively inexpensive raw material of production superfine silicon dioxide.
Zirconium carbonate liquid phase fractional precipitation synthetic method have technology controlling and process it is simpler, stable product quality, activity preferably etc. it is excellent
Point, is widely adopted.Liquid phase fractional precipitation synthetic method technique is configured to first certain using zirconium oxychloride as starting material
The aqueous solution of concentration adds the concentrated sulfuric acid or sodium sulphate in the solution, and heating hydrolysis generates zirconium basic sulphate, then, carbonic acid is added
Sodium solution is translated into zirconium carbonate product.It reacts, is as follows:
ZrOCl2+H2SO4→ZrOSO4+HCl
ZrOSO4+NaCO3→ZrOCO3+Na2SO4
In production process, preparation deionized water, the slurrying deionized water of intermediate products, spy of each step material solution
It is not that intermediate zirconium basic sulphate, zirconium carbonate crude product and final products zirconium carbonate are all washed with deionized water, generates a large amount of
Washing water and filtrated stock, it is more than 15 tons that product per ton, which consumes deionized water,.In the prior art, zirconium carbonate process units generates
The unrecovered utilization of waste water, it is chemical that deionized water carries excessive raw material, part intermediate products and byproduct and final products etc.
Product whole primary emission.
Specifically, the Sewage treatment use aspects of zirconium carbonate process units discharge in the prior art exist as follows not
Foot:
1. in production process, slurrying is all using no ion after the preparation of each step material solution, the washing of intermediate products
Water causes deionized water consumption excessive.
2. in the zirconium carbonate crude product washing water discharged in crude product zirconium carbonate device, containing a large amount of sulfate and soda ash, not
It is recycled and is all discharged.Lead to the sodium sulphate carried in a large amount of deionized waters and washing water and sodium carbonate chemicals
The wasting of resources also increases the load of water treatment facilities.
3. the zirconium carbonate washing water and filtrated stock of the discharge of zirconium carbonate product device, are not recycled and are all arranged
It puts.The loss for leading to deionized water and its chemicals carried, also increases the load of water treatment facilities.
In view of the above, it generated in preparing zirconium carbonate production process, discharge a large amount of industrial wastewater, including washing water and washed
Wash rear material vacuum suction strainer or centrifuge dripping mother liquor.Without direct emission is recycled, not only waste of resource but also environment is polluted, simultaneously
Also improve production cost.Anxious recoverying and utilizing method to be sought.Ideal recoverying and utilizing method is not yet seen in the prior art.
Summary of the invention
It is an object of the invention to avoid above-mentioned shortcoming in the prior art, and provides and a kind of fill zirconium carbonate product
The wastewater collection generated with crude product zirconium carbonate device is set, as the washing of zirconium basic sulphate intermediate, slurrying and dissolution of raw material water,
The Sewage treatment of the zirconium carbonate process units discharge of substitution deionized water completely utilizes method.
The purpose of the present invention can be reached by following measure:
The Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method, during the zirconium carbonate process units includes
The waste water of mesosome zirconium basic sulphate device, crude product zirconium carbonate device and product zirconium carbonate device, the process units discharge comes from
The zirconium basic sulphate filtrated stock and washing water of intermediate zirconium basic sulphate device, the zirconium carbonate crude product mistake of crude product zirconium carbonate device
Filter the zirconium carbonate filtrated stock and washing water of mother liquor and washing water and product zirconium carbonate device；It is characterized by: coming from crude product
The waste water of zirconium carbonate device and product zirconium carbonate device is used for zirconium basic sulphate device, substitutes deionized water, is used as alkali formula sulfuric acid
Raw material zirconium basic sulphate slurrying water in zirconium slurry and raw material preparation water and crude product zirconium carbonate device.
The present invention is used for zirconium basic sulphate device, substitution from the waste water of crude product zirconium carbonate device and product zirconium carbonate device
Deionized water, as the raw material alkali formula sulphur in zirconium basic sulphate slurry and raw material preparation water and crude product zirconium carbonate device
Sour zirconium slurrying water.With substantive distinguishing features outstanding.
Firstly, the present invention selects the washing water generated with product zirconium carbonate device, all collect, in zirconium basic sulphate
The washing of the mesosome first order；It is because the washing water that product zirconium carbonate device generates contains only sodium chloride (0.14%), other ions
Concentration is both less than 20ppm.But sodium chloride is not involved in the reaction of buck zirconium sulfate, will not adversely affect to washing effect.
Second, the washing water that the present invention selects crude product zirconium carbonate device to generate all is collected, among zirconium basic sulphate
The washing of the body second level；Or for the raw material midbody zirconium basic sulphate slurrying for crude product zirconium carbonate device to substitute no ion
Water；It is because of the washing water that crude product zirconium carbonate device generates, containing only sodium sulphate (0.18%), sodium chloride (0.12%), sodium carbonate
(0.54%), other ion concentrations are both less than 20ppm.But sodium sulphate, sodium chloride are not reacted with zirconium basic sulphate, only sodium carbonate
It is reacted with the adsorbed acid of zirconium basic sulphate, is conducive to material washing.
Third, zirconium basic sulphate are reacted with sodium carbonate in the reaction for generating zirconium carbonate crude product, and sodium carbonate must be one excessive
Point, sulfate radical could more thoroughly be cemented out.The present invention selects the filtrated stock generated with crude product zirconium carbonate device, all
It collects, is washed for the zirconium basic sulphate intermediate third level.It is because of the filtrated stock that crude product zirconium carbonate device generates, containing only sulphur
Sour sodium (6.94%), sodium chloride (0.42%), sodium carbonate (3.31%), other ion concentrations are both less than 20ppm.But sodium sulphate,
Sodium chloride is not reacted with zirconium basic sulphate, and only sodium carbonate is reacted with the adsorbed acid of zirconium basic sulphate, is conducive to material washing,
Zirconium basic sulphate can even be washed into neutrality, save in alkali tune reaction and neutralize sodium carbonate consumed by zirconium basic sulphate adsorber acid.
In addition, after the present invention washs the zirconium basic sulphate intermediate third level, the cleaning solution of discharge is all collected, is used for
The dissolution of starting material zirconium oxychloride substitutes deionized water completely to prepare zirconium oxychloride aqueous solution.It is because of zirconium basic sulphate
After the washing of the intermediate third level, (sulfur acid sodium 6.38%, sodium chloride 2.86%, other ion concentrations are all small for the cleaning solution of discharge
In 20ppm) it collects, for dissolving zirconium oxychloride.Sodium sulphate is not reacted with zirconium oxychloride under room temperature, and sodium chloride is also not involved in
Reaction, but heat up after sodium sulphate but can be reacted completely with zirconium oxychloride.In this way, most sulfate radicals can be passed through alkali formula again
Zirconium sulfate takes in alkali tune reaction, to achieve the purpose that recycle.
The purpose of the present invention can also be reached by following measure:
The Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method, it is characterised in that described to be used for alkali formula sulphur
Sour zirconium slurry, recoverying and utilizing method are as follows:
1. the zirconium carbonate washing water of the discharge of zirconium carbonate product device described in, is all collected, it to be used for intermediate zirconium basic sulphate
Zirconium basic sulphate intermediate first order washing in device；
2. the zirconium carbonate crude product washing water discharged in crude product zirconium carbonate device described in is all collected, it to be used for zirconium basic sulphate
Zirconium basic sulphate intermediate second level washing in device；
3. the zirconium carbonate crude product filtrated stock of the discharge of crude product zirconium carbonate device described in, is all collected, it to be used for zirconium basic sulphate
Zirconium basic sulphate intermediate third level washing in device.
It is preferred technical solution.
The Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method, described to match for zirconium basic sulphate raw material
System water, recoverying and utilizing method are the waste water discharged after the zirconium basic sulphate intermediate third level is washed, all collect, use
In the dissolution of starting material zirconium oxychloride, deionized water is substituted completely to prepare zirconium oxychloride aqueous solution.
It is a preferred technical solution.
The Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method, described in crude product zirconium carbonate device
Raw material zirconium basic sulphate slurrying water, recoverying and utilizing method be discharged in crude product zirconium carbonate device zirconium carbonate crude product washing
Water, substitution deionized water are used to intermediate zirconium basic sulphate slurry is made.It is a preferred technical solution.
The Sewage treatment of zirconium carbonate zirconium carbonate process units discharge of the invention utilizes method, in the zirconium basic sulphate
The quality of material proportion of mesosome first order washing is: with the zirconium basic sulphate of solid meter: washing water=1:2.5 of zirconium carbonate~
3.It is preferred technical solution.
The Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method, the zirconium basic sulphate intermediate the
The quality of material proportion of second level washing is: with the zirconium basic sulphate of solid meter: zirconium carbonate crude product washing water=1:2.5~3.It is
Preferred technical solution.
The Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method, the zirconium basic sulphate intermediate the
The quality of material proportion of three-level washing is: with the zirconium basic sulphate of solid meter: zirconium carbonate crude product is filtered dry mother liquor=1:3~4.It is
Preferred technical solution.
The Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method, the liquid for zirconium carbonate after first zirconium sulfate
Phase fractional precipitation synthetic method production technology, the zirconium carbonate product produced reach following technical indicator:
The Sewage treatment of zirconium carbonate process units discharge of the invention is using the claimed technical solution of method compared to existing
There is technology, following good effect can be generated:
1. a kind of wastewater collection for generating zirconium carbonate product device and crude product zirconium carbonate device is provided, as alkali formula sulphur
Sour zirconium intermediate washing, slurrying and dissolution of raw material water substitute the waste water of the zirconium carbonate process units discharge of deionized water completely
Recoverying and utilizing method.
2. the waste water from crude product zirconium carbonate device and product zirconium carbonate device be used for zirconium basic sulphate device, substitution without from
Sub- water, as the raw material alkali in zirconium basic sulphate slurry and raw material zirconium oxychloride preparation water and crude product zirconium carbonate device
Formula zirconium sulfate slurrying water.Zirconium carbonate product deionized water consumption per ton is reduced to 6.8 tons hereinafter, being equivalent in the prior art
45% or less deionized water consumption.
3. in the zirconium carbonate crude product washing water discharged in crude product zirconium carbonate device, the sulfate and soda ash contained is most of
It is recycled, cost of material is substantially reduced.Method more compared with prior art saves 89.8% or more anhydrous sodium sulfate,
32.8% or more sodium carbonate is saved, adding up to reduces about 342 yuan/ton of product raw materials consumption.
4. the zirconium carbonate washing water and filtrated stock of the discharge of zirconium carbonate product device, are largely recycled.Big portion
Divide deionized water and its chemical recovery carried to utilize, considerably reduces the load of water treatment facilities.
Detailed description of the invention
The Sewage treatment of zirconium carbonate process units discharge Fig. 1 of the invention utilizes method and process flow diagram
Fig. 2 is the waster water process flow diagram of the zirconium carbonate process units discharge of the prior art
In figure
Washing water 1 is the washing water of zirconium basic sulphate device discharge
Washing water 2 is the washing water of crude product zirconium carbonate device discharge
Washing water 3 is the washing water of product zirconium carbonate device discharge
Mother liquor 1 is the filtrated stock of zirconium basic sulphate device discharge
Mother liquor 1 is the filtrated stock of crude product zirconium carbonate device discharge
The filtrated stock of 1 product zirconium carbonate device of mother liquor discharge
Specific embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
A kind of Sewage treatment of zirconium carbonate process units discharge of the invention utilizes method
Waste water from crude product zirconium carbonate device and product zirconium carbonate device is used for zirconium basic sulphate device, substitutes without ion
Water, as the raw material zirconium basic sulphate system in zirconium basic sulphate slurry and raw material preparation water and crude product zirconium carbonate device
Slurry water, specific steps are as follows:
1. the zirconium basic sulphate intermediate first order is washed
The zirconium carbonate washing water of zirconium carbonate product device discharge, is all collected, in intermediate zirconium basic sulphate device
The zirconium basic sulphate intermediate first order washing；
The quality of material proportion of zirconium basic sulphate intermediate first order washing is: with the zirconium basic sulphate of solid meter: carbon
Washing water=200:500 of sour zirconium.
2. the zirconium basic sulphate intermediate second level is washed
The zirconium carbonate crude product washing water discharged in crude product zirconium carbonate device is all collected, in zirconium basic sulphate device
The zirconium basic sulphate intermediate second level washing；
The quality of material proportion of zirconium basic sulphate intermediate second level washing is: with the zirconium basic sulphate of solid meter: carbon
Sour zirconium crude product washing water=200:500.
3. the zirconium basic sulphate intermediate third level is washed
The zirconium carbonate crude product filtrated stock of crude product zirconium carbonate device discharge, is all collected, in zirconium basic sulphate device
The zirconium basic sulphate intermediate third level washing.
The quality of material proportion of zirconium basic sulphate intermediate third level washing is: with the zirconium basic sulphate of solid meter: carbon
Sour zirconium crude product is filtered dry mother liquor=200:600.
4. prepared by zirconium oxychloride aqueous solution
The waste water discharged after the washing of the zirconium basic sulphate intermediate third level, is all collected, and is used for starting material oxychlorination
The dissolution of zirconium substitutes deionized water completely to prepare zirconium oxychloride aqueous solution.
In the waste water discharged after the zirconium basic sulphate intermediate third level washing collected after measured, sodium sulphate content
6.94wt%,.Every kilogram of zirconium oxychloride, 3.42 liters of the waste water discharged after being washed with the third level dissolutions.It is prepared into zirconium oxychloride
Solution.
5. prepared by zirconium basic sulphate intermediate
A. in zirconium oxycarbonate reaction kettle, the zirconyl chloride solution for 4. preparing step under stirring is warming up to 80 DEG C, presses
0.03 kilogram of anhydrous sodium sulfate is added according to formula is drafted, is continuously heating to 98 DEG C, and that the reaction was continued is 1 small for heat preservation at a temperature of 98 DEG C
When.Then 60 DEG C are cooled to, vacuum filter, filter cake is standby to be washed.
B. zirconium basic sulphate intermediate washs
The zirconium basic sulphate filter cake of above-mentioned a preparation is washed according to the method for step 1. 2. 3., prepared by standby zirconium carbonate crude product；
6. prepared by crude product zirconium carbonate
A. zirconium basic sulphate slurrying
It will be put into crude product zirconium carbonate reaction kettle from the zirconium basic sulphate filter cake of step 5., under stirring, with crude product carbonic acid
The zirconium carbonate crude product washing water discharged in zirconium device substitutes deionized water for intermediate zirconium basic sulphate and slurry is made.Solid-liquid matter
Amount ratio is controlled in 200:500.
B. prepared by crude product zirconium carbonate
It under stirring, is made in slurry in the zirconium basic sulphate that above-mentioned a prepares, the sodium carbonate that concentration is 23wt% is added
Solution, reaction, the pH value of feed liquid is adjusted to 7.8.Then, 65 DEG C are warming up to, and at a temperature of 65 DEG C, insulation reaction half is small
When.It filters and crude product zirconium carbonate is made.In reaction process, 0.205 kilogram of sodium carbonate is consumed, 3.28 liters of output mother liquor, is less than and is added
3.42 liters, can by crude product zirconium carbonate filter generate mother liquor fully recovering.
7. the preparation of zirconium carbonate product
6. crude product zirconium carbonate that step is prepared is acidified with hydrochloric acid, adjusts the pH value of feed liquid between 3.5~4.5.Filtering, filter
After cake washs qualification with deionized water, centrifuge dripping.0.868 kilogram of zirconium carbonate product is made.
It is converted, produces 1 kilogram of zirconium carbonate product, consume 0.032 kilogram of anhydrous sodium sulfate, 0.236 kilogram of sodium carbonate.It is existing
Have in technology, produces 1 ton of 0.314 ton of anhydrous sodium sulfate of zirconium carbonate product consumption (market price is calculated by 600 yuan/ton), carbonic acid
0.351 ton of sodium (market price is by 1500 yuan/ton of calculating).Method of the invention compared with prior art, is saved without sodium sulphate
89.8%, sodium carbonate 32.8% is saved, adding up to reduces about 342 yuan/ton of product raw materials consumption.
The zirconyl carbonate produced reaches following technical indicator:
The quality standard of zirconyl carbonate product is reached.
Embodiment 2
Waste water from crude product zirconium carbonate device and product zirconium carbonate device is used for zirconium basic sulphate device, substitutes without ion
Water, as the raw material zirconium basic sulphate system in zirconium basic sulphate slurry and raw material preparation water and crude product zirconium carbonate device
Slurry water, specific steps are as follows:
1. the zirconium basic sulphate intermediate first order is washed
The zirconium carbonate washing water of zirconium carbonate product device discharge, is all collected, in intermediate zirconium basic sulphate device
The zirconium basic sulphate intermediate first order washing；
The quality of material proportion of zirconium basic sulphate intermediate first order washing is: with the zirconium basic sulphate of solid meter: carbon
Washing water=200:500 of sour zirconium.
2. the zirconium basic sulphate intermediate second level is washed
The zirconium carbonate crude product washing water discharged in crude product zirconium carbonate device is all collected, in zirconium basic sulphate device
The zirconium basic sulphate intermediate second level washing；
The quality of material proportion of zirconium basic sulphate intermediate second level washing is: with the zirconium basic sulphate of solid meter: carbon
Sour zirconium crude product washing water=200:500.
3. the zirconium basic sulphate intermediate third level is washed
The zirconium carbonate crude product filtrated stock of crude product zirconium carbonate device discharge, is all collected, in zirconium basic sulphate device
The zirconium basic sulphate intermediate third level washing.
The quality of material proportion of zirconium basic sulphate intermediate third level washing is: with the zirconium basic sulphate of solid meter: carbon
Sour zirconium crude product is filtered dry mother liquor=200:700.
4. prepared by zirconium oxychloride aqueous solution
The waste water discharged after the washing of the zirconium basic sulphate intermediate third level, is all collected, and is used for starting material oxychlorination
The dissolution of zirconium substitutes deionized water completely to prepare zirconium oxychloride aqueous solution.
In the waste water discharged after the zirconium basic sulphate intermediate third level washing collected after measured, sodium sulphate content
6.88wt%,.Every kilogram of zirconium oxychloride, 3.42 liters of the waste water discharged after being washed with the third level dissolutions.It is prepared into zirconium oxychloride
Solution.
5. prepared by zirconium basic sulphate intermediate
A. in zirconium oxycarbonate reaction kettle, the zirconyl chloride solution for 4. preparing step under stirring is warming up to 80 DEG C, presses
0.03 kilogram of anhydrous sodium sulfate is added according to formula is drafted, is continuously heating to 98 DEG C, and that the reaction was continued is 1 small for heat preservation at a temperature of 98 DEG C
When.Then 60 DEG C are cooled to, vacuum filter, filter cake is standby to be washed.
B. zirconium basic sulphate intermediate washs
The zirconium basic sulphate filter cake of above-mentioned a preparation is washed according to the method for step 1. 2. 3., prepared by standby zirconium carbonate crude product；
6. prepared by crude product zirconium carbonate
A. zirconium basic sulphate slurrying
It will be put into crude product zirconium carbonate reaction kettle from the zirconium basic sulphate filter cake of step 5., under stirring, with crude product carbonic acid
The zirconium carbonate crude product washing water discharged in zirconium device substitutes deionized water for intermediate zirconium basic sulphate and slurry is made.Solid-liquid matter
Amount ratio is controlled in 200:500.
B. prepared by crude product zirconium carbonate
It under stirring, is made in slurry in the zirconium basic sulphate that above-mentioned a prepares, the sodium carbonate that concentration is 23wt% is added
Solution, reaction, the pH value of feed liquid is adjusted to 7.8.Then, 65 DEG C are warming up to, and at a temperature of 65 DEG C, insulation reaction half is small
When.It filters and crude product zirconium carbonate is made.In reaction process, 0.197 kilogram of sodium carbonate is consumed, 3.25 liters of output mother liquor, is less than and is added
3.42 liters, can by crude product zirconium carbonate filter generate mother liquor fully recovering.
7. the preparation of zirconium carbonate product
6. crude product zirconium carbonate that step is prepared is acidified with hydrochloric acid, adjusts the pH value of feed liquid between 3.5~4.5.Filtering, filter
After cake washs qualification with deionized water, centrifuge dripping.0.872 kilogram of zirconium carbonate product is made.
It is converted, produces 1 kilogram of zirconium carbonate product, consume 0.034 kilogram of anhydrous sodium sulfate, 0.224 kilogram of sodium carbonate.It is existing
Have in technology, produces 1 ton of 0.314 ton of anhydrous sodium sulfate of zirconium carbonate product consumption (market price is calculated by 600 yuan/ton), carbonic acid
0.351 ton of sodium (market price is by 1500 yuan/ton of calculating).Method of the invention compared with prior art, is saved without sodium sulphate
89.2%, sodium carbonate 36.2% is saved, adding up to reduces about 359 yuan/ton of product raw materials consumption.
The zirconyl carbonate produced reaches following technical indicator:
The quality standard of zirconyl carbonate product is reached.
Embodiment 3
Waste water from crude product zirconium carbonate device and product zirconium carbonate device is used for zirconium basic sulphate device, substitutes without ion
Water, as the raw material zirconium basic sulphate system in zirconium basic sulphate slurry and raw material preparation water and crude product zirconium carbonate device
Slurry water, specific steps are as follows:
1. the zirconium basic sulphate intermediate first order is washed
The zirconium carbonate washing water of zirconium carbonate product device discharge, is all collected, in intermediate zirconium basic sulphate device
The zirconium basic sulphate intermediate first order washing；
The quality of material proportion of zirconium basic sulphate intermediate first order washing is: with the zirconium basic sulphate of solid meter: carbon
Washing water=200:500 of sour zirconium.
2. the zirconium basic sulphate intermediate second level is washed
The zirconium carbonate crude product washing water discharged in crude product zirconium carbonate device is all collected, in zirconium basic sulphate device
The zirconium basic sulphate intermediate second level washing；
The quality of material proportion of zirconium basic sulphate intermediate second level washing is: with the zirconium basic sulphate of solid meter: carbon
Sour zirconium crude product washing water=200:500.
3. the zirconium basic sulphate intermediate third level is washed
The zirconium carbonate crude product filtrated stock of crude product zirconium carbonate device discharge, is all collected, in zirconium basic sulphate device
The zirconium basic sulphate intermediate third level washing.
The quality of material proportion of zirconium basic sulphate intermediate third level washing is: with the zirconium basic sulphate of solid meter: carbon
Sour zirconium crude product is filtered dry mother liquor=200:800.
4. prepared by zirconium oxychloride aqueous solution
The waste water discharged after the washing of the zirconium basic sulphate intermediate third level, is all collected, and is used for starting material oxychlorination
The dissolution of zirconium substitutes deionized water completely to prepare zirconium oxychloride aqueous solution.
In the waste water discharged after the zirconium basic sulphate intermediate third level washing collected after measured, sodium sulphate content
6.84wt%,.Every kilogram of zirconium oxychloride, 3.42 liters of the waste water discharged after being washed with the third level dissolutions.It is prepared into zirconium oxychloride
Solution.
5. prepared by zirconium basic sulphate intermediate
A. in zirconium oxycarbonate reaction kettle, the zirconyl chloride solution for 4. preparing step under stirring is warming up to 80 DEG C, presses
0.032 kilogram of anhydrous sodium sulfate is added according to formula is drafted, is continuously heating to 98 DEG C, and the reaction was continued 1 for heat preservation at a temperature of 98 DEG C
Hour.Then 60 DEG C are cooled to, vacuum filter, filter cake is standby to be washed.
B. zirconium basic sulphate intermediate washs
The zirconium basic sulphate filter cake of above-mentioned a preparation is washed according to the method for step 1. 2. 3., prepared by standby zirconium carbonate crude product；
6. prepared by crude product zirconium carbonate
A. zirconium basic sulphate slurrying
It will be put into crude product zirconium carbonate reaction kettle from the zirconium basic sulphate filter cake of step 5., under stirring, with crude product carbonic acid
The zirconium carbonate crude product washing water discharged in zirconium device substitutes deionized water for intermediate zirconium basic sulphate and slurry is made.Solid-liquid matter
Amount ratio is controlled in 200:500.
B. prepared by crude product zirconium carbonate
It under stirring, is made in slurry in the zirconium basic sulphate that above-mentioned a prepares, the sodium carbonate that concentration is 23wt% is added
Solution, reaction, the pH value of feed liquid is adjusted to 7.8.Then, 65 DEG C are warming up to, and at a temperature of 65 DEG C, insulation reaction half is small
When.It filters and crude product zirconium carbonate is made.In reaction process, 0.192 kilogram of sodium carbonate is consumed, 3.22 liters of output mother liquor, is less than and is added
3.42 liters, can by crude product zirconium carbonate filter generate mother liquor fully recovering.
7. the preparation of zirconium carbonate product
6. crude product zirconium carbonate that step is prepared is acidified with hydrochloric acid, adjusts the pH value of feed liquid between 3.5~4.5.Filtering, filter
After cake washs qualification with deionized water, centrifuge dripping.0.875 kilogram of zirconium carbonate product is made.
It is converted, produces 1 kilogram of zirconium carbonate product, consume 0.037 kilogram of anhydrous sodium sulfate, 0.219 kilogram of sodium carbonate.It is existing
Have in technology, produces 1 ton of 0.314 ton of anhydrous sodium sulfate of zirconium carbonate product consumption (market price is calculated by 600 yuan/ton), carbonic acid
0.351 ton of sodium (market price is by 1500 yuan/ton of calculating).Method of the invention compared with prior art, is saved without sodium sulphate
88.2%, sodium carbonate 37.6% is saved, adding up to reduces about 364 yuan/ton of product raw materials consumption.
The zirconyl carbonate produced reaches following technical indicator:
The quality standard of zirconyl carbonate product is reached.
Above three are averagely saved 89.1% anhydrous sodium sulphate and 35.5% soda ash, reduce product raw materials consumption about 355
Yuan/ton.And zirconium basic sulphate device does not use deionized water, through workshop water meter statistical comparison, produces 1 ton of carbon of the invention
Sour zirconium product deionized water consumption drops to 6.8 tons or less by 15 tons or more of the prior art.
Claims (8)
1. a kind of Sewage treatment of zirconium carbonate process units discharge utilizes method, the zirconium carbonate process units includes intermediate alkali
The waste water of formula zirconium sulfate device, crude product zirconium carbonate device and product zirconium carbonate device, the process units discharge comes from intermediate
The zirconium basic sulphate filtrated stock and washing water of zirconium basic sulphate device, the zirconium carbonate crude product filtrated stock of crude product zirconium carbonate device
With the zirconium carbonate filtrated stock and washing water of washing water and product zirconium carbonate device；It is characterized in that being filled from crude product zirconium carbonate
It sets with the waste water of product zirconium carbonate device for zirconium basic sulphate device, substitutes deionized water, be used as zirconium basic sulphate washing and use
Raw material zirconium basic sulphate slurrying water in water and raw material preparation water and crude product zirconium carbonate device.
2. utilizing method according to the Sewage treatment that the zirconium carbonate process units of claim 1 discharges, it is characterised in that described to be used for
Zirconium basic sulphate slurry, recoverying and utilizing method are as follows:
1. the zirconium carbonate washing water of the discharge of zirconium carbonate product device described in, is all collected, it to be used for intermediate zirconium basic sulphate device
In the zirconium basic sulphate intermediate first order washing；
2. the zirconium carbonate crude product washing water discharged in crude product zirconium carbonate device described in is all collected, it to be used for zirconium basic sulphate device
In the zirconium basic sulphate intermediate second level washing；
3. the zirconium carbonate crude product filtrated stock of the discharge of crude product zirconium carbonate device described in, is all collected, it to be used for zirconium basic sulphate device
In the zirconium basic sulphate intermediate third level washing.
3. utilizing method according to the Sewage treatment that the zirconium carbonate process units of claim 1 discharges, it is characterised in that described to be used for
Zirconium basic sulphate raw material, which is prepared, uses water, and recoverying and utilizing method is discharged after the zirconium basic sulphate intermediate third level is washed
Waste water is all collected, and for the dissolution of starting material zirconium oxychloride, it is water-soluble to prepare zirconium oxychloride to substitute deionized water completely
Liquid.
4. utilizing method according to the Sewage treatment that the zirconium carbonate process units of claim 1 discharges, it is characterised in that described to be used for
Raw material zirconium basic sulphate slurrying water in crude product zirconium carbonate device, recoverying and utilizing method are discharged in crude product zirconium carbonate device
Zirconium carbonate crude product washing water, substitution deionized water are used to intermediate zirconium basic sulphate slurry is made.
5. utilizing method according to the Sewage treatment that the zirconium carbonate process units of claim 2 discharges, it is characterised in that described in 1.
The zirconium basic sulphate intermediate first order washing quality of material proportion be: with the zirconium basic sulphate of solid meter: zirconium carbonate
Washing water=1:2.5~3.
6. utilizing method according to the Sewage treatment that the zirconium carbonate process units of claim 2 discharges, it is characterised in that described in 2.
The zirconium basic sulphate intermediate second level washing quality of material proportion be: with the zirconium basic sulphate of solid meter: zirconium carbonate is thick
Product washing water=1:2.5~3.
7. utilizing method according to the Sewage treatment that the zirconium carbonate process units of claim 2 discharges, it is characterised in that described in 3.
The zirconium basic sulphate intermediate third level washing quality of material proportion be: with the zirconium basic sulphate of solid meter: zirconium carbonate is thick
Product are filtered dry mother liquor=1:3~4.
8. the Sewage treatment that the zirconium carbonate process units of claim 1 discharges utilizes method, it is characterised in that for first zirconium sulfate
The liquid phase fractional precipitation synthetic method production technology of zirconium carbonate, the zirconium carbonate product produced reach following technical indicator afterwards:
The quality standard of zirconium carbonate product is reached.
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