CN113800557A - Water recycling system and method for preparing titanium dioxide calcination crystal seeds by sulfuric acid method - Google Patents
Water recycling system and method for preparing titanium dioxide calcination crystal seeds by sulfuric acid method Download PDFInfo
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- CN113800557A CN113800557A CN202111137387.1A CN202111137387A CN113800557A CN 113800557 A CN113800557 A CN 113800557A CN 202111137387 A CN202111137387 A CN 202111137387A CN 113800557 A CN113800557 A CN 113800557A
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- 239000013078 crystal Substances 0.000 title claims abstract description 155
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 139
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000001354 calcination Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 45
- 238000004064 recycling Methods 0.000 title claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 279
- 239000012528 membrane Substances 0.000 claims abstract description 169
- 238000011282 treatment Methods 0.000 claims abstract description 65
- 238000000926 separation method Methods 0.000 claims abstract description 48
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000010865 sewage Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 235000010215 titanium dioxide Nutrition 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 55
- 150000003839 salts Chemical class 0.000 claims description 43
- 239000003513 alkali Substances 0.000 claims description 42
- 238000004090 dissolution Methods 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 42
- 239000002351 wastewater Substances 0.000 claims description 36
- 230000003472 neutralizing effect Effects 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 29
- 238000004061 bleaching Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 238000005374 membrane filtration Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000000053 physical method Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000012065 filter cake Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000009295 crossflow filtration Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 208000028659 discharge Diseases 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
- C01G23/0534—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts in the presence of seeds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of titanium dioxide preparation, and discloses a water recycling system and method for preparing titanium dioxide calcination crystal seeds by a sulfuric acid method, wherein the system comprises: the membrane washing unit is used for washing the calcined crystal seeds until qualified calcined crystal seeds are separated; a second neutralization unit connected to the membrane water washing unit; and the membrane separation unit is respectively connected with the second neutralization unit, the membrane washing unit and the sewage treatment unit, wherein the water neutralized by the second neutralization unit enters the membrane separation unit, the concentrated solution separated by the membrane separation unit enters the sewage treatment unit, and the clear solution separated by the membrane separation unit enters the membrane washing unit. According to the invention, the membrane washing unit is used for removing chloride ions in the calcined crystal seeds by using a physical method, so that the application of the calcined crystal seeds in the titanium dioxide calcining unit is not influenced, and the service lives of subsequent equipment and pipelines are prolonged; meanwhile, the treatment efficiency and the reuse rate of the washing water are improved through the second neutralization unit and the membrane separation unit.
Description
Technical Field
The invention relates to the technical field of titanium dioxide preparation, in particular to a water recycling system and method for preparing titanium dioxide calcination crystal seeds by a sulfuric acid method.
Background
With the gradual release of titanium dioxide productivity in China and the annual improvement of the national environmental protection index, alkaline wastewater generated in the preparation process of the calcined seed crystal and a large amount of chloride ions introduced by the calcined seed crystal in the titanium dioxide bleaching unit added by a sulfuric acid method are more and more emphasized by titanium dioxide manufacturers, a large amount of chloride ions introduced by the calcined seed crystal are discharged out of a white water discharge system along with the primary washing of the titanium dioxide (because secondary washing of the white water is recycled to the primary washing unit as primary washing water supplement water, the chloride ions introduced by the calcined seed crystal are discharged out of the system along with the primary washing of the white water), so that a large amount of chloride ions are contained in the primary washing of the white water, the chloride-containing wastewater severely corrodes subsequent water treatment equipment and pipelines, and the service life of the equipment and the pipelines is greatly shortened.
The calcined seed crystal is generally formed by alkali dissolution, water washing, neutralization and acid dissolution of the secondary washing qualified material, and a large amount of alkaline wastewater containing powder is generated in the water washing process. In addition, the calcined crystal seed formed after acid dissolution belongs to a colloid, and the particle size is too small, so that the calcined crystal seed cannot form a filter cake in a conventional titanium dioxide washing device for washing with water to remove chloride ions, such as a leaf filter, a plate frame and a mole machine. If the chlorine ions in the calcined seed crystal are to be removed by a chemical method, the calcined seed crystal is inactivated, so that the original conversion effect of the calcined seed crystal in a titanium dioxide calcining unit is lost.
Therefore, it is necessary to design a water recycling system for preparing the sulfuric acid method titanium dioxide calcination crystal seeds to solve the above problems.
Disclosure of Invention
In order to solve the technical problems, the invention provides a water recycling system and a water recycling method for preparing titanium dioxide calcination crystal seeds by a sulfuric acid method, wherein chloride ions in the calcination crystal seeds are removed by a membrane washing unit by using a physical method, so that the application of the calcination crystal seeds in a titanium dioxide calcination unit is not influenced, and the service lives of subsequent equipment and pipelines are prolonged; meanwhile, the treatment efficiency and the reuse rate of the washing water are improved through the second neutralization unit and the membrane separation unit.
The technical scheme provided by the invention is as follows:
a water recycling system for preparing sulfuric acid method titanium white calcination crystal seeds comprises:
the membrane washing unit is used for washing the calcined crystal seeds until qualified calcined crystal seeds are separated;
the second neutralization unit is connected with the membrane washing unit and is used for neutralizing the washing water in the membrane washing unit;
and the membrane separation unit is respectively connected with the second neutralization unit, the membrane washing unit and the sewage treatment unit, wherein the water neutralized by the second neutralization unit enters the membrane separation unit, the concentrated solution separated by the membrane separation unit enters the sewage treatment unit, and the clear solution separated by the membrane separation unit enters the membrane washing unit.
Further preferably, the membrane washing unit includes circulation jar, circulating pump and membrane washing device, the play liquid end of circulation jar with the feed liquor end of circulating pump is connected, the play liquid end of circulating pump with the feed liquor end of membrane washing device is connected, the membrane washing device with the circulation jar is connected.
Further preferably, the membrane water washing device is provided with a cross-flow filtering membrane, the precision of the cross-flow filtering membrane is 10-1000nm, the membrane surface flow rate of the cross-flow filtering membrane is 3-6m/s, and the transmembrane pressure difference of the cross-flow filtering membrane is 0.05-0.6 MPa.
Further preferably, the method further comprises the following steps:
the alkali dissolving unit is used for carrying out alkali dissolving on the qualified second-washing material;
the washing unit is connected with the alkali dissolving unit and is used for washing the qualified second-washing material after alkali dissolving;
the first neutralizing unit is connected with the water washing unit and is used for neutralizing the qualified second washing material after water washing;
and the acid dissolving unit is connected with the first neutralizing unit and is used for carrying out acid dissolving on the neutralized qualified secondary washing material and obtaining the calcined seed crystal.
Further preferably, the method further comprises the following steps:
and the membrane filtering unit is respectively connected with the water washing unit, the alkali dissolving unit and the second neutralizing unit, wherein the wastewater generated in the water washing unit enters the membrane filtering unit, the powder recovered by the membrane filtering unit enters the alkali dissolving unit, and the wastewater generated by the membrane filtering unit enters the second neutralizing unit.
Further preferably, the membrane separation unit is provided with a reverse osmosis membrane, the rejection rate of the reverse osmosis membrane on dissolved salts in a solution is more than 99%, and the operating pressure of the reverse osmosis membrane is 1 to 10 MPa.
Further preferably, the method further comprises the following steps:
the bleaching unit is used for bleaching a washing slurry to obtain a bleaching slurry;
the secondary washing unit is connected with the bleaching unit and is used for washing the bleaching pulp to obtain secondary washing pulp;
the salt treatment unit is respectively connected with the secondary washing unit and the membrane washing unit and is used for carrying out salt treatment on the secondary washing slurry;
and the calcining unit is connected with the salt treatment unit and is used for adding the qualified calcining seed crystal into the secondary washing slurry after salt treatment for calcining.
The other technical scheme provided by the invention is as follows:
a water recycling method for preparing titanium dioxide calcination crystal seeds by a sulfuric acid method comprises the following steps:
introducing the prepared calcined crystal seed into a membrane washing unit, introducing desalted water to wash the calcined crystal seed until the qualified calcined crystal seed is separated out, and then introducing the calcined crystal seed into a salt treatment unit;
introducing the water washing water in the membrane water washing unit into a second neutralization unit for neutralization;
and the water neutralized by the second neutralization unit enters a membrane separation unit for separation, the separated concentrated solution is discharged to a sewage treatment station for treatment, and the separated clear solution enters a membrane washing unit for washing the calcined seed crystal.
Further preferably, the method comprises the steps of introducing the prepared calcined seed crystal into a membrane washing unit, introducing desalted water to wash the calcined seed crystal, and introducing the calcined seed crystal into a salt treatment unit after qualified calcined seed crystals are separated out, and specifically comprises the following steps:
introducing the prepared calcining seed crystal into a circulating tank, and stopping introducing until the calcining seed crystal reaches a preset liquid level of the circulating tank;
and introducing desalted water into the circulating tank, starting a circulating pump at the same time, sending the calcined seed crystal in the circulating tank into a membrane washing device for solid-liquid separation, sending the separated clear liquid into a second neutralization unit, returning the separated slurry into the circulating tank for continuous washing separation until the contents of chloride ions and trace soluble metal ions in the calcined seed crystal reach a preset range, and sending the qualified calcined seed crystal into a salt treatment unit.
Further preferably, the method comprises the following steps of introducing the prepared calcined seed crystal into a membrane washing unit, introducing desalted water to wash the calcined seed crystal until qualified calcined seed crystal is separated, and then introducing the calcined seed crystal into a salt treatment unit:
taking the qualified material of the second washing, and carrying out alkali dissolution through an alkali dissolution unit;
washing the qualified second-washing material after the alkali dissolution by a washing unit;
neutralizing the washed qualified second washing material through a first neutralization unit;
and carrying out acid dissolution on the neutralized secondary-washing qualified material through an acid dissolution unit to obtain the calcined seed crystal.
Further preferably, the second-washing qualified material is subjected to alkali dissolution through an alkali dissolution unit, and the method specifically comprises the following steps: adding a sodium hydroxide solution with the concentration of 40-60% into the second-washing qualified material according to the proportion of 0.8-1.4 times of titanium dioxide, fully stirring, heating to boil, keeping the temperature for more than 100min, and then cooling to 40-80 ℃;
and/or washing the qualified second-washing material after the alkali dissolution by a washing unit, and specifically comprises the following steps: washing the second washing qualified material after alkali dissolution with water to remove redundant sodium hydroxide in the system after reaction and a small amount of sulfate radical brought by the second washing qualified material, washing with water until washing filtrate does not contain sulfate radical, feeding powder-containing wastewater generated by washing with water into a membrane filtration unit, recovering powder in the wastewater after treatment by the membrane filtration unit, returning the recovered powder to the alkali dissolution unit, and feeding alkaline wastewater generated by the membrane filtration unit into a second neutralization unit;
and/or neutralizing the qualified second washing material after washing through a first neutralization unit, and specifically comprising the following steps: neutralizing the washed qualified second-washing material, controlling the pH value to be 2.5-3.5 in the neutralization process, heating at a preset heating speed, and keeping the temperature for a preset time until the metal hydroxide is completely dissolved;
and/or performing acid dissolution on the neutralized qualified secondary washing material through an acid dissolution unit to obtain the calcined seed crystal, and specifically comprises the following steps: and adding a preset amount of hydrochloric acid into the neutralized secondary-washing qualified material for acid dissolution, heating to boil, keeping the boiling state for more than 100min, and finally quenching and diluting to obtain the calcined crystal seed.
Further preferably, the step of separating the qualified calcined seed crystal and then feeding the qualified calcined seed crystal into a salt treatment unit specifically comprises the steps of:
reacting titanium ore with sulfuric acid to obtain titanyl sulfate solution, hydrolyzing, washing with water once to obtain a washing slurry, and bleaching the washing slurry by a bleaching unit to obtain a bleached slurry;
and washing the bleaching slurry by a secondary washing unit to obtain secondary washing slurry, carrying out salt treatment on the secondary washing slurry by the salt treatment unit, adding the qualified calcining seed crystal, and calcining by the calcining unit to obtain the titanium dioxide.
Compared with the prior art, the water recycling system and method for preparing the sulfuric acid method titanium dioxide calcination seed crystal have the beneficial effects that:
in the invention, the membrane washing unit directly removes chloride ions in the calcined seed crystal by using a physical method, and the calcined seed crystal does not need to be subjected to treatments such as neutralization, flocculation and the like before membrane washing, so that the application of the calcined seed crystal in the titanium dioxide calcining unit is not influenced, and the service lives of subsequent equipment and pipelines are prolonged; meanwhile, under the condition that the quality of the calcined crystal seeds is not influenced, the alkaline wastewater generated in the preparation process of the calcined crystal seeds and the acidic wastewater generated in the washing process of the calcined crystal seeds are recycled, the water quality characteristics of the alkaline wastewater and the acidic wastewater are ingeniously utilized by the second neutralizing unit, a special separating device is not needed for the wastewater treatment after neutralization, only a conventional membrane separating device is needed for treatment, the project investment cost is reduced, the wastewater discharge is effectively reduced, the water consumption is reduced, and the economic benefit is improved.
Drawings
The foregoing features, technical features, advantages and embodiments are further described in the following detailed description of the preferred embodiments, which is to be read in connection with the accompanying drawings.
FIG. 1 is a process flow diagram of a system for preparing calcined seed crystals of titanium dioxide powder and recycling water according to an embodiment of the present invention;
FIG. 2 is a process flow diagram of a membrane water wash unit in accordance with one embodiment of the present invention.
The reference numbers illustrate:
1. the method comprises the following steps of washing qualified materials, washing qualified materials by 2, an alkali dissolution unit, 3, a water washing unit, 4, a first neutralization unit, 5, an acid dissolution unit, 6, a membrane filtration unit, 7, a calcination crystal seed, 8, a second neutralization unit, 9, a membrane separation unit, 10, a sewage treatment unit, 11, a membrane washing unit, 12, desalted water, 13, a bleaching unit, 14, a secondary water washing unit, 15, a salt treatment unit, 16, a calcination unit, 17, a circulation tank, 18, a circulation pump and 19, and a membrane washing device.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth, such as particular system structures, techniques, etc. in order to provide a thorough understanding of the embodiments of the present application. However, it will be apparent to one skilled in the art that the present application may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present application with unnecessary detail.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
For the sake of simplicity, the drawings only schematically show the parts relevant to the present invention, and they do not represent the actual structure as a product. In addition, in order to make the drawings concise and understandable, components having the same structure or function in some of the drawings are only schematically illustrated or only labeled. In this document, "one" means not only "only one" but also a case of "more than one".
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
In the embodiments shown in the drawings, the directions such as up, down, left, right, front, and rear are used to explain the structure and movement of various components of the present invention not absolutely but relatively. These illustrations are appropriate when these components are in the positions shown in the figures. If the description of the positions of these components changes, the indication of these directions changes accordingly.
In addition, in the description of the present application, the terms "first", "second", and the like are used only for distinguishing the description, and are not intended to indicate or imply relative importance.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will be made with reference to the accompanying drawings. It is obvious that the drawings in the following description are only some examples of the invention, and that for a person skilled in the art, other drawings and embodiments can be derived from them without inventive effort.
As a specific embodiment, as shown in fig. 1, this embodiment provides a water recycling system for preparing a seed crystal for calcining titanium dioxide by a sulfuric acid method, including: the membrane washing unit 11 is used for washing the calcined seed crystal 7 until the qualified calcined seed crystal is separated; the second neutralization unit 8 is connected with the membrane water washing unit 11 and is used for neutralizing the acidic water washing generated in the membrane water washing unit 11; and the membrane separation unit 9 is respectively connected with the second neutralization unit 8, the membrane washing unit 11 and the sewage treatment unit 10, wherein the water neutralized by the second neutralization unit 8 enters the membrane separation unit 9, the concentrated solution separated by the membrane separation unit 9 enters the sewage treatment unit 10, and the clear solution separated by the membrane separation unit 9 enters the membrane washing unit 11 to be recycled as washing make-up water.
Specifically, as shown in fig. 2, the membrane washing unit 11 includes a circulation tank 17, a circulation pump 18 and a membrane washing device 19, a liquid outlet end of the circulation tank 17 is connected to a liquid inlet end of the circulation pump 18, a liquid outlet end of the circulation pump 18 is connected to a liquid inlet end of the membrane washing device 19, and the membrane washing device 19 is connected to the circulation tank 17. The membrane washing device 19 is provided with a cross-flow filtration membrane, the precision of the cross-flow filtration membrane is 10-1000nm, the membrane surface flow rate of the cross-flow filtration membrane is 3-6m/s, and the transmembrane pressure difference of the cross-flow filtration membrane is 0.05-0.6 MPa.
Further, as shown in fig. 1, the water recycling system for preparing the sulfuric acid method titanium dioxide calcination seed crystal further comprises: the alkali dissolving unit 2 is used for carrying out alkali dissolving on the second-washing qualified material 1; the washing unit 3 is connected with the alkali dissolving unit 2 and is used for washing the qualified second-washing material 1 after alkali dissolving; the first neutralizing unit 4 is connected with the water washing unit 3 and is used for neutralizing the second washing qualified material 1 after water washing; and the acid dissolving unit 5 is connected with the first neutralizing unit 4 and is used for carrying out acid dissolving on the neutralized secondary washing qualified material 1 and obtaining a calcined seed crystal 7.
Further, as shown in fig. 1, the water recycling system for preparing the sulfuric acid method titanium dioxide calcination seed crystal further comprises: the membrane filtration unit 6, the membrane filtration unit 6 is connected with washing unit 3, alkali dissolving unit 2, second neutralization unit 8 respectively, wherein, the waste water that produces in the washing unit 3 gets into membrane filtration unit 6, and the powder that membrane filtration unit 6 was retrieved gets into alkali dissolving unit 2, and the alkaline waste water that membrane filtration unit 6 produced gets into second neutralization unit 8.
Further, the membrane separation unit 9 is provided with a reverse osmosis membrane, the rejection rate of the reverse osmosis membrane to dissolved salts in the solution is more than 99%, and the operating pressure of the reverse osmosis membrane is 1MPa to 10 MPa.
Further, as shown in fig. 1, the water recycling system for preparing the sulfuric acid method titanium dioxide calcination seed crystal further comprises: the bleaching unit 13 is used for bleaching a washing slurry to obtain a bleaching slurry; the secondary washing unit 14 is connected with the bleaching unit 13 and is used for washing the bleaching pulp to obtain secondary washing pulp; the salt treatment unit 15 is respectively connected with the secondary washing unit 14 and the membrane washing unit 11 and is used for carrying out salt treatment on the secondary washing slurry; and the calcining unit 16 is connected with the salt treatment unit 15 and is used for adding qualified calcining seed crystals into the salt-treated secondary washing slurry for calcining.
In another embodiment, as shown in fig. 1 and fig. 2, on the basis of the foregoing embodiment, this embodiment provides a method for recycling water prepared by calcining seed crystals of titanium dioxide by a sulfuric acid process, including the steps of: introducing the prepared calcined crystal seed 7 into a membrane washing unit 11, introducing desalted water 12 to wash the calcined crystal seed 7 until qualified calcined crystal seeds are separated, and then introducing the calcined crystal seeds into a salt treatment unit 15; acidic water washing water generated in the membrane water washing unit 11 is introduced into the second neutralization unit 8 for neutralization; and the water neutralized by the second neutralization unit 8 enters a membrane separation unit 9 for separation, the separated concentrated solution is discharged to a sewage treatment unit 10 for treatment, and the separated clear solution enters a membrane washing unit 11 for washing the calcined seed crystal 7.
The method comprises the following steps of introducing prepared calcined seed crystals 7 into a membrane washing unit 11, introducing desalted water 12 to wash the calcined seed crystals 7, and introducing the calcined seed crystals into a salt treatment unit 15 after qualified calcined seed crystals are separated out, wherein the method specifically comprises the following steps: introducing the prepared calcined seed crystal 7 into a circulating tank 17 through a pipeline, and stopping introducing the calcined seed crystal 7 after the feeding material in the circulating tank 17 reaches a certain liquid level; and introducing desalted water 12 into the circulating tank 17, starting the circulating pump 18 at the same time, sending the calcined seed crystal 7 in the circulating tank 17 into a membrane water washing device 19 for solid-liquid separation, feeding the separated clear liquid into the second neutralizing unit 8 along with a clear liquid pipeline, and returning the separated slurry to the circulating tank 17 for continuous water washing separation. Because the calcined seed crystal 7 is separated by the membrane washing device 19 and simultaneously the desalted water 12 is introduced, the calcined seed crystal 7 is continuously washed by water, when the chloride ions in the calcined seed crystal 7 are washed to a certain degree, the chloride ions and trace soluble metal ions in the calcined seed crystal 7 are removed by washing separation through the circulating tank 17 and the membrane washing device 19 until the conductivity of the washing clear liquid is less than 100us/cm, the introduction of the desalted water 12 is stopped, the calcined seed crystal 7 qualified in washing enters the salt treatment unit 15 through a qualified slurry pipeline, and then a certain amount of the calcined seed crystal 7 is introduced again for washing separation.
For example: sending 10% of calcined seed crystal 7 slurry to a circulating tank 17, starting a circulating pump 18 when the circulating tank 17 reaches 70% of liquid level, sending the slurry to a membrane washing device 19, wherein a membrane element of the membrane washing device 19 is a cross-flow filtration membrane, the precision of the filtration membrane is 500nm, the membrane surface flow rate is 4m/s, and the transmembrane pressure difference is 0.3MPa, adding desalted water 12 into the circulating tank 17 at the same time, continuously discharging clear liquid from the membrane washing device 19, simultaneously continuously adding the desalted water 12 into the circulating tank 17 to continuously reduce the content of chloride ions in the calcined seed crystal 7 until the conductivity of the washed clear liquid is less than 100us/cm, stopping introducing the desalted water 12, inputting the qualified calcined seed crystal 7 into a salt treatment unit 15, and then adding a new batch of calcined seed crystal 7 into the circulating tank 17. The interception rate of the membrane washing device 19 to the calcined seed crystal 7 is more than 99.9 percent, the calcined seed crystal 7 almost has zero loss, the activity and the calcination conversion rate of the calcined seed crystal 7 cannot be influenced, and the performance of the calcined seed crystal 7 before membrane washing is completely the same as that after membrane washing.
As shown in fig. 1, the prepared calcined seed crystal 7 is introduced into a membrane washing unit 11, and desalted water 12 is introduced to wash the calcined seed crystal 7 until qualified calcined seed crystals are separated and then enter a salt treatment unit 15, and the method also comprises the following steps: taking the qualified material 1 after the second washing, and carrying out alkali dissolution through an alkali dissolution unit 2; washing the second-washing qualified material 1 after the alkali dissolution by a washing unit 3; neutralizing the washed qualified second washing material 1 through a first neutralization unit 4; and performing acid dissolution on the neutralized secondary washing qualified material 1 through an acid dissolution unit 5 to obtain a calcined seed crystal 7.
Specifically, the qualified material 1 after secondary washing (TiO2 is 300g/L) is taken, a 50% sodium hydroxide solution is added according to the proportion of 1.2 times of titanium dioxide, the mixture is fully stirred, heated to boiling, kept for 120min, cooled to 60 ℃ and then washed with water. And (3) removing redundant sodium hydroxide in the system after the reaction and a small amount of sulfate radical brought by the qualified material 1 after secondary washing by washing, and washing by water until the washing filtrate does not contain sulfate radical. The powder-containing wastewater generated by water washing enters a membrane filtration unit 6, the powder in the wastewater is recovered after being treated by the membrane filtration unit 6, and the recovered powder returns to the alkali dissolution unit 2; the alkaline waste water produced by the membrane filtration unit 6 enters a second neutralization unit 8. The material treated by the water washing unit 3 enters a first neutralization unit 4, the PH value is controlled to be 2.5-3.5 in the neutralization process, the temperature is increased at a specified temperature increase speed and kept for a period of time to completely dissolve the metal hydroxide, then the material enters an acid dissolving unit 5, a large amount of hydrochloric acid is added into the material entering the acid dissolving unit 5 for acid dissolution, the temperature is increased to boiling, and the boiling state is kept for more than 100 min. And finally, quenching and diluting to 100g/L, wherein the obtained material is the calcined seed crystal 7.
As shown in fig. 1, the salt treatment unit 15 further includes a bleaching unit 13 and a secondary water washing unit 14, and the salt treatment unit 15 further includes a calcining unit 16. Specifically, titanium ore and sulfuric acid are reacted to obtain titanyl sulfate solution, then hydrolysis is carried out, washing is carried out for one time to obtain washing slurry, and the washing slurry is bleached through a bleaching unit 13 to obtain bleaching slurry; and washing the bleaching slurry by a secondary washing unit 14 to obtain secondary washing slurry, performing salt treatment on the secondary washing slurry by a salt treatment unit 15, adding qualified calcining seed crystals, and calcining by a calcining unit 16 to obtain the titanium dioxide.
In this embodiment, the calcined seed crystal 7 after acid dissolution enters the membrane washing unit 11, and is washed by the membrane washing unit 11 to remove chloride ions and trace soluble metal ions in the calcined seed crystal 7, and the washing end point is controlled to be the conductivity of the washing clear liquid less than 100 us/cm. The calcined seed crystal 7 which is qualified after being washed by the membrane washing unit 11 directly enters the salt treatment unit 15, and enters the calcining unit 16 after being treated by the salt treatment unit 15, wherein the calcined seed crystal 7 has a conversion function. The acidic wastewater generated by the washing of the membrane washing unit 11 and the alkaline wastewater generated by the membrane filtering unit 6 enter the second neutralizing unit 8 at the same time, the acidic wastewater and the alkaline wastewater are fully mixed in the second neutralizing unit 8 and then enter the membrane separation unit 9, the wastewater treated by the second neutralizing unit 8 just meets the water quality requirement of the inlet water entering the membrane separation unit 9 (a small amount of acid and alkali can be properly supplemented in the second neutralizing unit 8 for adjustment according to the change of the water washing amount of the washing unit 3 and the membrane washing unit 11), the neutralized wastewater entering the membrane separation unit 9 is treated by the membrane separation unit 9, the generated clear liquid is recycled to the membrane washing unit 11 to be recycled as the washing make-up water of the membrane washing unit 11, and the generated concentrated solution directly enters the sewage treatment unit 10 for sewage treatment or is subjected to zero discharge treatment according to the requirements of an owner. The recovery rate of the membrane separation unit 9 to the neutralization wastewater is more than 60 percent, the conductivity of clear liquid generated by the membrane separation unit 9 is less than 10us/cm, the requirement of the membrane washing unit 11 to the washing water is completely met, and the calcined seed crystal 7 washed by the membrane washing unit 11 can be directly added into the salt treatment unit 15 without adding a bleaching unit.
The following detection analyses were performed in specific cases:
case one, take 1m3Adding 50% sodium hydroxide solution into qualified material 1(TiO2 is 300g/L) after secondary washing according to the proportion of 1.2 times of titanium dioxide, fully stirring, heating to boil, keeping the temperature for 120min, diluting, cooling, performing pressure filtration, and washing with water to obtain an alkali-soluble filter cake;
and pulping the alkali-soluble filter cake until TiO2 is 300g/L, heating to 60 ℃, adding metered concentrated hydrochloric acid to adjust the pH of the slurry to be 2.5-3.5, continuously adding concentrated hydrochloric acid (HCL/TiO2 is 0.35) to perform acid dissolution, keeping boiling for 120min, and adding water to dilute until TiO2 is 100g/L to obtain the calcined seed crystal A.
Case two, 1m3Adding 50% sodium hydroxide solution into qualified material 1(TiO2 is 300g/L) after secondary washing according to the proportion of 1.2 times of titanium dioxide, fully stirring, heating to boil, keeping the temperature for 120min, diluting, cooling, performing pressure filtration, and washing with water to obtain an alkali-soluble filter cake;
pulping the alkali-soluble filter cake until TiO2 is 300g/L, heating to 60 ℃, adding metered concentrated hydrochloric acid to adjust the pH of the slurry to be 2.5-3.5, continuously adding concentrated hydrochloric acid (HCL/TiO2 is 0.35) to perform acid dissolution, keeping boiling for 120min, adding water to dilute until TiO2 is 100g/L, and obtaining a primary calcined seed crystal;
and (3) the primary calcined seed crystal enters a membrane washing unit 11, and after 20 times (relative to the ratio of TiO 2) of water washing is carried out in the membrane washing unit 11, the water washing is qualified through detection, and the slurry after the water washing is qualified is the final calcined seed crystal B.
Through detection and analysis: calcining the seed crystal A: the activity is more than 99 percent, the conversion rate is 98 percent, the brightness is 94.3, and the blue light whiteness is 93.4. And (3) calcining the seed crystal B: the activity is more than 99 percent, the conversion rate is 98.9 percent, the brightness is 94 percent, and the blue light whiteness is 93.7. Cases (1) and (2) illustrate that the calcined seed after washing with water through the membrane does not affect any of the properties of the calcined seed.
Case three, 1m3Adding 50% sodium hydroxide solution into qualified material 1(TiO2 is 300g/L) after secondary washing according to the proportion of 1.2 times of titanium dioxide, fully stirring, heating to boil, keeping the temperature for 120min, diluting, cooling, performing pressure filtration, and washing with water to obtain an alkali-soluble filter cake;
wastewater generated by the filter pressing and water washing unit enters a membrane filtering unit 6, powder slurry recovered by the membrane filtering unit 6 is recycled to an alkali dissolving unit 2, and alkaline wastewater generated by the membrane filtering unit 6 enters a second neutralizing unit 8;
pulping the alkali-soluble filter cake until TiO2 is 300g/L, heating to 60 ℃, adding metered concentrated hydrochloric acid to adjust the pH of the slurry to be 2.5-3.5, continuously adding concentrated hydrochloric acid (HCL/TiO2 is 0.35) to perform acid dissolution, keeping boiling for 120min, adding water to dilute until TiO2 is 100g/L, and obtaining a primary calcined seed crystal;
the primary calcined seed crystal enters a membrane washing unit 11, after 20 times (relative to the ratio of TiO 2) of water washing is carried out in the membrane washing unit 11, the water washing is qualified through detection, and the slurry after the water washing is qualified is the final calcined seed crystal C;
the acid washing water generated by the membrane washing unit 11 also enters the second neutralizing unit 8, and the acid wastewater generated by the membrane washing unit 11 and the alkaline wastewater generated by the membrane filtering unit 6 are fully and homogeneously neutralized in the second neutralizing unit 8;
the neutralized wastewater enters a membrane separation unit 9, the neutral wastewater entering the membrane separation unit 9 is desalted under the action of a high-pressure pump and a membrane element, clear liquid generated by the membrane separation unit 9 is about 60% of the total water entering the membrane separation unit 9 (the conductivity is less than 10us/cm), the clear liquid is recycled to a membrane washing unit 11 to be used as washing water replenishing water of the membrane washing unit 11 for cyclic utilization, high-salt concentrated water generated by the membrane separation unit 9 is about 40% of the total water entering the membrane separation unit 11 and enters a sewage treatment station, and calcined crystal seeds C obtained after the membrane washing is qualified are directly added into a salt treatment unit.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and reference may be made to the related descriptions of other embodiments for parts that are not described or recited in detail in a certain embodiment.
It should be noted that the above embodiments can be freely combined as necessary. The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (12)
1. The utility model provides a water recycling system of seed preparation is calcined to sulfuric acid process titanium white powder which characterized in that includes:
the membrane washing unit is used for washing the calcined crystal seeds until qualified calcined crystal seeds are separated;
the second neutralization unit is connected with the membrane washing unit and is used for neutralizing the washing water in the membrane washing unit;
and the membrane separation unit is respectively connected with the second neutralization unit, the membrane washing unit and the sewage treatment unit, wherein the water neutralized by the second neutralization unit enters the membrane separation unit, the concentrated solution separated by the membrane separation unit enters the sewage treatment unit, and the clear solution separated by the membrane separation unit enters the membrane washing unit.
2. The water recycling system for preparing the sulfuric acid method titanium dioxide calcining seed crystal according to claim 1, characterized in that:
the membrane washing unit comprises a circulating tank, a circulating pump and a membrane washing device, wherein the liquid outlet end of the circulating tank is connected with the liquid inlet end of the circulating pump, the liquid outlet end of the circulating pump is connected with the liquid inlet end of the membrane washing device, and the membrane washing device is connected with the circulating tank.
3. The water recycling system for preparing the sulfuric acid method titanium dioxide calcining seed crystal according to claim 2, characterized in that:
the membrane washing device is provided with a cross-flow filtering membrane, the precision of the cross-flow filtering membrane is 10-1000nm, the membrane surface flow rate of the cross-flow filtering membrane is 3-6m/s, and the transmembrane pressure difference of the cross-flow filtering membrane is 0.05-0.6 MPa.
4. The water recycling system for preparing the sulfuric acid method titanium dioxide calcining seed crystal according to claim 1, further comprising:
the alkali dissolving unit is used for carrying out alkali dissolving on the qualified second-washing material;
the washing unit is connected with the alkali dissolving unit and is used for washing the qualified second-washing material after alkali dissolving;
the first neutralizing unit is connected with the water washing unit and is used for neutralizing the qualified second washing material after water washing;
and the acid dissolving unit is connected with the first neutralizing unit and is used for carrying out acid dissolving on the neutralized qualified secondary washing material and obtaining the calcined seed crystal.
5. The water recycling system for preparing the sulfuric acid method titanium dioxide calcining seed crystal according to claim 4, further comprising:
and the membrane filtering unit is respectively connected with the water washing unit, the alkali dissolving unit and the second neutralizing unit, wherein the wastewater generated in the water washing unit enters the membrane filtering unit, the powder recovered by the membrane filtering unit enters the alkali dissolving unit, and the wastewater generated by the membrane filtering unit enters the second neutralizing unit.
6. The water recycling system for preparing the sulfuric acid method titanium dioxide calcining seed crystal according to claim 1, characterized in that:
the membrane separation unit is provided with a reverse osmosis membrane, the rejection rate of the reverse osmosis membrane to dissolved salts in a solution is more than 99%, and the operating pressure of the reverse osmosis membrane is 1MPa to 10 MPa.
7. The water recycling system for preparing the sulfuric acid method titanium dioxide calcining seed crystal according to claim 1, further comprising:
the bleaching unit is used for bleaching a washing slurry to obtain a bleaching slurry;
the secondary washing unit is connected with the bleaching unit and is used for washing the bleaching pulp to obtain secondary washing pulp;
the salt treatment unit is respectively connected with the secondary washing unit and the membrane washing unit and is used for carrying out salt treatment on the secondary washing slurry;
and the calcining unit is connected with the salt treatment unit and is used for adding the qualified calcining seed crystal into the secondary washing slurry after salt treatment for calcining.
8. A water recycling method for preparing titanium dioxide calcination crystal seeds by a sulfuric acid method is characterized by comprising the following steps:
introducing the prepared calcined crystal seed into a membrane washing unit, introducing desalted water to wash the calcined crystal seed until the qualified calcined crystal seed is separated out, and then introducing the calcined crystal seed into a salt treatment unit;
introducing the water washing water in the membrane water washing unit into a second neutralization unit for neutralization;
and the water neutralized by the second neutralization unit enters a membrane separation unit for separation, the separated concentrated solution is discharged to a sewage treatment station for treatment, and the separated clear solution enters a membrane washing unit for washing the calcined seed crystal.
9. The water recycling method for preparing the sulfuric acid method titanium dioxide calcination seed crystal according to claim 8, wherein the prepared calcination seed crystal is introduced into a membrane washing unit, and desalted water is introduced to wash the calcination seed crystal until qualified calcination seed crystal is separated, and the washed calcination seed crystal enters a salt treatment unit, and the method specifically comprises the following steps:
introducing the prepared calcining seed crystal into a circulating tank, and stopping introducing until the calcining seed crystal reaches a preset liquid level of the circulating tank;
and introducing desalted water into the circulating tank, starting a circulating pump at the same time, sending the calcined seed crystal in the circulating tank into a membrane washing device for solid-liquid separation, sending the separated clear liquid into a second neutralization unit, returning the separated slurry into the circulating tank for continuous washing separation until the contents of chloride ions and trace soluble metal ions in the calcined seed crystal reach a preset range, and sending the qualified calcined seed crystal into a salt treatment unit.
10. The method for recycling water produced by calcining the seed crystal in the titanium dioxide powder produced by the sulfuric acid process according to claim 8, wherein the method for recycling water produced by introducing the prepared calcining seed crystal into a membrane washing unit and introducing desalted water to wash the calcining seed crystal until the qualified calcining seed crystal is separated and then the qualified calcining seed crystal enters a salt treatment unit, and comprises the following steps:
taking the qualified material of the second washing, and carrying out alkali dissolution through an alkali dissolution unit;
washing the qualified second-washing material after the alkali dissolution by a washing unit;
neutralizing the washed qualified second washing material through a first neutralization unit;
and carrying out acid dissolution on the neutralized secondary-washing qualified material through an acid dissolution unit to obtain the calcined seed crystal.
11. The method for recycling water prepared by calcining the seed crystal of titanium dioxide by the sulfuric acid process according to claim 10, which is characterized in that:
and taking the second-washing qualified material to perform alkali dissolution through an alkali dissolution unit, and specifically comprising the following steps: adding a sodium hydroxide solution with the concentration of 40-60% into the second-washing qualified material according to the proportion of 0.8-1.4 times of titanium dioxide, fully stirring, heating to boil, keeping the temperature for more than 100min, and then cooling to 40-80 ℃;
and/or washing the qualified second-washing material after the alkali dissolution by a washing unit, and specifically comprises the following steps: washing the second washing qualified material after alkali dissolution with water to remove redundant sodium hydroxide in the system after reaction and a small amount of sulfate radical brought by the second washing qualified material, washing with water until washing filtrate does not contain sulfate radical, feeding powder-containing wastewater generated by washing with water into a membrane filtration unit, recovering powder in the wastewater after treatment by the membrane filtration unit, returning the recovered powder to the alkali dissolution unit, and feeding alkaline wastewater generated by the membrane filtration unit into a second neutralization unit;
and/or neutralizing the qualified second washing material after washing through a first neutralization unit, and specifically comprising the following steps: neutralizing the washed qualified second-washing material, controlling the pH value to be 2.5-3.5 in the neutralization process, heating at a preset heating speed, and keeping the temperature for a preset time until the metal hydroxide is completely dissolved;
and/or performing acid dissolution on the neutralized qualified secondary washing material through an acid dissolution unit to obtain the calcined seed crystal, and specifically comprises the following steps: and adding a preset amount of hydrochloric acid into the neutralized secondary-washing qualified material for acid dissolution, heating to boil, keeping the boiling state for more than 100min, and finally quenching and diluting to obtain the calcined crystal seed.
12. The water recycling method for preparing the sulfuric acid method titanium dioxide calcination seed crystal according to claim 8, wherein the qualified calcination seed crystal is separated and enters a salt treatment unit, and the method specifically comprises the following steps:
reacting titanium ore with sulfuric acid to obtain titanyl sulfate solution, hydrolyzing, washing with water once to obtain a washing slurry, and bleaching the washing slurry by a bleaching unit to obtain a bleached slurry;
and washing the bleaching slurry by a secondary washing unit to obtain secondary washing slurry, carrying out salt treatment on the secondary washing slurry by the salt treatment unit, adding the qualified calcining seed crystal, and calcining by the calcining unit to obtain the titanium dioxide.
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