WO2020082916A1 - 一种新型硫酸法钛白粉水洗工艺及系统 - Google Patents

一种新型硫酸法钛白粉水洗工艺及系统 Download PDF

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Publication number
WO2020082916A1
WO2020082916A1 PCT/CN2019/104812 CN2019104812W WO2020082916A1 WO 2020082916 A1 WO2020082916 A1 WO 2020082916A1 CN 2019104812 W CN2019104812 W CN 2019104812W WO 2020082916 A1 WO2020082916 A1 WO 2020082916A1
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Prior art keywords
washing
slurry
phase separation
tank
water
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PCT/CN2019/104812
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English (en)
French (fr)
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杨积志
单祥雷
李海波
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上海安赐环保科技股份有限公司
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Publication of WO2020082916A1 publication Critical patent/WO2020082916A1/zh
Priority to ZA2021/03437A priority Critical patent/ZA202103437B/en

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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Definitions

  • the invention relates to the technical field of production of titanium dioxide by sulfuric acid method, in particular to a new type of washing process and system of titanium dioxide by sulfuric acid method.
  • the titanium dioxide plant in China is dominated by the sulfuric acid method.
  • the sulfuric acid method is an acid hydrolysis reaction between ferro-titanium powder and concentrated sulfuric acid to produce titanyl sulfate, which is hydrolyzed to produce metatitanic acid, and then calcined and crushed to obtain a titanium dioxide product.
  • This method can produce anatase and rutile titanium dioxide.
  • the sulfuric acid method can use ilmenite and sulfuric acid as raw materials with low price and availability. The technology is relatively mature, the equipment is simple, and the anti-corrosion materials are easy to solve.
  • the washing process is divided into three stages: one washing, bleaching, and two washing.
  • the second washing water is applied to one washing, and the one washing water is discharged directly. Poor, high drug consumption.
  • the traditional production process needs to add concentrated sulfuric acid and reducing agent after washing the metatitanic acid filter cake to reduce the ferric ions formed in the washing process After it is bivalent iron, it is washed again for a second time to remove it. The entire process is long and the operation is cumbersome.
  • the object of the present invention is to provide a novel sulfuric acid process titanium dioxide water washing process, which can simplify the process of the sulfuric acid process titanium dioxide and the operation is simple.
  • Another object of the present invention is to provide a novel sulfuric acid method titanium dioxide water washing system.
  • a new type of sulfuric acid method titanium dioxide washing process including:
  • the hydrolyzed material is separated into phases, and the hydrolyzed material is subjected to phase separation treatment to obtain metatitanic acid slurry and liquid phase clean waste acid;
  • Washing water treatment treating the washed effluent obtained by washing the slurry film, intercepting impurity iron ions;
  • phase separation of the hydrolysate, the washing of the slurry film, and the washing water treatment are all performed in a closed environment. Further, in the step of phase separation of the hydrolyzed material, the hydrolyzed material is subjected to phase separation treatment through a phase separation membrane module.
  • the metatitanic acid slurry is washed by continuous water inlet and continuous water outlet; the water is continuously replenished from the water tank before washing, and at the same time, the water is continuously discharged from the slurry washing process to after washing sink;
  • the metatitanic acid slurry is washed by washing the membrane module.
  • both the phase separation membrane module and the washing membrane module include but are not limited to tubular cross flow microfiltration membranes, and the accuracy of the tubular cross flow microfiltration membranes is 50-1000 nm, and the temperature resistance is ⁇ 50 °C.
  • the flow velocity of the slurry in the membrane module is 2-8m / s
  • the liquid phase in the slurry penetrates the membrane under the pressure difference of 0.1-0.5MPa
  • the solid phase is intercepted on the slurry side
  • the membrane produces a clear liquid Turbidity is less than 1NTU.
  • the concentration of metatitanic acid slurry obtained in the phase separation step of the hydrolyzed material is 300-500 g / L;
  • the slurry concentration of the washing qualified material obtained in the slurry film washing step is 150-350 g / L, and the content of elemental iron is 10 ppm or less.
  • the washed effluent is treated by a washing water treatment module;
  • the washing water treatment module includes but is not limited to nanofiltration membrane and reverse osmosis membrane.
  • the treated clear liquid is returned to the pre-washing water tank to realize the recycling of washing water.
  • the water source used for water washing includes supplementary fresh water, and the supplementary fresh water is deoxygenated and demineralized water, and the water temperature is 20-50 ° C.
  • the method further includes:
  • metatitanic acid slurry dilute the metatitanic acid slurry obtained by phase separation of the hydrolysate to a preset concentration, and the concentration of the slurry obtained by beating is 150-350g / L; the slurry used for beating uses the slurry The supernatant produced by the membrane washing process.
  • the invention also provides a new type of titanium dioxide production system of sulfuric acid method, which includes:
  • Hydrolysis phase separation unit which includes a phase separation membrane component for phase separation treatment of hydrolyzed material to obtain metatitanic acid slurry and liquid phase clean waste acid;
  • a slurry film washing unit which includes a washing film assembly for washing the metatitanic acid slurry;
  • a washing water treatment unit which includes a washing water treatment component for treating the washed effluent obtained by the slurry film washing unit;
  • the hydrolysis phase separation unit, the slurry film washing unit, and the washing water treatment unit are all in a closed structure.
  • the hydrolysis phase separation unit includes a hydrolysis phase separation tank, a phase separation circulation pump, and a phase separation membrane module.
  • the hydrolysis phase separation tank and the phase separation membrane module are established between the phase separation circulation pumps. Slurry circulation; the outlet of the hydrolyzed material phase separation tank communicates with the inlet of the phase separation circulation pump, the outlet of the phase separation circulation pump communicates with the phase separation membrane assembly, and the slurry of the phase separation membrane assembly The side is in communication with the hydrolyzed material phase separation tank;
  • the slurry membrane washing unit includes an elution tank, a qualified material tank, an elution circulation pump, a qualified material transfer pump, an elution inlet water pump, and a washing membrane assembly.
  • the inlet of the elution tank is separated from the hydrolyzed material
  • the other outlet of the tank is in communication, and a slurry circulation is established between the elution tank and the washing membrane assembly through the elution circulation pump;
  • the outlet of the elution tank is in communication with the inlet of the elution circulation pump,
  • the outlet of the elution circulation pump communicates with the washing membrane module, and the slurry side of the washing membrane module communicates with the elution tank.
  • the inlet of the qualified material tank is communicated with the outlet of the elution tank, and the outlet of the qualified material tank is communicated with the qualified material transfer pump.
  • the outlet of the elution inlet water pump communicates with the inlet of the elution tank, and the inlet of the elution inlet water pump communicates with the outlet of the water tank before washing;
  • the washing water treatment unit includes a washing water treatment inlet pump, a washing water treatment assembly, a pre-washing water tank, and a after-washing water tank.
  • the outlet of the water pump is in communication with the washing water treatment assembly;
  • the inlet of the pre-washing water tank is in communication with the clear liquid side of the washing water treatment assembly;
  • the new type of titanium dioxide production system of sulfuric acid method further includes:
  • Slurry pulping unit which includes a beating tank and an auxiliary stirring device; the inlet of the beating tank communicates with the outlet of the hydrolyzed material phase separation tank, and the outlet of the beating tank communicates with the elution tank; the accessory
  • the stirring device is arranged inside the beating tank; the outlet of the washed water tank is also in communication with the inlet of the beating tank at the same time.
  • the hydrolyzed material phase separation tank, beating tank, elution tank, qualified feed tank, water tank before washing, water tank after washing, phase separation membrane assembly, washing membrane assembly, and washing water treatment assembly are all closed structures.
  • the inlet of the pre-washing water tank is also in communication with an external deoxygenated and demineralized water port.
  • phase separation membrane module and the washing membrane module include but are not limited to tubular cross flow microfiltration membranes
  • washing water treatment component includes but is not limited to a nanofiltration membrane and a reverse osmosis membrane;
  • hydrolyzed material phase separation tank and the elution tank are integrated into one body;
  • waste acid side of the phase separation membrane module is connected to a waste acid treatment device.
  • the invention adopts the production method of totally enclosed and isolated air to prevent the oxidation of divalent iron in the metatitanic acid slurry into ferric iron; more preferably, deoxidized and demineralized water is used for beating and washing, which can further prevent the iron ion Oxidation, so that the bleach reduction process of the traditional process can be omitted, and the washing process can be completed at one time, which is more concise, efficient, energy-saving and environmentally friendly than the traditional process.
  • the content of impurity iron in the product discharge of the process of the present invention is lower, and there is no need to add bleach, sulfuric acid and other agents for processing, which saves the process and is more environmentally friendly.
  • the high-efficiency membrane module of the tubular cross flow microfiltration membrane of the present invention can realize continuous operation and high degree of automation, avoiding the inefficiency and high energy consumption of equipment such as tubular filter, vacuum leaf filter and diaphragm filter press 3.
  • the present invention uses a high-efficiency membrane module, without the risk of powder filtration, waste acid does not need to be recycled, and can be directly introduced into the waste acid treatment device, saving processing costs
  • the nanofiltration membrane water treatment technology is applied to the recovery of titanium dioxide water washing for the first time.
  • the product water recovery rate is high and the concentrated water discharge is small.
  • the cleaned water after washing treatment is used as the injection water in the membrane washing process to achieve The recycling of washing water greatly reduces the amount of fresh deoxidized water and the amount of waste water discharged, and reduces the cost of sewage treatment.
  • Some embodiments of the present invention may also omit the step of preparing metatitanic acid slurry, and the concentration of metatitanic acid slurry obtained by hydrolytic phase separation has met the requirements and can be directly washed.
  • FIG. 1 is a schematic diagram of an embodiment of the novel sulfuric acid method titanium dioxide water washing process of the present invention
  • FIG. 2 is a schematic diagram of another embodiment of the novel sulfuric acid method titanium dioxide water washing process of the present invention.
  • FIG. 3 is a schematic diagram of an embodiment of a novel sulfuric acid method titanium dioxide water washing system of the present invention
  • FIG. 4 is a schematic diagram of another embodiment of the novel sulfuric acid method titanium dioxide water washing system of the present invention.
  • the production process includes the following steps:
  • the hydrolyzed material is separated into phases, and the hydrolyzed material is subjected to phase separation treatment to obtain metatitanic acid slurry and liquid phase clean waste acid;
  • washing water treatment the washed effluent obtained by washing the slurry film is treated to intercept the impurity iron ions;
  • phase separation of the hydrolysate, the washing of the slurry film and the washing water treatment are all carried out in a closed environment.
  • the hydrolyzed material is metatitanic acid obtained after hydrolysis, and the hydrolyzed material is phase-separated to obtain a metatitanic acid slurry, and at the same time, a liquid-phase clean waste acid is obtained.
  • the metatitanic acid slurry is washed to remove impurity iron ions. Further, the washed effluent water obtained by washing is treated to intercept the impurity iron ions and meet the requirements for recycling of washing water.
  • phase separation of the hydrolysate, the washing of the slurry film and the washing water treatment are all carried out in a hermetically sealed environment, which can effectively prevent the oxidation of the divalent iron in the metatitanic acid slurry to ferric iron, which can save the traditional process
  • the bleaching and reducing process realizes the washing process at one time, which is more concise, efficient, energy-saving and environmentally friendly than the traditional process.
  • Embodiment 2 of the novel sulfuric acid method titanium dioxide water washing process of the present invention refinement is performed on the basis of the foregoing Embodiment 1.
  • the hydrolyzed material is subjected to phase separation treatment through a phase separation membrane module.
  • the metatitanic acid slurry is continuously washed in water by washing the membrane module.
  • the phase separation membrane module and the washing membrane module have high filtration accuracy, low energy consumption and small space consumption.
  • the core components of the phase separation membrane module and the washing membrane module are tubular cross flow microfiltration membranes, and the accuracy of the tubular cross flow microfiltration membranes is 50-1000 nm, and the temperature resistance is ⁇ 50 ° C.
  • the flow rate of the slurry in the membrane module is 2-8m / s, and the liquid phase in the slurry permeates the membrane under the pressure difference of 0.1-0.5MPa.
  • the flow rate and pressure difference can be controlled by the circulation pump .
  • the solid phase is intercepted on the slurry side.
  • the microfiltration membrane can achieve effective interception of metatitanic acid powder, and the turbidity of the membrane produced clear liquid is less than 1 NTU.
  • the concentration of metatitanic acid slurry obtained in the phase separation step of the hydrolyzed material is 300-500 g / L; the slurry concentration of the washing qualified material obtained in the slurry film washing step is 150-350 g / L, in which the content of elemental iron is 10 ppm or less.
  • the effluent after washing is treated by the washing water treatment module;
  • the washing water treatment module includes a nanofiltration membrane and a reverse osmosis membrane.
  • the core element of the water treatment module is composed of nanofiltration membrane and reverse osmosis membrane.
  • the iron content in the clear liquid can reach below 2ppm.
  • the nanofiltration membrane water treatment technology is applied to the washing of the titanium dioxide powder for the first time, and the water quality is high.
  • the clear liquid obtained by the washing water treatment is returned to the step of washing the slurry membrane as a main water source, so that the recovery rate of the produced water in the washing water treatment is high, and the concentrated water discharge is small, which realizes the washing water. Recycling greatly reduces the amount of fresh deoxygenated water and the amount of waste water discharged, and reduces the cost of sewage treatment.
  • a sealed environment is achieved by sealing with an inert gas, and the sealing pressure is 1-10 KPa, which can perfectly isolate oxygen and prevent the oxidation of ferrous iron.
  • the sealing pressure is 1-10 KPa, which can perfectly isolate oxygen and prevent the oxidation of ferrous iron.
  • the fresh water is supplemented with deoxygenated and demineralized water, and the water temperature is 20-50 ° C.
  • the new sulfuric acid method titanium dioxide water washing process of the present invention will now be described with reference to FIG. 1.
  • inert gas is introduced into each slurry tank and water tank of the system to remove air, and the sample is analyzed at the vent of each equipment. After the oxygen content is qualified, the system is ready to feed.
  • the hydrolysate is introduced, and the phases are separated through a high-efficiency membrane module to obtain metatitanic acid slurry and waste acid.
  • the waste acid is directly sent to the waste acid treatment device for treatment.
  • the metatitanic acid slurry is sent to the slurry film washing unit.
  • the pre-washing water tank continuously replenishes the slurry membrane washing process.
  • the washing process continuously discharges water and collects the discharged water to the after-washing water tank.
  • a small amount of deoxygenated and demineralized water was added to the sink before washing. In the end, the qualified washing materials can be obtained.
  • the method further includes:
  • the metatitanic acid slurry is made into pulp, and the metatitanic acid slurry obtained by phase separation of the hydrolyzed material is diluted and beaten to a preset concentration.
  • the concentration may be 150-350 g / L.
  • the water used for beating uses the clear liquid produced by the aforementioned slurry film washing process, and the clear liquid of the washed water tank can be led to the beating process to save water consumption.
  • the new sulfuric acid method titanium dioxide washing process includes the following steps:
  • inert gas is introduced into each slurry tank and water tank of the system (except the pump body) to remove air, and samples are analyzed at the vent of each equipment. After the oxygen content is qualified, the system is ready to feed.
  • the hydrolysate is introduced, and the phases are separated through a high-efficiency membrane module to obtain metatitanic acid slurry and waste acid.
  • the waste acid is directly sent to the waste acid treatment device for treatment.
  • the metatitanic acid slurry is sent to the slurry film washing unit.
  • the water tank before washing continuously makes up water to the washing process of the slurry film, and the water is continuously discharged during the washing process, and the effluent is collected into the water tank after washing.
  • a small amount of deoxygenated and demineralized water was added to the sink before washing. In the end, the qualified washing materials can be obtained.
  • the invention also provides a novel sulfuric acid method titanium dioxide washing system.
  • a novel sulfuric acid method titanium dioxide washing system In the first embodiment of the production system, it includes:
  • Hydrolysis phase separation unit which includes a phase separation membrane module for phase separation treatment of hydrolyzed material, to obtain metatitanic acid slurry and liquid phase clean waste acid;
  • Slurry membrane washing unit which includes a washing membrane assembly for washing metatitanic acid slurry
  • a washing water treatment unit which includes a washing water treatment component for treating the washed effluent obtained by the slurry film washing unit;
  • the hydrolysis and phase separation unit, the slurry membrane washing unit, and the washing water treatment unit are all closed structures.
  • the phase separation membrane module and the washing membrane module are high-efficiency membrane modules, which can realize continuous operation and high degree of automation, avoiding the inefficiency of equipment such as tubular filter, vacuum leaf filter, and membrane filter press.
  • the closed structure can be achieved by passing inert gas, which can effectively prevent the oxidation of ferrous iron to ferric iron.
  • the hydrolysis phase separation unit includes a hydrolysis material phase separation tank, a phase separation circulation pump, and a phase separation membrane component.
  • a slurry circulation is established between the hydrolysis material phase separation tank and the phase separation membrane component through a phase separation circulation pump.
  • the slurry membrane washing unit includes an elution tank, an elution circulation pump, and a washing membrane component.
  • the inlet of the elution tank is connected to the outlet of the hydrolysate phase separation tank, and the elution tank and the washing membrane component establish a slurry through the elution circulation pump.
  • the washing water treatment unit includes a washing water treatment inlet pump and a washing water treatment assembly.
  • the inlet of the washing water treatment inlet water pump is connected to the waste liquid outlet of the washing membrane assembly, and the outlet of the washing water treatment inlet water pump is connected to the washing water treatment assembly.
  • the hydrolyzed material phase separation tank, phase separation membrane module, elution tank, washing membrane module, and washing water treatment module are all closed structures.
  • the other outlet of the hydrolyzed material phase separation tank communicates with the inlet of the phase separation circulation pump, the outlet of the phase separation circulation pump communicates with the phase separation membrane module, and the slurry side of the phase separation membrane module is connected to the entrance of the hydrolyzed material phase separation tank Connected; the outlet of the elution tank communicates with the inlet of the elution circulation pump, the outlet of the elution circulation pump communicates with the washing membrane module, and the slurry side of the washing membrane module communicates with the inlet of the elution tank.
  • the slurry film washing unit further includes a qualified material tank and a qualified material transfer pump; the inlet of the qualified material tank is connected to the outlet of the elution tank, and the outlet of the qualified material tank is connected to the qualified material transfer pump.
  • Qualified material tank is used to store qualified material and send qualified material through qualified material transfer pump.
  • the slurry membrane washing unit further includes an elution inlet water pump;
  • the washing water treatment unit further includes a pre-washing water tank and a after-washing water tank;
  • the inlet of the pre-washing water tank communicates with the clear liquid side of the washing water treatment assembly, and the outlet of the pre-washing water tank It is connected to the inlet of the elution inlet pump, the outlet of the elution inlet pump is connected to the inlet of the elution tank;
  • the inlet of the washed water tank is connected to the waste liquid side of the washing membrane assembly, and the outlet of the washed water tank is connected to the inlet pump of the washing water treatment .
  • the cleaning solution of the washing water treatment component is introduced into the pre-washing water tank for recycling, which greatly saves water consumption.
  • the fresh water introduced is deoxygenated and demineralized water in consideration of the oxidation of ferrous iron. Therefore, the inlet of the water tank before washing is also connected to the external deoxygenated and demineralized water port.
  • the phase separation membrane module includes a tubular cross flow microfiltration membrane
  • the washing membrane module includes a tubular cross flow microfiltration membrane.
  • Tubular cross flow microfiltration membrane, a high-efficiency membrane module can achieve continuous operation and high degree of automation, avoiding the inefficiency, high energy consumption and large footprint of tubular filter, vacuum leaf filter, diaphragm filter press and other equipment Disadvantages.
  • the washing water treatment module includes a nanofiltration membrane and a reverse osmosis membrane.
  • the nanofiltration membrane water treatment technology is applied to the titanium dioxide powder washing and recycling for the first time.
  • the product water recovery rate is high and the concentrated water discharge is small.
  • the cleaned liquid after washing treatment is used as the injection water in the membrane washing process to achieve water washing.
  • the recycling of water greatly reduces the amount of fresh deoxygenated water and the amount of waste water discharged, and reduces the cost of sewage treatment.
  • the hydrolyzed material phase separation tank and the elution tank are integrated into one body. After the hydrolyzed material phase separation is completed, the slurry remains in the hydrolyzed material phase separation tank, and the hydrolyzed material phase separation tank can continue to be used as the elution tank for washing process. There is no need to set up the elution tank separately.
  • the waste acid side of the phase separation membrane module is connected to a waste acid treatment device. Due to the use of a high-efficiency membrane module such as a phase separation membrane module, there is no risk of powder filtration. Waste acid does not need to be recycled, and can be directly introduced into a waste acid treatment device, saving processing costs.
  • FIG. 3 is a schematic diagram of an embodiment of a production system for a sulfuric acid method titanium dioxide according to the present invention.
  • the production system includes a hydrolysis phase separation unit, a slurry film washing unit, and a washing water treatment unit.
  • the hydrolysis phase separation unit includes: a hydrolysis material phase separation tank 101, a phase separation circulation pump 201, and a phase separation membrane module 301.
  • the slurry membrane washing unit includes: an elution tank 103, an elution circulation pump 202, a washing membrane assembly 302, a qualified feed tank 104, an elution feed water pump 204, and a qualified material transfer pump 203.
  • the wash water treatment unit includes: a pre-wash water tank 105, a post-wash water tank 106, a wash water treatment inlet pump 205, and a wash water treatment assembly 303.
  • the core elements of the phase separation membrane module 301 and the washing membrane module 302 are tubular cross-flow microfiltration membranes, and the phase separation membrane module 301 and the washing membrane module 302 both establish a slurry between the membrane module and the slurry tank by a circulation pump Material circulation.
  • the core element of the washing water treatment unit 303 in the washing water treatment unit is composed of nanofiltration membrane and reverse osmosis membrane. use.
  • the new sulfuric acid method titanium dioxide production system also includes a slurry pulping unit, which includes a beating tank and an auxiliary stirring device.
  • the inlet of the beating tank is connected with the outlet of the split phase tank of the hydrolysate, and the outlet of the beating tank is connected with the elution tank; the auxiliary stirring device is arranged inside the beating tank.
  • the concentration of the slurry can be adjusted to meet the requirements of the subsequent washing process.
  • the water used in the beating tank is provided by the water tank after washing, which further realizes the recycling of water.
  • FIG. 4 is a schematic diagram of a preferred embodiment of the production system of sulfuric acid method titanium dioxide according to the present invention.
  • the production system includes a hydrolysis phase separation unit, a slurry film washing unit, and a washing water treatment unit.
  • the hydrolysis phase separation unit includes: a hydrolysis material phase separation tank 101, a phase separation circulation pump 201, and a phase separation membrane module 301.
  • the slurry making unit includes: a beating tank 102 and an auxiliary stirring device.
  • the slurry membrane washing unit includes: an elution tank 103, an elution circulation pump 202, a washing membrane assembly 302, a qualified feed tank 104, an elution feed water pump 204, and a qualified material transfer pump 203.
  • the wash water treatment unit includes: a pre-wash water tank 105, a post-wash water tank 106, a wash water treatment inlet pump 205, and a wash water treatment assembly 303.
  • the core elements of the phase separation membrane module 301 and the washing membrane module 302 are tubular cross-flow microfiltration membranes, and the phase separation membrane module 301 and the washing membrane module 302 both establish a slurry between the membrane module and the slurry tank by a circulation pump Material circulation, in order to prevent the membrane module from clogging, the velocity of the slurry in the membrane module is 2-8m / s, the liquid phase in the slurry penetrates the membrane under the pressure difference of 0.1-0.5MPa, and the solid phase is intercepted on the slurry side
  • the precision of the microfiltration membrane is 50 ⁇ 1000nm, and the temperature resistance is ⁇ 50 ° C, which can effectively intercept the meta-titanate powder, and the turbidity of the clear liquid produced by the membrane is less than 1NTU.
  • the core element of the washing water treatment module 303 in the washing water treatment unit is composed of a nanofiltration membrane and a reverse osmosis membrane. After being treated by the nanofiltration membrane and the reverse osmosis membrane, a small amount of concentrated liquid produced by the washing water treatment unit is introduced into the wastewater treatment workshop, and a large amount of cleaning The liquid is returned to the pre-washing water tank 105 for recycling, and the iron content in the clear liquid can reach 2 ppm or less.
  • the process mainly includes the following steps:
  • inert gas is introduced into the tanks and tanks of the system except the split-phase circulation pump 201, the elution circulation pump 202, the qualified material transfer pump 203, the elution inlet pump 204, and the wash water treatment inlet pump 205.
  • Inert gas is introduced into 303 to exclude air, and samples are analyzed at the vent of each equipment. After the oxygen content is qualified, the system is ready to feed.
  • the qualified hydrolysis material is introduced into the hydrolysis material phase separation tank 101, and the slurry circulation between the hydrolysis material phase separation tank 101 and the phase separation membrane module 301 is established by the phase separation circulation pump 201, and the clear end of the phase separation membrane module 301 is continuously produced Clean the waste acid, and then introduce it into the subsequent waste acid treatment device; after the slurry concentration in the hydrolyzed material phase separation tank 101 reaches the set value, discharge to the beating tank 102, start stirring, and at the same time, wash the water into the water pump 205, after self-washing
  • the water tank 106 leads acidic water to the beating tank 102 for beating; after beating of the beating tank 102 is completed, it is discharged to the elution tank 103, and through the elution circulation pump 202, a slurry circulation between the elution tank 103 and the washing membrane module 302 is established , And continue to produce clear liquid to the water tank 106 after washing, at the same time start the elution inlet pump 204, from the
  • washing In order to maintain the water balance of the system, continue to add a small amount of fresh water to the sink 105 before washing.
  • the fresh water supplemented by the water tank 105 before washing is deoxygenated and demineralized water, and the water temperature is 20-50 ° C; the phase separation membrane module, washing membrane module, slurry tank, water tank, etc. involved in the system are all closed systems, and the whole system Inert gas is used for sealing, and the sealing pressure is 1 ⁇ 10KPa.
  • the concentration of the slurry obtained by the phase separation unit of the hydrolyzed material is 300-500 g / L; the concentration of the slurry after beating is 150-350 g / L; the concentration of the slurry after washing the qualified material is 150-350 g / L,
  • the content of elemental iron can reach below 10ppm.
  • the metatitanic acid slurry pulping step can be eliminated, and the hydrolyzed material phase separation tank and the elution tank are integrated into one body.
  • the slurry After the hydrolyzed material phase separation is completed, the slurry The material remains in the hydrolyzed material phase separation tank, and the hydrolyzed material phase separation tank can continue to be used as the elution tank for the washing process. There is no need to set up the elution tank separately.
  • inert gas is introduced into each slurry tank and water tank of the system to remove air, and the sample is analyzed at the vent of each equipment. After the oxygen content is qualified, the system is ready to feed.
  • the hydrolyzed material with a concentration of 180g / L is introduced into the hydrolyzed material phase separation tank 101, the outlet pressure of the phase separation circulation pump 201 is controlled to be 0.3MPa, and the slurry circulation is established.
  • the phase separation membrane module 301 produces clean waste acid, and the waste acid turbidity is 0.8NTU, 1h
  • the concentration of the slurry in the hydrolyzed material phase separation tank 101 reaches 400 g / L
  • the phase separation membrane module 301 stops the clear liquid, and the slurry in the hydrolyzed material phase separation tank 101 is discharged to the beating tank 102 depending on the position difference. Turn on the agitation, open the water inlet valve of the beating tank 102, and the beating and beating continue for 15min.
  • the beating tank 102 discharges to the elution tank 103 by position difference, controls the outlet pressure of the elution circulation pump 202 to 0.5 MPa, establishes the slurry circulation, and cleans the membrane module 302 to produce clear liquid to the washed water tank 106 with a flow rate of 15 m 3 / h.
  • the turbidity of the clear liquid is 0.5NTU.
  • the elution inlet pump 204 is turned on to supply water to the elution tank 103.
  • the water supply flow control is 15m 3 / h. After washing for 220min, the slurry is sampled for testing.
  • the elemental iron content in the slurry is 8.4ppm. If it is qualified, the elution tank 103 stops replenishing water, and the washing membrane module 302 stops the clear liquid. The qualified slurry in the elution tank 103 is replaced into the qualified material tank 104 according to the position difference, and is transferred out through the qualified material transfer pump 203; during this period, The washing water treatment unit continues to operate and produces 13.5m 3 / h of clear liquid, all of which are returned to the pre-washing water tank 105, and the flow rate of fresh deoxygenated and demineralized water in the pre-washing water tank 105 is 1.5m 3 / h.

Abstract

本发明公开了一种新型硫酸法钛白粉水洗工艺及系统，其中，所述工艺包括：水解料分相，将水解料进行相分离处理，得到偏钛酸浆料和液相洁净废酸；浆料膜洗涤，将所述偏钛酸浆料进行水洗，去除偏钛酸浆料中的杂质铁离子；洗水处理，将所述浆料膜洗涤得到的洗涤后出水进行处理，拦截杂质铁离子；所述水解料分相、所述浆料膜洗涤及所述洗水处理均在密闭环境下进行。本发明提供的一种新型硫酸法钛白粉水洗工艺及系统省去了传统工艺的漂白还原过程，实现洗涤过程一次完成，比传统工艺流程更简洁、高效、节能环保；该工艺产品出料中杂质铁含量更低，无须添加漂白剂、硫酸等药剂，同时实现洗水的循环利用，减少了生产成本，降低了三废排放量。

Description

一种新型硫酸法钛白粉水洗工艺及系统 技术领域
本发明涉及硫酸法钛白粉生产技术领域，具体涉及一种新型硫酸法钛白粉水洗工艺及系统。
背景技术
钛白粉制造方法有两种：硫酸法和氯化法。中国的钛白粉工厂以硫酸法为主。硫酸法是将钛铁粉与浓硫酸进行酸解反应生产硫酸氧钛，经水解生成偏钛酸，再经煅烧、粉碎即得到钛白粉产品。此法可生产锐钛型和金红石型钛白粉。硫酸法能以价低易得的钛铁矿与硫酸为原料，技术较成熟，设备简单，防腐蚀材料易解决。
传统的硫酸法钛白粉水洗生产过程中，水洗工艺分为一洗、漂白、二洗三个阶段，二洗水套用至一洗，一洗水直接排放，洗涤水量大，洗涤流程长，洗涤效果差，药剂消耗大。同时，为了消除偏钛酸浆料中三价铁离子的影响，传统的生产工艺需要将水洗后偏钛酸滤饼打浆后加入浓硫酸和还原剂，把水洗过程中形成的三价铁离子还原为二价铁后，再进行第二次水洗将其去除。整个工艺流程长，操作繁琐。
发明内容
本发明的目的是提供一种新型硫酸法钛白粉水洗工艺，能够简化硫酸法钛白粉的流程，操作简单。
本发明的另一个目的是提供一种新型硫酸法钛白粉水洗系统。
本发明提供的技术方案如下：
一种新型硫酸法钛白粉水洗工艺，其包括：
水解料分相，将水解料进行相分离处理，得到偏钛酸浆料和液相洁净废酸；
浆料膜洗涤，将所述偏钛酸浆料进行水洗，去除偏钛酸浆料中的杂质铁离子；
洗水处理，将所述浆料膜洗涤得到的洗涤后出水进行处理，拦截杂质铁离子；
所述水解料分相、所述浆料膜洗涤及所述洗水处理均在密闭环境下进行。进一步地，在所述水解料分相的步骤中，通过分相膜组件对水解料进行相分离处理。
进一步地，在所述浆料膜洗涤步骤中，对所述偏钛酸浆料进行连续进水连续出水式的洗涤；由洗前水槽持续补水，同时，浆料洗涤过程中连续出水至洗后水槽；
进一步地，在所述浆料膜洗涤步骤中，通过洗涤膜组件对所述偏钛酸浆料进行洗涤。
进一步地，所述分相膜组件和所述洗涤膜组件均包括但不限定于管式十字流微滤膜，且所述管式十字流微滤膜的精度为50-1000nm，耐温为≥50℃。
进一步地，浆料在膜组件内的流速为2～8m/s，浆料内液相在0.1～0.5MPa压差作用下透过膜，固相被拦截在浆料侧，膜产出清液浊度小于1NTU。
进一步地，所述水解料分相步骤得到的偏钛酸浆料浓度为300～500g/L；
进一步地，所述浆料膜洗涤步骤得到的洗涤合格料的浆料浓度为150～350g/L，其中单质铁含量为10ppm以下。
进一步地，在所述洗水处理的步骤中，通过洗水处理组件将所述洗涤后出水进行处理；所述洗水处理组件包括但不限定于纳滤膜和反渗透膜。
在所述洗水处理的步骤中，处理后的清液返回所述洗前水槽，实现洗水的循环利用。
进一步地，在所述浆料膜洗涤步骤中，用于水洗的水源包括补充新鲜水， 且该补充新鲜水为脱氧脱盐水，水温20-50℃。
进一步地，在所述水解料分相和所述浆料膜洗涤之间还包括：
偏钛酸浆料制浆，将所述水解料分相得到的偏钛酸浆料稀释打浆至预设浓度，打浆得到的浆料浓度为150～350g/L；打浆所用水采用所述浆料膜洗涤过程产出的清液。
本发明还提供了一种新型硫酸法钛白粉生产系统，其包括：
水解分相单元，其包括用于对水解料进行相分离处理的分相膜组件，得到偏钛酸浆料和液相洁净废酸；
浆料膜洗涤单元，其包括用于对所述偏钛酸浆料进行洗涤的洗涤膜组件；
洗水处理单元，其包括用于对所述浆料膜洗涤单元得到的洗涤后出水进行处理的洗水处理组件；
所述水解分相单元、所述浆料膜洗涤单元、所述洗水处理单元均为密闭结构。
进一步地，所述水解分相单元包括水解料分相槽、分相循环泵、分相膜组件，所述水解料分相槽和所述分相膜组件之间通过所述分相循环泵建立浆料循环；所述水解料分相槽的出口与所述分相循环泵的入口连通，所述分相循环泵的出口与所述分相膜组件连通，所述分相膜组件的浆料侧与所述水解料分相槽连通；
所述浆料膜洗涤单元包括洗脱槽、合格料槽、洗脱循环泵、合格料转料泵、洗脱进水泵、洗涤膜组件，所述洗脱槽的入口与所述水解料分相槽的另一出口连通，所述洗脱槽和所述洗涤膜组件之间通过所述洗脱循环泵建立浆料循环；所述洗脱槽的出口与所述洗脱循环泵的入口连通，所述洗脱循环泵的出口与所述洗涤膜组件连通，所述洗涤膜组件的浆料侧与所述洗脱槽连通。所述合格料槽的入口与所述洗脱槽的出口连通，所述合格料槽的出口与所述合格料转料泵连通。所述洗脱进水泵的出口与所述洗脱槽的入口连通，所述洗脱进水泵的进 口与洗前水槽的出口连通；
所述洗水处理单元包括洗水处理进水泵、洗水处理组件、洗前水槽、洗后水槽，所述洗水处理进水泵的入口与所述洗后水槽出口连通，所述洗水处理进水泵的出口与所述洗水处理组件连通；所述洗前水槽的入口与所述洗水处理组件的清液侧连通；
进一步地，所述的新型硫酸法钛白粉生产系统还包括：
浆料制浆单元，其包括打浆槽和附属搅拌装置；所述打浆槽的入口与所述水解料分相槽的出口连通，所述打浆槽的出口与所述洗脱槽连通；所述附属搅拌装置设置于所述打浆槽内部；所述洗后水槽的出口同时还和所述打浆槽的入口连通。
所述水解料分相槽、打浆槽、洗脱槽、合格料槽、洗前水槽、洗后水槽、分相膜组件、洗涤膜组件、洗水处理组件均为密闭结构。
进一步地，所述洗前水槽的入口还与外部脱氧脱盐水口连通。
进一步地，所述分相膜组件和洗涤膜组件包括但不限定于管式十字流微滤膜；
进一步地，所述洗水处理组件包括但不限定于纳滤膜和反渗透膜；
进一步地，所述水解料分相槽和所述洗脱槽集成为一体；
进一步地，所述分相膜组件的废酸侧与废酸处理装置连接。
本发明提供的一种新型硫酸法钛白粉水洗工艺及系统，能够带来以下至少一种有益效果：
1、本发明采用全封闭隔绝空气的生产方式，防止偏钛酸浆料中二价铁氧化为三价铁；更优地，还采用脱氧脱盐水进行打浆和水洗，也能够进一步防止铁离子的氧化，从而可以省去传统工艺的漂白还原过程，实现洗涤过程一次完成，比传统工艺流程更简洁、高效、节能环保。
2、本发明工艺的产品出料中杂质铁含量更低，无须添加漂白剂、硫酸等 药剂再进行处理，节约流程，更为环保。
3、本发明的管式十字流微滤膜这种高效膜组件可以实现连续操作、自动化程度高，避免了管式过滤机、真空叶滤机、隔膜压滤机等设备低效、能耗高、占地大的弊端。
4、本发明使用高效膜组件，无粉体穿滤的风险，废酸无需进行粉体回收处理，可直接引入废酸处理装置，节省处理成本
5、本发明首次将纳滤膜水处理技术应用在钛白粉水洗回收上，产水回收率高、浓水排放量少，将洗水处理后的清液用于膜洗涤过程的注入水，实现了水洗水的循环利用，极大地降低了新鲜脱氧水的用量和外排废水量，减少了污水处理成本。
6、本发明的部分实施例还可以省去偏钛酸浆料制浆步骤，水解分相得到的偏钛酸浆料浓度已符合要求，可直接进行洗涤。
附图说明
下面将以明确易懂的方式，结合附图说明优选实施方式，对本申请的上述特性、技术特征、优点及其实现方式予以进一步说明。
图1是本发明新型硫酸法钛白粉水洗工艺一种实施例的示意图；
图2是本发明新型硫酸法钛白粉水洗工艺另一种实施例的示意图；
图3是本发明新型硫酸法钛白粉水洗系统一种实施例的示意图；
图4是本发明新型硫酸法钛白粉水洗系统另一种实施例的示意图。
附图标记：
101-水解料分相槽；102-打浆槽；103-洗脱槽；104-合格料槽；105-洗前水槽；106-洗后水槽；201-分相循环泵；202-洗脱循环泵；203-合格料转料泵；204-洗脱进水泵；205-洗水处理进水泵；301-分相膜组件；302-洗涤膜组件；303-洗水处理组件。
具体实施方式
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对照附图说明本发明的具体实施方式。显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图，并获得其他的实施方式。
为使图面简洁，各图中的只示意性地表示出了与本发明相关的部分，它们并不代表其作为产品的实际结构。
在本发明新型硫酸法钛白粉水洗工艺的实施例一中，生产工艺包括如下步骤：
水解料分相，将水解料进行相分离处理，得到偏钛酸浆料和液相洁净废酸；
浆料膜洗涤，将偏钛酸浆料进行水洗，去除偏钛酸浆料中的杂质铁离子；
洗水处理，将浆料膜洗涤得到的洗涤后出水进行处理，拦截杂质铁离子；
水解料分相、浆料膜洗涤及洗水处理均在密闭环境下进行。
在实施例一中，水解料为水解后得到的偏钛酸，将该水解料进行相分离，以得到偏钛酸浆料，同时得到液相洁净废酸。对偏钛酸浆料进行洗涤，以去除杂质铁离子。进一步地，对洗涤得到的洗涤后出水进行处理，以拦截杂质铁离子，满足洗水循环利用的要求。水解料分相、浆料膜洗涤及洗水处理均在全封闭隔绝空气的密闭环境下进行，可以有效防止偏钛酸浆料中的二价铁氧化为三价铁，从而可以省去传统工艺的漂白还原过程，实现洗涤过程一次完成，比传统工艺流程更简洁、高效、节能环保。
在本发明新型硫酸法钛白粉水洗工艺的实施例二中，在前述实施例一的基础上进行细化。在水解料分相的步骤中，通过分相膜组件对水解料进行相分离处理。在浆料膜洗涤步骤中，通过洗涤膜组件对偏钛酸浆料进行连续出水式的洗涤。分相膜组件和洗涤膜组件相较于现有的管式过滤机、真空叶滤机、隔膜压滤机等大型设备来说，这种高效膜组件过滤精度高，能耗低，占用空间小。 优选地，分相膜组件和洗涤膜组件的核心部件为管式十字流微滤膜，且管式十字流微滤膜的精度为50-1000nm，耐温为≥50℃。
为防止膜组件发生堵塞，浆料在膜组件内流速为2～8m/s，浆料内液相在0.1～0.5MPa压差作用下透过膜，可通过循环泵实现流速和压差的控制。固相被拦截在浆料侧，该微滤膜可以实现偏钛酸粉体的有效拦截，膜产出清液浊度小于1NTU。
水解料分相步骤得到的偏钛酸浆料浓度为300～500g/L；浆料膜洗涤步骤得到的洗涤合格料的浆料浓度为150～350g/L，其中单质铁含量为10ppm以下。
在本实施例中，在洗水处理的步骤中，通过洗水处理组件将洗涤后出水进行处理；洗水处理组件包括纳滤膜和反渗透膜。洗水处理组件的核心元件由纳滤膜和反渗透膜组成，经处理后，清液中铁含量可达到2ppm以下。本发明首次将纳滤膜水处理技术应用在钛白粉水洗回收上，产水质量较高。优选地，将洗水处理得到的清液返回用于浆料膜洗涤的步骤中，作为主要的水源补充，从而洗水处理产水的回收率高、浓水排放量少，实现了水洗水的循环利用，极大地降低了新鲜脱氧水的用量和外排废水量，减少了污水处理成本。
本实施例通过惰性气体的密封实现密闭环境，密封压力为1-10KPa，可以极佳地隔绝氧气，杜绝对二价铁的氧化。进一步地，在浆料膜洗涤步骤中，由于还需补充少量新鲜水，考虑到对二价铁的氧化影响，补充新鲜水使用脱氧脱盐水，水温20-50℃。
现结合图1对本发明新型硫酸法钛白粉水洗工艺进行描述。首先向系统各浆料罐、水罐中通入惰性气体，排除空气，并在各设备放空口取样分析，含氧量合格后，系统准备进料。
(1)水解料引入，并通过高效膜组件进行分相，得到偏钛酸浆料和废酸。废酸直接送去废酸处理装置进行处理。
(2)偏钛酸浆料送入浆料膜洗涤单元。在浆料膜洗涤过程中，由洗前水 槽持续向浆料膜洗涤过程补水，洗涤过程连续出水，并将出水汇集至洗后水槽。洗前水槽同时有少量脱氧脱盐水进行补充。最终得到满足要求的洗涤合格料。
(3)洗后水槽的水被送去进行洗水处理，得到的清液送回洗前水槽循环使用，洗水处理单元得到的浓水排出进行废水处理。
在本发明新型硫酸法钛白粉水洗工艺的实施例三中，在前述实施例二的基础上进行调整和优化。在所述水解料分相和所述浆料膜洗涤之间还包括：
偏钛酸浆料制浆，将水解料分相得到的偏钛酸浆料稀释打浆至预设浓度。该浓度可以为150～350g/L。且优选地，打浆所用水采用前述浆料膜洗涤过程产出的清液，将洗后水槽的清液引至打浆过程即可，节约用水量。
参照图2所示，新型硫酸法钛白粉水洗工艺包括以下步骤：
首先向系统(除泵体外的)各浆料罐、水罐中通入惰性气体，排除空气，并在各设备放空口取样分析，含氧量合格后，系统准备进料。
(1)水解料引入，并通过高效膜组件进行分相，得到偏钛酸浆料和废酸。废酸直接送去废酸处理装置进行处理。
(2)将水解分相得到的偏钛酸浆料稀释打浆至预设浓度。打浆用水由浆料膜洗涤过程中的洗后水槽提供。
(3)偏钛酸浆料送入浆料膜洗涤单元。在浆料膜洗涤过程中，由洗前水槽持续向浆料膜洗涤过程补水，洗涤过程连续出水，并将出水汇集至洗后水槽。洗前水槽同时有少量脱氧脱盐水进行补充。最终得到满足要求的洗涤合格料。
(4)洗后水槽的水被送去进行洗水处理，得到的清液送回洗前水槽循环使用，洗水处理单元得到的浓水排出进行废水处理。
本发明还提供了一种新型硫酸法钛白粉水洗系统。在该生产系统的实施例一中，包括：
水解分相单元，其包括用于对水解料进行相分离处理的分相膜组件，得到 偏钛酸浆料和液相洁净废酸；
浆料膜洗涤单元，其包括用于对偏钛酸浆料进行洗涤的洗涤膜组件；
洗水处理单元，其包括用于对浆料膜洗涤单元得到的洗涤后出水进行处理的洗水处理组件；
水解分相单元、浆料膜洗涤单元、洗水处理单元均为密闭结构。
在本实施例中，分相膜组件和洗涤膜组件均是高效膜组件，可以实现连续操作、自动化程度高，避免了管式过滤机、真空叶滤机、隔膜压滤机等设备低效、能耗高、占地大的弊端。另外，密闭结构可通过通入惰性气体实现，能够有效避免二价铁被氧化为三价铁。
在生产系统的实施例二中，对前述的实施例一进行优化。具体地，水解分相单元包括水解料分相槽、分相循环泵、分相膜组件，水解料分相槽和分相膜组件之间通过分相循环泵建立浆料循环。浆料膜洗涤单元包括洗脱槽、洗脱循环泵、洗涤膜组件，洗脱槽的入口与水解料分相槽的出口连通，洗脱槽和洗涤膜组件之间通过洗脱循环泵建立浆料循环。洗水处理单元包括洗水处理进水泵、洗水处理组件，洗水处理进水泵的入口与洗涤膜组件的废液出口连通，洗水处理进水泵的出口与洗水处理组件连通。水解料分相槽、分相膜组件、洗脱槽、洗涤膜组件、洗水处理组件均为密闭结构。
进一步地，水解料分相槽的另一出口与分相循环泵的入口连通，分相循环泵的出口与分相膜组件连通，分相膜组件的浆料侧与水解料分相槽的入口连通；洗脱槽的出口与洗脱循环泵的入口连通，洗脱循环泵的出口与洗涤膜组件连通，洗涤膜组件的浆料侧与洗脱槽的入口连通。
进一步地，浆料膜洗涤单元还包括合格料槽、合格料转料泵；合格料槽的入口与洗脱槽的出口连通，合格料槽的出口与合格料转料泵连通。合格料槽用于存储合格料，并通过合格料转料泵将合格料送出。
进一步地，浆料膜洗涤单元还包括洗脱进水泵；洗水处理单元还包括洗前 水槽和洗后水槽；洗前水槽的入口与洗水处理组件的清液侧连通，洗前水槽的出口与洗脱进水泵的入口连通，洗脱进水泵的出口与洗脱槽的入口连通；洗后水槽的入口与洗涤膜组件的废液侧连通，洗后水槽的出口与洗水处理进水泵连通。将洗水处理组件的清液引入洗前水槽循环使用，极大地节约了用水量。
由于洗前水槽的少量水需新鲜水补充，考虑到对二价铁的氧化影响，引入的新鲜水为脱氧脱盐水，因而，洗前水槽的入口还与外部脱氧脱盐水口连通。
进一步地，分相膜组件包括管式十字流微滤膜，洗涤膜组件包括管式十字流微滤膜。管式十字流微滤膜这种高效膜组件可以实现连续操作、自动化程度高，避免了管式过滤机、真空叶滤机、隔膜压滤机等设备低效、能耗高、占地大的弊端。
进一步地，洗水处理组件包括纳滤膜和反渗透膜。本发明首次将纳滤膜水处理技术应用在钛白粉水洗回收上，产水回收率高、浓水排放量少，将洗水处理后的清液用于膜洗涤过程的注入水，实现了水洗水的循环利用，极大地降低了新鲜脱氧水的用量和外排废水量，减少了污水处理成本。
进一步地，水解料分相槽和洗脱槽集成为一体，水解料分相结束后，浆料留在水解料分相槽中，可将水解料分相槽继续作为洗脱槽使用，进行洗涤过程。不用再单独设置洗脱槽。
进一步地，分相膜组件的废酸侧与废酸处理装置连接。由于使用了分相膜组件这种高效膜组件，无粉体穿滤的风险，废酸无需进行粉体回收处理，可直接引入废酸处理装置，节省处理成本。
图3为本发明硫酸法钛白粉生产系统的一种实施例的示意图，如图所示，生产系统包括水解分相单元、浆料膜洗涤单元、洗水处理单元。其中，水解分相单元包括：水解料分相槽101、分相循环泵201、分相膜组件301。浆料膜洗涤单元包括：洗脱槽103、洗脱循环泵202、洗涤膜组件302、合格料槽104、洗脱进水泵204、合格料转料泵203。洗水处理单元包括：洗前水槽105、洗后 水槽106、洗水处理进水泵205、洗水处理组件303。
其中，分相膜组件301和洗涤膜组件302的核心元件是管式十字流微滤膜，分相膜组件301和洗涤膜组件302均是通过循环泵在膜组件与浆料槽之间建立浆料循环。洗水处理单元中洗水处理组件303的核心元件由纳滤膜和反渗透膜组成，经处理后，洗水处理单元产生的少量浓液引入废水处理车间，大量清液返回洗前水槽105循环利用。
在本发明生产系统的实施例三中，在前述实施例二的基础上进行补充。新型硫酸法钛白粉生产系统还包括浆料制浆单元，浆料制浆单元包括打浆槽和附属搅拌装置。打浆槽的入口与水解料分相槽的出口连通，打浆槽的出口与洗脱槽连通；附属搅拌装置设置于打浆槽内部。通过打浆槽和附属搅拌装置可以调整浆料的浓度，以满足后续洗涤过程的要求。
进一步地，打浆槽所用水由洗后水槽提供，进一步实现了水的循环利用。
图4为本发明硫酸法钛白粉生产系统的优选实施例的示意图，如图所示，生产系统包括水解分相单元、浆料膜洗涤单元、洗水处理单元。其中，水解分相单元包括：水解料分相槽101、分相循环泵201、分相膜组件301。浆料制浆单元包括：打浆槽102和附属搅拌装置。浆料膜洗涤单元包括：洗脱槽103、洗脱循环泵202、洗涤膜组件302、合格料槽104、洗脱进水泵204、合格料转料泵203。洗水处理单元包括：洗前水槽105、洗后水槽106、洗水处理进水泵205、洗水处理组件303。
其中，分相膜组件301和洗涤膜组件302的核心元件是管式十字流微滤膜，分相膜组件301和洗涤膜组件302均是通过循环泵在膜组件与浆料槽之间建立浆料循环，为防止膜组件发生堵塞，浆料在膜组件内流速为2～8m/s，浆料内液相在0.1～0.5MPa压差作用下透过膜，固相被拦截在浆料侧，该微滤膜精度50～1000nm，耐温≥50℃，可以有效实现偏钛酸粉体的拦截，膜产出清液浊度小于1NTU。
洗水处理单元中洗水处理组件303的核心元件由纳滤膜和反渗透膜组成，经纳滤膜和反渗透膜处理后，洗水处理单元产生的少量浓液引入废水处理车间，大量清液返回洗前水槽105循环利用，该清液中铁含量可达到2ppm以下。
在使用图4所示的新型硫酸法钛白粉水洗系统时，工艺主要包括如下步骤：
首先向系统中除了分相循环泵201、洗脱循环泵202、合格料转料泵203、洗脱进水泵204、洗水处理进水泵205以外的各罐体、槽体通入惰性气体。具体地，向水解料分相槽101、打浆槽102、洗脱槽103、合格料槽104、洗前水槽105、洗后水槽106、分相膜组件301、洗涤膜组件302、洗水处理组件303中通入惰性气体，排除空气，并在各设备放空口取样分析，含氧量合格后，系统准备进料。
水解合格料引入水解料分相槽101，经分相循环泵201，建立水解料分相槽101与分相膜组件301之间的浆料循环，同时分相膜组件301清液端连续产出洁净废酸，进而引入后续废酸处理装置；水解料分相槽101内浆料浓度达到设定值后，卸料至打浆槽102，开启搅拌，同时经洗水处理进水泵205，自洗后水槽106引酸性水至打浆槽102进行打浆；打浆槽102打浆完成后，卸料至洗脱槽103，经洗脱循环泵202，建立洗脱槽103与洗涤膜组件302之间的浆料循环，并持续产出清液至洗后水槽106，同时启动洗脱进水泵204，自洗前水槽105引水至洗脱槽103，保持洗脱槽103内浆料浓度不变，批次浆料洗涤合格后，洗脱槽103停止进水，洗涤膜组件302停止出水，洗脱槽103内的合格浆料卸料至合格料槽104，进而经由合格料转料泵203转出至下一工段；洗后水槽106内酸性水少量引入打浆槽102进行打浆，其余水经由洗水处理进水泵205引入洗水处理组件303，经处理后，产出少量浓液引入废水处理车间，产出大量清液返回洗前水槽105，循环用于洗脱单元的浆料洗涤；为保持系统水平衡，持续补充少量新鲜水至洗前水槽105。
其中，洗前水槽105所补充的新鲜水为脱氧脱盐水，水温20～50℃；系统中 所涉及的分相膜组件、洗涤膜组件、浆料罐、水罐等均为密闭系统，全系统采用惰性气体进行密封，密封压力为1～10KPa。
在本实施例中，水解料分相单元得到的浆料浓度为300～500g/L；打浆后的浆料浓度为150～350g/L；洗涤合格料的浆料浓度为150～350g/L，其中单质铁含量可达到10ppm以下。
在本发明中，通过控制水解料分相单元的浆料浓度，可以取消偏钛酸浆料制浆步骤，将水解料分相槽和洗脱槽集成为一体，水解料分相结束后，浆料留在水解料分相槽中，可将水解料分相槽继续作为洗脱槽使用，进行洗涤过程。不用再单独设置洗脱槽。
以下列举一具体应用实施例：
首先向系统各浆料罐、水罐中通入惰性气体，排除空气，并在各设备放空口取样分析，含氧量合格后，系统准备进料。
浓度180g/L的水解料引入水解料分相槽101，控制分相循环泵201出口压力0.3MPa，建立浆料循环，分相膜组件301产出洁净废酸，废酸浊度0.8NTU，1h后，水解料分相槽101中浆料浓度达到400g/L，分相膜组件301停止出清液，水解料分相槽101中浆料依靠位差卸料至打浆槽102。开启搅拌，打开打浆槽102进水阀门，补水打浆持续15min，浆料浓度达到300g/L后，停止补水打浆。打浆槽102靠位差卸料至洗脱槽103，控制洗脱循环泵202出口压力0.5MPa，建立浆料循环，洗涤膜组件302产出清液至洗后水槽106，流量15m 3/h，清液浊度0.5NTU，同时开启洗脱进水泵204向洗脱槽103补水，补水流量控制15m 3/h，洗涤220min后，浆料取样进行检测，浆料中单质铁含量8.4ppm，认定水洗合格，洗脱槽103停止补水，洗涤膜组件302停止出清液，洗脱槽103中合格浆料靠位差换入合格料槽104，经由合格料转料泵203转出；在此期间，洗水处理单元持续运行，产出清液13.5m 3/h，全部返回洗前水槽105，洗前水槽105补充新鲜脱氧脱盐水流量为1.5m 3/h。
应当说明的是，上述实施例均可根据需要自由组合。以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (20)

  1. 一种新型硫酸法钛白粉生产工艺，其特征在于，包括：
    水解料分相，将水解料进行相分离处理，得到偏钛酸浆料和液相洁净废酸；
    浆料膜洗涤，将所述偏钛酸浆料进行水洗，去除偏钛酸浆料中的杂质铁离子；
    洗水处理，将所述浆料膜洗涤得到的洗涤后出水进行处理，拦截杂质铁离子；
    所述水解料分相、所述浆料膜洗涤及所述洗水处理均在密闭环境下进行。
  2. 根据权利要求1所述的新型硫酸法钛白粉生产工艺，其特征在于：
    在所述水解料分相的步骤中，通过分相膜组件对水解料进行相分离处理。
  3. 根据权利要求1所述的新型硫酸法钛白粉生产工艺，其特征在于：
    在所述浆料膜洗涤步骤中，通过洗涤膜组件对所述偏钛酸浆料进行洗涤；且所述洗涤的过程采用连续进水连续出水的方式。
  4. 根据权利要求2或3所述的新型硫酸法钛白粉生产工艺，其特征在于：
    所述分相膜组件和所述洗涤膜组件均包括管式十字流微滤膜，且所述管式十字流微滤膜的精度为50-1000nm，耐温为≥50℃。
  5. 根据权利要求4所述的新型硫酸法钛白粉生产工艺，其特征在于：
    浆料在膜组件内的流速为2～8m/s，浆料内液相在0.1～0.5MPa压差作用下透过膜，固相被拦截在浆料侧，膜产出清液浊度小于1NTU。
  6. 根据权利要求2或3所述的新型硫酸法钛白粉生产工艺，其特征在于：
    所述水解料分相步骤得到的偏钛酸浆料浓度为300～500g/L；
    和/或，
    所述浆料膜洗涤步骤得到的洗涤合格料的浆料浓度为150～350g/L，其中单质铁含量为10ppm以下。
  7. 根据权利要求1所述的新型硫酸法钛白粉生产工艺，其特征在于：
    在所述洗水处理的步骤中，通过洗水处理组件将所述洗涤后出水进行处理；所述洗水处理组件包括纳滤膜和反渗透膜。
  8. 根据权利要求1所述的新型硫酸法钛白粉生产工艺，其特征在于：
    在所述洗水处理的步骤中，处理后的清液返回为所述浆料膜洗涤的步骤进行供水，实现洗水的循环利用。
  9. 根据权利要求1所述的新型硫酸法钛白粉生产工艺，其特征在于：
    所述密闭环境通过惰性气体密封实现，密封压力为1-10KPa；
    和/或，
    在所述浆料膜洗涤步骤中，用于水洗的水源包括补充新鲜水，且该补充新鲜水为脱氧脱盐水，水温20-50℃。
  10. 根据权利要求1，2，3，5，7，8，9中任一项所述的新型硫酸法钛白粉生产工艺，其特征在于，在所述水解料分相和所述浆料膜洗涤之间还包括：
    偏钛酸浆料制浆，将所述水解料分相得到的偏钛酸浆料稀释打浆至预设浓度。
  11. 根据权利要求10所述的新型硫酸法钛白粉生产工艺，其特征在于：
    打浆得到的浆料浓度为150～350g/L；
    和/或，
    打浆所用水采用所述浆料膜洗涤过程产出的清液。
  12. 一种新型硫酸法钛白粉生产系统，其特征在于，包括：
    水解分相单元，其包括用于对水解料进行相分离处理的分相膜组件，得到偏钛酸浆料和液相洁净废酸；
    浆料膜洗涤单元，其包括用于对所述偏钛酸浆料进行洗涤的洗涤膜组件；
    洗水处理单元，其包括用于对所述浆料膜洗涤单元得到的洗涤后出水进行水洗的洗水处理组件；
    所述水解分相单元、所述浆料膜洗涤单元、所述洗水处理单元均为密闭结构。
  13. 根据权利要求12所述的新型硫酸法钛白粉生产系统，其特征在于：
    所述水解分相单元包括水解料分相槽、分相循环泵、分相膜组件，所述水解料分相槽和所述分相膜组件之间通过所述分相循环泵建立浆料循环；
    所述浆料膜洗涤单元包括洗脱槽、洗脱循环泵、洗涤膜组件，所述洗脱槽的入口与所述水解料分相槽的出口连通，所述洗脱槽和所述洗涤膜组件之间通过所述洗脱循环泵建立浆料循环；
    所述洗水处理单元包括洗水处理进水泵、洗水处理组件，所述洗水处理进水泵的入口与所述洗涤膜组件的废液出口连通，所述洗水处理进水泵的出口与所述洗水处理组件连通；
    所述水解料分相槽、所述分相膜组件、所述洗脱槽、所述洗涤膜组件、所述洗水处理组件均为密闭结构。
  14. 根据权利要求13所述的新型硫酸法钛白粉生产系统，其特征在于：
    所述水解料分相槽的另一出口与所述分相循环泵的入口连通，所述分相循环泵的出口与所述分相膜组件连通，所述分相膜组件的浆料侧与所述水解料分相槽的入口连通；
    所述洗脱槽的出口与所述洗脱循环泵的入口连通，所述洗脱循环泵的出口与所述洗涤膜组件连通，所述洗涤膜组件的浆料侧与所述洗脱槽的入口连通。
  15. 根据权利要求13所述的新型硫酸法钛白粉生产系统，其特征在于：
    所述浆料膜洗涤单元还包括合格料槽、合格料转料泵；
    所述合格料槽的入口与所述洗脱槽的出口连通，所述合格料槽的出口与所述合格料转料泵连通。
  16. 根据权利要求13所述的新型硫酸法钛白粉生产系统，其特征在于：
    所述浆料膜洗涤单元还包括洗脱进水泵；
    所述洗水处理单元还包括洗前水槽和洗后水槽；
    所述洗前水槽的入口与所述洗水处理组件的清液侧连通，所述洗前水槽的出口与所述洗脱进水泵的入口连通，所述洗脱进水泵的出口与所述洗脱槽的入口连通；
    所述洗后水槽的入口与所述洗涤膜组件的废液侧连通，所述洗后水槽的出口与所述洗水处理进水泵连通。
  17. 根据权利要求16所述的新型硫酸法钛白粉生产系统，其特征在于：
    所述洗前水槽的入口还与外部脱氧脱盐水口连通。
  18. 根据权利要求13所述的新型硫酸法钛白粉生产系统，其特征在于：
    所述分相膜组件包括管式十字流微滤膜；
    和/或，
    所述洗涤膜组件包括管式十字流微滤膜；
    和/或，
    所述洗水处理组件包括纳滤膜和反渗透膜；
    和/或，
    所述水解料分相槽和所述洗脱槽集成为一体；
    和/或，
    所述分相膜组件的废酸侧与废酸处理装置连接。
  19. 根据权利要求13-17任一项所述的新型硫酸法钛白粉生产系统，其特征在于，还包括：
    浆料制浆单元，其包括打浆槽和附属搅拌装置；
    所述打浆槽的入口与所述水解料分相槽的出口连通，所述打浆槽的出口与所述洗脱槽连通；
    所述附属搅拌装置设置于所述打浆槽内部。
  20. 根据权利要求19所述的新型硫酸法钛白粉生产系统，其特征在于，
    所述洗水处理单元还包括洗前水槽和洗后水槽；
    所述洗后水槽的入口与所述洗涤膜组件的废液侧连通，所述洗后水槽的出口与所述洗水处理进水泵连通；
    所述洗后水槽的出口同时还和所述打浆槽的入口连通。
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