WO2017020547A1 - 一种高效的硫酸法钛白粉水洗系统及其水洗工艺 - Google Patents

一种高效的硫酸法钛白粉水洗系统及其水洗工艺 Download PDF

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WO2017020547A1
WO2017020547A1 PCT/CN2016/070457 CN2016070457W WO2017020547A1 WO 2017020547 A1 WO2017020547 A1 WO 2017020547A1 CN 2016070457 W CN2016070457 W CN 2016070457W WO 2017020547 A1 WO2017020547 A1 WO 2017020547A1
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water
water washing
washing
sulfuric acid
filtration system
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PCT/CN2016/070457
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English (en)
French (fr)
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杨积志
单祥雷
吴科
李达开
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上海安赐环保科技股份有限公司
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Publication of WO2017020547A1 publication Critical patent/WO2017020547A1/zh

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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
    • 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
    • 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
    • C01G23/0475—Purification

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  • the invention relates to a water washing system for sulfuric acid method titanium white powder, in particular to an efficient sulfuric acid method titanium dioxide water washing system and a water washing process thereof.
  • the current production line will add concentrated sulfuric acid and a reducing agent after the water-washed metatitanic acid filter cake, and dissolve the precipitate or high-valent oxide formed in the water washing process into an ionic state, and then perform a second water washing. It is removed. The entire process is long and the operation is cumbersome.
  • the present invention provides an efficient sulfuric acid method titanium dioxide water washing system and a water washing process thereof.
  • An efficient sulfuric acid method titanium dioxide water washing system comprises:
  • waste acid recovery device wherein the waste acid recovery device is connected to a waste acid discharge port of the filter
  • a beater wherein the beater is connected to a filter cake outlet of the filter
  • the first filtration system being in communication with the water washing cycle tank;
  • a second filtration system wherein the second filtration system is respectively connected to the water washing circulation tank, the first filtration system, and the waste acid recovery device;
  • the first filtration system is a cross-flow microfiltration membrane having an accuracy of 50-1000 nm and a transmembrane pressure difference of 0.05-0.8 MPa.
  • the second filtration system is composed of a nanofiltration membrane and a reverse osmosis membrane, and the rejection ratio of the nanofiltration membrane to ferrous ions is 85-99.8%, and the retention of titanium oxysulfate
  • the rate is 80-99.8%
  • the sulfuric acid concentration is 0-30%
  • the operating pressure is 1.0-6.5MPa
  • the rejection rate of the reverse osmosis membrane to ferrous ions is 85-99.8%
  • the rejection rate of sulfuric acid is 85-99.8%
  • the sulfuric acid resistance is 0-15%
  • the operating pressure is 1.5-6.5 MPa.
  • the water washing circulation tank is a closed container, and the water washing circulation tank is sealed with a non-oxidizing gas, and the pressure inside the tank is maintained at 1-10 KPa.
  • both the soft water and the water wash water used in the beater are oxygen-free water.
  • An efficient sulfuric acid method titanium dioxide water washing process comprises the following steps:
  • the filter machine will fully extrude the filter cake containing concentrated acid and metal ions in metatitanic acid in the hydrolyzed material, and the filter will transport the filter cake to the beater, and the filter will squeeze the remaining in the hydrolyzed material.
  • the waste acid is transported to the waste acid recovery unit;
  • the slurry enters the water washing circulation tank, and the soft water used for the first water washing also enters the water washing circulation tank, the impurity ions in the slurry and the slurry are diluted, and then the water is filtered out through the first filtering system, so that The impurity ions in the slurry are reduced. If the soft water continues to enter, the supernatant of the first filtration system is continuously discharged, and the impurity ions in the slurry are continuously reduced until it is lowered to a qualified standard;
  • the water-washed qualified water-washing material is sent to the first filtration system, and after the delivery is completed, the next batch of the slurry is washed into the water-washing circulation tank to continue washing;
  • the first filtration system intercepts the slurry conveyed from the water washing circulation tank and the metatitanic acid particles in the water washing water, and re-delivers the retained concentrated liquid containing the metatitanic acid particles into the water washing circulation tank, and the water washing circulating tank is intercepted.
  • the concentrated solution containing metatitanic acid particles is re-washed, and the first filtration system delivers the filtered supernatant to the second Filtering again in the filtration system;
  • a part of the supernatant of the first filtration system is pumped to the reverse osmosis membrane for filtration, and a part of it is filtered into the nanofiltration membrane.
  • the reverse osmosis can retain sulfuric acid, ferrous iron, titanium oxysulfate, and the nanofiltration only retains ferrous iron and
  • the acidity of the sulphate titanate, the nanofiltration membrane water and the reverse osmosis membrane water supply are maintained in an appropriate range, neither because the reverse osmosis membrane is completely used, the water is lower, nor because the nanofiltration membrane is completely used.
  • the concentration of ferrous ions in the supernatant of the nanofiltration membrane and the reverse osmosis membrane is lower than the design value, which fully meets the requirements of the washing water.
  • the second filtration system transports the supernatant to the washing tank and continues to use.
  • the filtered concentrate is sent to a waste acid recovery unit for recovery.
  • the dosage of the bleaching agent is 0-50% of the original process dosage.
  • the invention eliminates the operation steps of the bleaching kettle in the existing water washing system, and does not distinguish between one washing and two washing in the conventional water washing system, and is more concise than the conventional water washing system.
  • the invention according to the requirement of the content of ferrous iron in the water-washed qualified slurry, with little or no bleaching agent, without adding sulfuric acid, reduces the production cost and reduces the discharge amount of the three wastes; can realize the recycling of the washing water, so the demand for soft water is greatly increased Reduced, the amount of wastewater treatment is also greatly reduced; the loss of metatitanic acid particles can be reduced, thereby improving the recovery rate of titanium dioxide.
  • Figure 1 is a schematic view of the structure of the present invention
  • FIG. 2 is a process flow diagram of the present invention
  • FIG 3 is a schematic view of the cooperation between the first filter system and the second filter system.
  • the present invention provides a highly efficient sulfuric acid process titanium dioxide water wash system comprising a filter 100, a spent acid recovery unit 200, a beater 300, a water wash cycle tank 400, a first filtration system 500, and a second filtration system 600.
  • the filter 100 is used for filtering a hydrolyzate, and a filter cake having a solid content of 40-85% containing concentrated acid and metal ions in metatitanic acid is sufficiently extruded in the hydrolyzate.
  • the beater 300 is connected to the filter 100 for beating the filter cake filtered by the filter 100 and delivering the beaten slurry to the water washing circulation tank 400.
  • Both the soft water and the water-washing water used in the beater 300 are anaerobic water.
  • the water washing circulation tank 400 is connected to the beater 300, which is a closed container, specifically sealed by a non-oxidizing gas, and maintains the pressure inside the tank to 1-10 KPa, which can wash the slurry conveyed by the beater 300.
  • the washed slurry and water wash water are sent to the first filtration system 500 for filtration.
  • the first filtration system 500 is connected to the water washing circulation tank 400, which is specifically a cross-flow microfiltration membrane with an accuracy of 50-1000 nm and a transmembrane pressure difference of 0.05-0.8 MPa, which is used for intercepting slurry and water washing water.
  • the metatitanic acid particles are re-delivered into the water washing circulation tank 400 and the filtered supernatant is sent to the second filtration system 600.
  • the second filter system 600 is respectively coupled with the first filter system 500 and the water washing circulation tank 400, and is used for filtering the filtered supernatant conveyed by the first filter system 500 and filtering into a water-washing circulation tank. 400 washed water wash water, so that the water wash cycle tank 400 does not need to add water wash water.
  • the second filtration system 600 is specifically composed of a nanofiltration membrane and a reverse osmosis membrane.
  • the nanofiltration membrane has a rejection rate of ferrous ions of 85-99.8%, a rejection rate of titanium oxysulfate of 80-99.8%, a sulfuric acid resistant concentration of 0-30%, and an operating pressure of 1.5-6.5 MPa, which is resistant.
  • Sulfuric acid with a mass concentration of 30%, and allows sulfuric acid to permeate, but can retain ferrous ions and titanium oxysulfate;
  • the reverse osmosis membrane has a rejection rate of ferrous ions of 85-99.8%, a rejection rate of titanium oxysulfate of 80-99.8%, a rejection of sulfuric acid of 85-99.8%, and a sulfuric acid resistant concentration of 0-15%.
  • the operating pressure is 1.5-6.5 MPa, which is resistant to sulfuric acid having a mass concentration of 15%, and can retain sulfuric acid, ferrous ions and titanyl sulfate.
  • the concentration of sulfuric acid in the purified water produced by the second filtration system 600 is 0.05-10%, the ferrous ion concentration is 0-10ppm, the overall recovery rate is 75-95%, and the acidity of the clear solution after the nanofiltration membrane water production and the reverse osmosis membrane water production are maintained in an appropriate range, neither will be completely used.
  • the reverse osmosis membrane is lower than the influent water, and is not higher than the influent water due to the complete use of the nanofiltration membrane, and the ferrous ferrous ion concentration of the supernatant after the combined production of the nanofiltration membrane and the reverse osmosis membrane is lower than the design value, thereby Can fully meet the requirements of washing water.
  • the amount of soft water supplied to the water washing circulation tank 400 is equal to the amount of water discharged from the second filtration system 600 to the waste acid recovery unit 200.
  • a spent acid recovery unit 200 which is coupled to the filter 100 and the second filtration system 600, respectively, is used to recover the filtered wastewater from the filter 100 and the second filtration system 600.
  • the filter 100 will sufficiently extrude a filter cake containing concentrated acid and metal ions in metatitanic acid in the hydrolyzate, and the filter will transport the filter cake to the beater 300, and the filter 100 will squeeze the hydrolyzed material. Pressing the remaining waste acid to the waste acid recovery device 200;
  • the slurry enters the water washing circulation tank 400, and the soft water used for the first water washing also enters the water washing circulation tank 400, the impurity ions in the slurry and the slurry are diluted, and then the water is filtered out through the first filtration system 500. In this way, the impurity ions in the slurry are reduced. If the soft water continues to enter, the supernatant of the first filtration system 500 is continuously discharged, and the impurity ions in the slurry are continuously reduced until the standard is lowered;
  • the water-washed qualified water-washing material is sent to the first filtration system 500, and after the delivery is completed, the next batch of the slurry is sent to the water-washing circulation tank 400 to continue the water washing;
  • the first filtration system 500 intercepts the slurry conveyed from the water washing circulation tank 400 and the metatitanic acid particles in the water washing water, and re-delivers the retained concentrated liquid containing metatitanic acid particles to the water washing circulation tank 400, and washes the circulating tank 400 re-washing the trapped di-titanate-containing particle dope, and the first filtration system 500 delivers the filtered supernatant to the second filtration system 600 for re-filtration;
  • a part of the supernatant of the first filtration system 500 is pumped by high pressure to a reverse osmosis membrane for filtration, and a part of it is filtered by a nanofiltration membrane.
  • the reverse osmosis can retain sulfuric acid, ferrous iron, titanium oxysulfate, and the nanofiltration only retains ferrous iron.
  • the acidity of the supernatant after the combination of the titanyl sulfate and the nanofiltration membrane water and the reverse osmosis membrane water is maintained.
  • the second filtering system 600 transports the clear liquid to the water washing circulating tank 400 for further use, and transports the filtered concentrated liquid to the waste acid recovery device 200 for recovery.
  • a small amount or no bleaching agent is added to the water washing circulation tank 400 within 10 to 60 minutes before the end of the washing, and the dosage of the bleaching agent is 0-50% of the original process dosage.
  • the second filtration system 600 When the first batch of slurry enters the water washing circulation tank 400, the second filtration system 600 does not produce water, so the first water washing must use soft water, and when the second filtration system 600 has water production, the soft water consumption can be reduced.
  • the second filtration system 600 is to produce a concentrated liquid, and the second filtration system 600 produces a clear liquid that is insufficient to wash the slurry to a pass, so the slurry should be replenished with a portion of the soft water when it is washed.
  • the acid concentration in the qualified material will be lower than the acid concentration in the slurry; if the supernatant of the second filtration system 600 is used for water washing, the acid concentration in the qualified material will be higher than that in the soft water alone.
  • the acid concentration in the qualified material is high. Therefore, a reverse osmosis membrane is introduced to remove a portion of the sulfuric acid to maintain the acid concentration in the acceptable water wash.
  • the hydrolyzed material is filtered by the filter 100 to produce a filter cake having a solid content of 65%, and the filter cake is then sent to beating.
  • the machine 300 and the anaerobic water are formulated into a slurry having a solid content of 18%; the slurry is introduced into the water washing circulation tank 400, and the precision of the first filtration system 500 is 500 nm tubular microfiltration membrane, and the transmembrane pressure difference is 0.2 MPa.
  • the concentrated solution containing metatitanic acid is returned to the water washing circulation tank 400, and the supernatant is sent to the second filtration system 600.
  • zinc powder was added to the water washing circulation tank 400 25 minutes before the end of washing, and the dosage was 1.5 ⁇ (for the material titanium).
  • the nanofiltration membrane operating pressure of the second filtration system 600 is 2 MPa
  • the reverse osmosis operating pressure is 3.5 MPa
  • the ferrous ion concentration in the supernatant after the two-stage nanofiltration membrane and the two-stage reverse osmosis membrane treatment is 1.2 mg/L, sulfuric acid.
  • the content is 0.5%.
  • This supernatant is sent to the water washing circulation tank 400 as a washing water.
  • the amount of concentrated liquid produced by the second filtration system 600 is 8.5% of the amount of water entering the first filtration system 500.

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Abstract

提供一种高效的硫酸法钛白粉水洗系统及水洗工艺。水洗系统包括滤机（100）、废酸回收装置（200）、打浆机（300）、水洗循环罐（400）、第一过滤系统（500）和第二过滤系统（600）。水洗工艺包括：（1）将水解料放入滤机中进行过滤；（2）滤机将从水解料中挤压出的滤饼输送到打浆机中；（3）打浆机对滤饼进行打浆，并将打浆后的浆料输送至水洗循环罐；（4）水洗循环罐将洗涤后的浆料和水洗水送至第一过滤系统；（5）第一过滤系统将截留的含偏钛酸颗粒浓液重新输送至水洗循环罐中，并将过滤后的清液输送至第二过滤系统；（6）第二过滤系统将清液输送至水洗循环罐继续使用，将过滤后的浓液输送至废酸回收装置进行回收。该方法取消了现有水洗系统中的的漂白釜操作步骤，不区分传统水洗系统中的一洗和二洗，比传统水洗系统流程更简洁。

Description

一种高效的硫酸法钛白粉水洗系统及其水洗工艺 技术领域
本发明涉及一种硫酸法钛白粉的水洗系统，具体涉及一种高效的硫酸法钛白粉水洗系统及其水洗工艺。
背景技术
传统的硫酸法钛白粉水洗过程中，随着水洗的进行，滤机滤饼中的酸度、金属离子及还原性物质均逐步降低，由于水洗水中含有溶解氧，所以偏钛酸中的Fe2+有被氧化成Fe3+的机会存在，而且在水洗末期更有这种倾向。同时由于酸度的降低，Fe3+就会生成Fe(OH)3沉淀，其它金属离子在酸度降低到一定程度时也会生成沉淀。这些沉淀夹杂在偏钛酸中，对最终产品的质量会产生很大的影响。为了消除上述影响，目前的生产线都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沉淀或者高价氧化物溶解为离子状态后，再进行第二次水洗将其去除。整个工艺流程长，操作繁琐。
目前的水洗工艺对水的需求相当大，常用的是二洗水直接套用至一洗，一洗水(即白水)经过滤或沉淀后排放至水处理车间，白水水量为20-30吨/吨钛白粉，而且白水中还含有不少穿滤的偏钛酸颗粒，造成了钛白粉的流失。
发明内容
本发明为了解决上述问题，从而提供一种高效的硫酸法钛白粉水洗系统及其水洗工艺。
为达到上述目的，本发明的技术方案如下：
一种高效的硫酸法钛白粉水洗系统,所述硫酸法钛白粉水洗系统包括:
滤机；
废酸回收装置，所述废酸回收装置与滤机的废酸出料口连接；
打浆机，所述打浆机与滤机的滤饼出料口连接；
水洗循环罐，所述水洗循环罐与打浆机连通；
第一过滤系统，所述第一过滤系统与水洗循环罐连通；
第二过滤系统，所述第二过滤系统分别与水洗循环罐、第一过滤系统和废酸回收装置连通；
在本发明的一个优选实施例中，所述第一过滤系统为错流式微滤膜，所述错流式微滤膜的精度为50-1000纳米，跨膜压差为0.05-0.8MPa。
在本发明的一个优选实施例中，所述第二过滤系统由纳滤膜和反渗透膜组成，所述纳滤膜对亚铁离子的截留率为85-99.8％，对硫酸氧钛的截留率为80-99.8％，耐硫酸浓度为0-30％，操作压力为1.0-6.5MPa，所述反渗透膜对亚铁离子的截留率为85-99.8％，对硫酸氧钛的截留率为80-99.8％，对硫酸的截留率为85-99.8％，耐硫酸浓度为0-15％，操作压力为1.5-6.5MPa。
在本发明的一个优选实施例中，所述水洗循环罐为密闭容器，所述水洗循环罐采用无氧化性气体密封，并维持罐体内压力为1-10KPa。
在本发明的一个优选实施例中，所述打浆机中采用的软水和水洗补给水都为无氧水。
一种高效的硫酸法钛白粉水洗工艺，该水洗工艺包括如下步骤：
(1)将水解料放入滤机中进行过滤；
(2)滤机将在水解料中充分挤压出含偏钛酸中的浓酸和金属离子的滤饼，滤机将滤饼输送到打浆机中，滤机将水解料中挤压剩余的废酸输送至废酸回收装置中；
(3)在打浆机中添加软水与滤机输送来的滤饼一起打浆，并将打浆后的浆料输送至水洗循环罐；
(4)打浆料进入水洗循环罐，首次水洗时使用的软水也进入水洗循环罐，打浆料和打浆料中的杂质离子得以稀释，然后通过第一过滤系统把水过滤出去，这样打浆料中的杂质离子就降低了，如果软水持续进入，第一过滤系统清液不断排出，打浆料中的杂质离子就会不断降低，直至降低到合格的标准；
(5)水洗合格的水洗料输送到第一过滤系统，输送完毕后，下一批打浆料进入水洗循环罐继续水洗；
(6)第一过滤系统将水洗循环罐输送来的浆料和水洗水中的偏钛酸颗粒截留，将截留的含偏钛酸颗粒浓液重新输送至水洗循环罐中，水洗循环罐对截留的含偏钛酸颗粒浓液重新水洗，第一过滤系统将过滤后的清液输送至第二过 滤系统中进行再次过滤；
(7)第一过滤系统的清液一部分经高压泵送至反渗透膜进行过滤，一部分进入纳滤膜行过滤，反渗透能截留硫酸、亚铁、硫酸氧钛，纳滤只截留亚铁和硫酸氧钛，纳滤膜产水和反渗透膜产水合并后的清液酸度维持适当范围，既不会因为完全使用反渗透膜而较进水低，也不会因为完全使用纳滤膜而较进水高，纳滤膜产水和反渗透膜产水合并后的清液亚铁离子浓度低于设计值，完全满足水洗水要求，第二过滤系统将清液输送至水洗循环罐继续使用，将过滤后的浓液输送至废酸回收装置进行回收。
(8)在洗涤结束前的10-60分钟内往水洗循环罐内加入少量或不加漂白剂，漂白剂的投加量为原工艺投加量的0-50％。
通过上述技术方案，本发明的有益效果是：
本发明取消了现有水洗系统中的的漂白釜操作步骤，不区分传统水洗系统中的一洗和二洗，比传统水洗系统流程更简洁。
本发明根据水洗合格浆料中亚铁的含量要求，少量或不添加漂白剂，同时不添加硫酸，减少了生产成本，降低了三废排放量；能够实现水洗水的循环利用，因此软水需求量大大降低，废水处理量也大幅降低；能减少偏钛酸颗粒的流失，从而提高了钛白粉的回收率。
附图说明
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，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，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。
图1为本发明的结构示意图；
图2为本发明的工艺流程图；
图3为第一过滤系统与第二过滤系统配合示意图。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解， 下面结合具体图示，进一步阐述本发明。
参见图1，本发明提供的高效的硫酸法钛白粉水洗系统，其包括滤机100、废酸回收装置200、打浆机300、水洗循环罐400、第一过滤系统500、第二过滤系统600。
滤机100，其是用于对水解料进行过滤，在水解料中充分挤压出含偏钛酸中的浓酸和金属离子的含固量为40-85％的滤饼。
打浆机300，其与滤机100连接，其是用于对滤机100过滤后的滤饼进行打浆，并将打浆后的浆料输送至水洗循环罐400。
打浆机300中采用的软水和水洗补给水都为无氧水。
水洗循环罐400，其与打浆机300连接，其为密闭容器，具体采用无氧化性气体密封，并维持罐体内压力为1-10KPa，其可对打浆机300输送来的浆料进行洗料，并将洗涤后的浆料和水洗水送至第一过滤系统500进行过滤。
第一过滤系统500，其与水洗循环罐400连接，其具体为错流式微滤膜，精度为50-1000纳米，跨膜压差为0.05-0.8MPa，其是用于截留浆料和水洗水中的偏钛酸颗粒，并将截留的含偏钛酸颗粒浓液重新输送至水洗循环罐400中，并将过滤后的清液输送至第二过滤系统600。
第二过滤系统600，其分别与第一过滤系统500和水洗循环罐400配合连接，其是用于对第一过滤系统500输送来的过滤后的清液进行再次过滤，过滤成符合水洗循环罐400水洗的水洗水，这样水洗循环罐400就不需要添加水洗水。
第二过滤系统600具体纳滤膜和反渗透膜组成。
纳滤膜，其对亚铁离子的截留率为85-99.8％，对硫酸氧钛的截留率为80-99.8％，耐硫酸浓度为0-30％，操作压力为1.5-6.5MPa，其能耐质量浓度为30％的硫酸，并允许硫酸透过，但能截留亚铁离子和硫酸氧钛；
反渗透膜，其对亚铁离子的截留率为85-99.8％，对硫酸氧钛的截留率为80-99.8％，对硫酸的截留率为85-99.8％，耐硫酸浓度为0-15％，操作压力为1.5-6.5MPa，其能耐质量浓度为15％的硫酸，能截留硫酸、亚铁离子和硫酸氧钛。
这样，通过上述方式，第二过滤系统600产生的净水中硫酸浓度为 0.05-10％，亚铁离子浓度为0-10ppm，总体回收率为75-95％，纳滤膜产水和反渗透膜产水合并后的清液酸度维持适当范围，既不会因为完全使用反渗透膜而较进水低，也不会因为完全使用纳滤膜而较进水高，纳滤膜产水和反渗透膜产水合并后的清液亚铁离子浓度低于设计值，从而能完全满足水洗水要求。
另外，为了节约资源，补充至水洗循环罐400的软水水量与第二过滤系统600排放至废酸回收装置200的水量相等。
废酸回收装置200，其分别与滤机100和第二过滤系统600连接，其是用于回收滤机100和第二过滤系统600过滤后的废水。
参见图2和图3，下面是对于上述水洗系统的水洗工艺，该水洗工艺包括如下步骤：
(1)将水解料放入滤机100中进行过滤；
(2)滤机100将在水解料中充分挤压出含偏钛酸中的浓酸和金属离子的滤饼，滤机将滤饼输送到打浆机300中，滤机100将水解料中挤压剩余的废酸输送至废酸回收装置200中；
(3)在打浆机300中添加软水与滤机100输送来的滤饼一起打浆，并将打浆后的浆料输送至水洗循环罐400；
(4)打浆料进入水洗循环罐400，首次水洗时使用的软水也进入水洗循环罐400，打浆料和打浆料中的杂质离子得以稀释，然后通过第一过滤系统500把水过滤出去，这样打浆料中的杂质离子就降低了，如果软水持续进入，第一过滤系统500清液不断排出，打浆料中的杂质离子就会不断降低，直至降低到合格的标准；
(5)水洗合格的水洗料输送到第一过滤系统500，输送完毕后，下一批打浆料进入水洗循环罐400继续水洗；
(6)第一过滤系统500将水洗循环罐400输送来的浆料和水洗水中的偏钛酸颗粒截留，将截留的含偏钛酸颗粒浓液重新输送至水洗循环罐400中，水洗循环罐400对截留的含偏钛酸颗粒浓液重新水洗，第一过滤系统500将过滤后的清液输送至第二过滤系统600中进行再次过滤；
(7)第一过滤系统500的清液一部分经高压泵送至反渗透膜进行过滤，一部分进入纳滤膜行过滤，反渗透能截留硫酸、亚铁、硫酸氧钛，纳滤只截留亚铁和硫酸氧钛，纳滤膜产水和反渗透膜产水合并后的清液酸度维持适当范 围，既不会因为完全使用反渗透膜而较进水低，也不会因为完全使用纳滤膜而较进水高，纳滤膜产水和反渗透膜产水合并后的清液亚铁离子浓度低于设计值，完全满足水洗水要求，第二过滤系统600将清液输送至水洗循环罐400继续使用，将过滤后的浓液输送至废酸回收装置200进行回收。
(8)在洗涤结束前的10-60分钟内往水洗循环罐400内加入少量或不加漂白剂，漂白剂的投加量为原工艺投加量的0-50％。
在第一批打浆料进入水洗循环罐400时，第二过滤系统600并没有产水，所以首次水洗必须用软水，等到第二过滤系统600有产水时，可减少软水用量。
从水量平衡来看，第二过滤系统600要产生浓液，第二过滤系统600产生的清液不足以将打浆料洗至合格，所以打浆料在水洗时应补充一部分软水。
如果始终用软水进行水洗，合格料中的酸浓度会比打浆料中的酸浓度低；如果用第二过滤系统600的清液进行水洗，合格料中的酸浓度会比只用软水洗涤的合格料中的酸浓度高。所以引入了反渗透膜去掉一部分硫酸，以维持合格水洗料中的酸浓度。
下面是针对上述工艺的一个具体实施例：
水解料经过滤机100过滤后产生含固量为65％的滤饼，滤饼随即送至打浆
机300和无氧水配制成固含量18％的打浆料；打浆料进入水洗循环罐400，第一过滤系统500采用的精度为500纳米管式微滤膜，跨膜压差为0.2MPa。第一过滤系统500处理后含偏钛酸的浓液返回水洗循环罐400，清液送至第二过滤系统600。为了达到水洗后合格料中亚铁含量低于10ppm，在一洗结束前25分钟往水洗循环罐400内投加锌粉，投加量为1.5‰(对物料钛)。第二过滤系统600的纳滤膜操作压力为2MPa，反渗透操作压力为3.5MPa，两级纳滤膜和两级反渗透膜处理后的清液中亚铁离子浓度为1.2mg/L，硫酸含量为0.5％。该清液送往水洗循环罐400作为水洗水使用。第二过滤系统600产生的浓液量为第一过滤系统500进水量的8.5％。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (6)

  1. 一种高效的硫酸法钛白粉水洗系统,其特征在于，所述硫酸法钛白粉水洗系统包括:
    滤机；
    废酸回收装置，所述废酸回收装置与滤机的废酸出料口连接；
    打浆机，所述打浆机与滤机的滤饼出料口连接；
    水洗循环罐，所述水洗循环罐与打浆机连通；
    第一过滤系统，所述第一过滤系统与水洗循环罐连通；
    第二过滤系统，所述第二过滤系统分别与水洗循环罐、第一过滤系统和废酸回收装置连通；
  2. 根据权利要求1所述的一种高效的硫酸法钛白粉水洗系统，其特征在于，所述第一过滤系统为错流式微滤膜，所述错流式微滤膜的精度为50-1000纳米，跨膜压差为0.05-0.8MPa。
  3. 根据权利要求1所述的一种高效的硫酸法钛白粉水洗系统，其特征在于，所述第二过滤系统由纳滤膜和反渗透膜组成，所述纳滤膜对亚铁离子的截留率为85-99.8％，对硫酸氧钛的截留率为80-99.8％，耐硫酸浓度为0-30％，操作压力为1.0-6.5MPa，所述反渗透膜对亚铁离子的截留率为85-99.8％，对硫酸氧钛的截留率为80-99.8％，对硫酸的截留率为85-99.8％，耐硫酸浓度为0-15％，操作压力为1.5-6.5MPa。
  4. 根据权利要求1所述的一种高效的硫酸法钛白粉水洗系统，其特征在于，所述水洗循环罐为密闭容器，所述水洗循环罐采用无氧化性气体密封，并维持罐体内压力为1-10KPa。
  5. 根据权利要求1所述的一种高效的硫酸法钛白粉水洗系统，其特征在于，所述打浆机中采用的软水和水洗补给水都为无氧水。
  6. 一种高效的硫酸法钛白粉水洗工艺，特征在于，该水洗工艺包括如下步骤：
    (1)将水解料放入滤机中进行过滤；
    (2)滤机将在水解料中充分挤压出含偏钛酸中的浓酸和金属离子的滤饼，滤机将滤饼输送到打浆机中，滤机将水解料中挤压剩余的废酸输送至废酸回收 装置中；
    (3)在打浆机中添加软水与滤机输送来的滤饼一起打浆，并将打浆后的浆料输送至水洗循环罐；
    (4)打浆料进入水洗循环罐，首次水洗时使用的软水也进入水洗循环罐，打浆料和打浆料中的杂质离子得以稀释，然后通过第一过滤系统把水过滤出去，这样打浆料中的杂质离子就降低了，如果软水持续进入，第一过滤系统清液不断排出，打浆料中的杂质离子就会不断降低，直至降低到合格的标准；
    (5)水洗合格的水洗料输送到第一过滤系统，输送完毕后，下一批打浆料进入水洗循环罐继续水洗；
    (6)第一过滤系统将水洗循环罐输送来的浆料和水洗水中的偏钛酸颗粒截留，将截留的含偏钛酸颗粒浓液重新输送至水洗循环罐中，水洗循环罐对截留的含偏钛酸颗粒浓液重新水洗，第一过滤系统将过滤后的清液输送至第二过滤系统中进行再次过滤；
    (7)第一过滤系统的清液一部分经高压泵送至反渗透膜进行过滤，一部分进入纳滤膜行过滤，反渗透能截留硫酸、亚铁、硫酸氧钛，纳滤只截留亚铁和硫酸氧钛，纳滤膜产水和反渗透膜产水合并后的清液酸度维持适当范围，既不会因为完全使用反渗透膜而较进水低，也不会因为完全使用纳滤膜而较进水高，纳滤膜产水和反渗透膜产水合并后的清液亚铁离子浓度低于设计值，完全满足水洗水要求，第二过滤系统将清液输送至水洗循环罐继续使用，将过滤后的浓液输送至废酸回收装置进行回收。
    (8)在洗涤结束前的10-60分钟内往水洗循环罐内加入少量或不加漂白剂，漂白剂的投加量为原工艺投加量的0-50％。
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