CN112777616A - Impurity removal process for lithium hydroxide heavy solution - Google Patents

Impurity removal process for lithium hydroxide heavy solution Download PDF

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CN112777616A
CN112777616A CN202110131231.6A CN202110131231A CN112777616A CN 112777616 A CN112777616 A CN 112777616A CN 202110131231 A CN202110131231 A CN 202110131231A CN 112777616 A CN112777616 A CN 112777616A
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nanofiltration
water
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lithium hydroxide
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何志
许锦鹏
肖松林
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Sichuan Scsdn Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00Lithium compounds
    • C01D15/02Oxides; Hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025Reverse osmosis; Hyperfiltration
    • B01D61/026Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2319/00Membrane assemblies within one housing
    • B01D2319/02Elements in series
    • B01D2319/025Permeate series
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2319/00Membrane assemblies within one housing
    • B01D2319/04Elements in parallel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

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  • Inorganic Chemistry (AREA)
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Abstract

The invention provides a lithium hydroxide heavy solution impurity removal process, which comprises the following steps: pumping the lithium hydroxide heavy solution into a precise filtering system, wherein the obtained precise filtering water ss is less than 1 mg/L; then, storing the precision filtration water production into a nanofiltration raw water tank, pumping the precision filtration water production in the nanofiltration raw water tank into a primary nanofiltration system to obtain primary nanofiltration water production, storing the obtained primary nanofiltration water production into a nanofiltration water production tank, and storing the obtained primary nanofiltration concentrated water into the primary nanofiltration concentrated water tank; and then pumping the primary nanofiltration concentrated water in the primary nanofiltration concentrated water tank into a secondary nanofiltration system to obtain secondary nanofiltration water product, pumping the secondary nanofiltration water product into the nanofiltration water product tank to form nanofiltration water product together with the primary nanofiltration water product, and then conveying the nanofiltration water product and the primary nanofiltration water product to an evaporation crystallization device together, and storing the secondary nanofiltration concentrated water obtained by the secondary nanofiltration system into the secondary nanofiltration concentrated water tank. The invention has the advantages of high-power concentration of the whole body, low power consumption, stable and reliable operation and low later maintenance cost, and finally ensures the quality of produced water.

Description

Impurity removal process for lithium hydroxide heavy solution
Technical Field
The invention relates to the technical field of lithium industry, in particular to a lithium hydroxide heavy solution impurity removal process.
Background
The lithium hydroxide heavy solution refers to that LiOH in raw water is about 118.4g/L, wherein calcium is 45mg/L, silicon is 17mg/L, and sulfate is 330 mg/L. In the prior art, when the impurity removal is carried out on the lithium hydroxide heavy solution, the sulfate radical in the lithium hydroxide heavy solution is not removed to the content of less than 50mg/L in a better way.
Disclosure of Invention
The invention mainly aims to provide a lithium hydroxide solution impurity removal process to solve the problem of poor sulfate radical removal effect in the prior art.
In order to achieve the purpose, the invention provides a lithium hydroxide heavy solution impurity removal process, which comprises the following steps:
firstly, the lithium hydroxide heavy solution enters a raw water tank for storage, then the lithium hydroxide heavy solution is pumped into a precision filtration system for enriching and removing ss of raw water, and the obtained precision filtration produced water ss is less than 1 mg/L;
then, storing the precision filtration water produced by the precision filtration system into a nanofiltration raw water tank, pumping the precision filtration water produced by the nanofiltration raw water tank into a primary nanofiltration system, enriching and removing calcium ions, silicon ions, sulfate radicals and other ions of raw water to obtain primary nanofiltration water produced, storing the obtained primary nanofiltration water produced into a nanofiltration water produced tank, and storing the obtained primary nanofiltration water produced into a primary nanofiltration water concentrated tank;
and then pumping the primary nanofiltration concentrated water in the primary nanofiltration concentrated water tank into a secondary nanofiltration system, enriching and removing calcium, silicon, sulfate radical and other ions in the concentrated water to obtain secondary nanofiltration water, pumping the secondary nanofiltration water into the nanofiltration water tank to form nanofiltration water together with the primary nanofiltration water, conveying the nanofiltration water and the primary nanofiltration water to an evaporation crystallization device, and storing the secondary nanofiltration water obtained by the secondary nanofiltration system into the secondary nanofiltration concentrated water tank.
Further, the LiOH content of the lithium hydroxide heavy solution in the raw water tank was 118.4g/L, SO42-The content is 330.0mg/L, Si content < 17.0mg/L, Ca content is 45.0mg/L, SS content < 10.0 mg/L.
Further, the LiOH content of the precision filtration produced water in the nanofiltration raw water tank is 118.4g/L, SO 42-the content is 330.0mg/L, Si-the content is 17.0mg/L, Ca-the content is 45.0mg/L, SS-1.0 mg/L.
Further, the nanofiltration product in the nanofiltration water production tankThe LiOH content of the water is 118.39g/L, SO42-The content is less than 50mg/L, Si, the content is less than 9.0mg/L, Ca, the content is less than 16.0mg/L, SS, and the content is less than 1.0 mg/L.
Furthermore, the precise filtration system adopts a titanium-based membrane filtration element, the primary nanofiltration system and the secondary nanofiltration system both adopt alkali-resistant nanofiltration membrane elements, and the alkali-resistant nanofiltration membrane elements are resistant to alkali of 20% sodium hydroxide, resistant to pressure of 600psi and resistant to temperature of 70 ℃.
Further, the water flux produced by the precise filtering system is 500L/m2H, the precise filtering system comprises a plurality of precise filters connected in parallel, and the water yield of a single precise filter is 31.58m3The filtration precision is 0.1-0.2 μm.
Further, the water flux produced by the primary nanofiltration system is 15L/m2H, the primary nanofiltration system comprises a plurality of primary nanofiltration devices connected in parallel, and the water yield of a single primary nanofiltration device is 20.99m3/h。
Further, the water flux produced by the secondary nanofiltration system is 10L/m2H, the secondary nanofiltration system comprises a plurality of secondary nanofiltration devices connected in parallel, and the water yield of a single secondary nanofiltration device is 9.41m3/h。
Furthermore, the precise filtering system is connected with a backwashing system, the backwashing system comprises a backwashing pump and a backwashing water tank, concentrated water obtained by precise filtering backwashing is stored in the slag liquid tank, and the concentrated water obtained by precise filtering backwashing is conveyed back to the front end plate frame through the pump for filtering or the wastewater treatment system.
Further, the microfiltration system is connected with a microfiltration chemical cleaning system, and the microfiltration chemical cleaning system comprises a cleaning water pump and an acid/alkali dosing pump.
Therefore, the invention realizes the effective removal of sulfate ions in the lithium hydroxide heavy solution, ensures the integral high-power concentration, low power consumption, stable and reliable operation and low later maintenance cost, and finally ensures the quality of the produced water.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
FIG. 1 is a schematic view of the equipment flow of the lithium hydroxide heavy solution impurity removal process of the present invention.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions.
The invention relates to a lithium hydroxide heavy solution impurity removal process, which comprises the following steps:
firstly, the lithium hydroxide heavy solution enters a raw water tank for storage, then the lithium hydroxide heavy solution is pumped into a precision filtration system for enriching and removing ss of raw water, and the obtained precision filtration produced water ss is less than 1 mg/L;
then, storing the precision filtration water produced by the precision filtration system into a nanofiltration raw water tank, pumping the precision filtration water produced by the nanofiltration raw water tank into a primary nanofiltration system, enriching and removing calcium ions, silicon ions, sulfate radicals and other ions of raw water to obtain primary nanofiltration water produced, storing the obtained primary nanofiltration water produced into a nanofiltration water produced tank, and storing the obtained primary nanofiltration water produced into a primary nanofiltration water concentrated tank;
and then pumping the primary nanofiltration concentrated water in the primary nanofiltration concentrated water tank into a secondary nanofiltration system, enriching and removing calcium, silicon, sulfate radical and other ions in the concentrated water to obtain secondary nanofiltration water, pumping the secondary nanofiltration water into the nanofiltration water tank to form nanofiltration water together with the primary nanofiltration water, conveying the nanofiltration water and the primary nanofiltration water to an evaporation crystallization device, and storing the secondary nanofiltration water obtained by the secondary nanofiltration system into the secondary nanofiltration concentrated water tank.
The LiOH content of the lithium hydroxide heavy solution in the raw water tank is 118.4g/L, SO42-The content is 330.0mg/L, Si content < 17.0mg/L, Ca content is 45.0mg/L, SS content < 10.0 mg/L.
The LiOH content of the precision filtration produced water in the nanofiltration raw water tank is 118.4g/L, SO 42-330.0 mg/L, Si content is 17.0mg/L, Ca content is 45.0mg/L, SS content is less than 1.0 mg/L.
The LiOH content of nanofiltration water produced in the nanofiltration water production tank is 118.39g/L, SO42-The content is less than 50mg/L, Si, the content is less than 9.0mg/L, Ca, the content is less than 16.0mg/L, SS, and the content is less than 1.0 mg/L.
The precise filtration system adopts a titanium-based membrane filtration element, the primary nanofiltration system and the secondary nanofiltration system both adopt alkali-resistant nanofiltration membrane elements, and the alkali-resistant nanofiltration membrane elements are resistant to alkali of 20% sodium hydroxide, pressure of 600psi and temperature of 70 ℃.
The water production flux of the precise filtering system is 500L/m2H, the precise filtering system comprises a plurality of precise filters connected in parallel, and the water yield of a single precise filter is 31.58m3The filtration precision is 0.1-0.2 μm.
The water production flux of the primary nanofiltration system is 15L/m2H, the primary nanofiltration system comprises a plurality of primary nanofiltration devices connected in parallel, and the water yield of a single primary nanofiltration device is 20.99m3/h。
The water production flux of the secondary nanofiltration system is 10L/m2H, the secondary nanofiltration system comprises a plurality of secondary nanofiltration devices connected in parallel, and the water yield of a single secondary nanofiltration device is 9.41m3/h。
The precise filtering system is connected with a backwashing system, the backwashing system comprises a backwashing pump and a backwashing water tank, and concentrated water obtained by precise filtering backwashing is stored in the slag liquid tank.
The precise filtering system is connected with a precise filtering chemical cleaning system, and the precise filtering chemical cleaning system comprises a cleaning water pump and an acid/alkali dosing pump.
As shown in fig. 1, in the impurity removal process of the lithium hydroxide heavy solution, a filtrate obtained by filtering through a front-end secondary plate-and-frame filter device 1 firstly enters a raw water tank 2 for storage, then the lithium hydroxide heavy solution is pumped into a precise filtering system 3 for enrichment and removal of ss of the raw water, the obtained precision filtering produced water ss is less than 1mg/L, and pure water pumped through a backwashing tank 9 is used for backwashing the precise filtering system 3 to obtain concentrated water which is stored in a slag liquid tank 10;
then, storing the precision filtration water produced by the precision filtration system 3 into a nanofiltration raw water tank 4, pumping the precision filtration water produced by the nanofiltration raw water tank 4 into a primary nanofiltration system 5, enriching and removing calcium, silicon, sulfate radical and other ions of raw water to obtain primary nanofiltration water produced, storing the primary nanofiltration water produced into a nanofiltration water produced tank 11, and storing the primary nanofiltration water produced into a primary nanofiltration water concentrated tank 6;
and then pumping the primary nanofiltration concentrated water in the primary nanofiltration concentrated water tank 6 into a secondary nanofiltration system 7, enriching and removing calcium, silicon, sulfate radical and other ions in the concentrated water to obtain secondary nanofiltration water, pumping the secondary nanofiltration water into a nanofiltration water production tank 11 to form nanofiltration water together with the primary nanofiltration water, then conveying the nanofiltration water and the primary nanofiltration water to an evaporative crystallization device 12, evaporating in the evaporative crystallization device to obtain lithium hydroxide with high purity, storing the secondary nanofiltration concentrated water obtained by the secondary nanofiltration system 7 into a secondary nanofiltration concentrated water tank 8, and returning the concentrated water in the secondary nanofiltration concentrated water tank 8 to the front end for impurity removal.
The LiOH content of the lithium hydroxide heavy solution in the raw water tank is 118.4g/L, SO42-The content is 330.0mg/L, Si content < 17.0mg/L, Ca content is 45.0mg/L, SS content < 10.0 mg/L. The LiOH content of the precision filtration produced water in the nanofiltration raw water tank is 118.4g/L, SO 42-330.0 mg/L, Si content is 17.0mg/L, Ca content is 45.0mg/L, SS content is less than 1.0 mg/L. The LiOH content of nanofiltration water produced in the nanofiltration water production tank is 118.39g/L, SO42-The content is less than 50mg/L, Si, the content is less than 9.0mg/L, Ca, the content is less than 16.0mg/L, SS, and the content is less than 1.0 mg/L. The precise filtration system adopts a titanium-based membrane filtration element, the primary nanofiltration system and the secondary nanofiltration system both adopt alkali-resistant nanofiltration membrane elements, and the alkali-resistant nanofiltration membrane elements are resistant to alkali of 20% sodium hydroxide, pressure of 600psi and temperature of 70 ℃. The water production flux of the precise filtering system is 500L/m2H, the precise filtering system comprises a plurality of precise filters connected in parallel, and the water yield of a single precise filter is 31.58m3The filtration precision is 0.1-0.2 μm. The water production flux of the primary nanofiltration system is 15L/m2H, the primary nanofiltration system comprises a plurality of primary nanofiltration devices connected in parallel, and the water yield of a single primary nanofiltration device is 20.99m3H is used as the reference value. The water production flux of the secondary nanofiltration system is 10L/m2H, the secondary nanofiltration system comprises a plurality of secondary nanofiltration devices connected in parallel, and the water yield of a single secondary nanofiltration device is 9.41m3H is used as the reference value. The precise filtering system is connected with a backwashing system, the backwashing system comprises a backwashing pump and a backwashing water tank, and concentrated water obtained by precise filtering backwashing is stored in the slag liquid tank. The precise filtering system is connected with a precise filtering chemical cleaning system, and the precise filtering chemical cleaning system comprises a cleaning water pump and an acid/alkali dosing pump.
The parameters of the precision filtration, the first-stage nanofiltration filtration and the second-stage nanofiltration filtration during the production process of the invention are shown in the following table 1:
table 1:
Figure BDA0002925387140000051
wherein NF represents nanofiltration, NF-1 represents primary nanofiltration, and NF-2 represents secondary nanofiltration. Finally summarizing the content of sulfate radical S042-in the obtained NF produced water to be 40.09, and realizing that the content of sulfate radical in the lithium hydroxide heavy solution is removed to be below 50 mg/L. The invention adopts a full physical separation method for purification treatment, and no additional substance is introduced, thereby realizing the purification of lithium hydroxide and the concentration of sulfate radicals; the period of calcium sulfate scaling of the evaporation crystallizer in the subsequent process is reduced, the evaporation crystallizer is cleaned once in half a year and is cleaned once in 2 years after the technology is used; the single crystallization yield of the lithium hydroxide is improved by 5-10% when the high-purity lithium hydroxide is produced by the technology; reducing the consumption of the agent for removing sulfate radicals at the front end; the risk that the lithium hydroxide sulfate radical content of the crystallization product of the original evaporator is unqualified is basically avoided.
Therefore, the method realizes effective removal of sulfate ions in the lithium hydroxide heavy solution, ensures integral high-power concentration, low power consumption, stable and reliable operation and low later maintenance cost, and finally ensures the quality of produced water.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.

Claims (10)

1. The impurity removal process of the lithium hydroxide heavy solution is characterized by comprising the following steps:
firstly, the lithium hydroxide heavy solution enters a raw water tank for storage, then the lithium hydroxide heavy solution is pumped into a precision filtration system for enriching and removing ss of raw water, and the obtained precision filtration produced water ss is less than 1 mg/L;
then, storing the precision filtration water produced by the precision filtration system into a nanofiltration raw water tank, pumping the precision filtration water produced by the nanofiltration raw water tank into a primary nanofiltration system, enriching and removing calcium ions, silicon ions, sulfate radicals and other ions of raw water to obtain primary nanofiltration water produced, storing the obtained primary nanofiltration water produced into a nanofiltration water produced tank, and storing the obtained primary nanofiltration water produced into a primary nanofiltration water concentrated tank;
and then pumping the primary nanofiltration concentrated water in the primary nanofiltration concentrated water tank into a secondary nanofiltration system, enriching and removing calcium, silicon, sulfate radical and other ions in the concentrated water to obtain secondary nanofiltration water, pumping the secondary nanofiltration water into the nanofiltration water tank to form nanofiltration water together with the primary nanofiltration water, conveying the nanofiltration water and the primary nanofiltration water to an evaporation crystallization device, and storing the secondary nanofiltration water obtained by the secondary nanofiltration system into the secondary nanofiltration concentrated water tank.
2. The process for removing impurities from lithium hydroxide heavy solution according to claim 1, wherein the LiOH content of the lithium hydroxide heavy solution in the raw water tank is 118.4g/L, SO42-The content is 330.0mg/L, Si content < 17.0mg/L, Ca content is 45.0mg/L, SS content < 10.0 mg/L.
3. The process for removing impurities from lithium hydroxide heavy solution according to claim 1, wherein the LiOH content of the precision filtration produced water in the nanofiltration raw water tank is 118.4g/L, SO 42-the content is 330.0mg/L, Si-the content is 17.0mg/L, Ca-the content is 45.0mg/L, SS-the content is less than 1.0 mg/L.
4. The impurity removal process for lithium hydroxide heavy solution according to claim 1, wherein the LiOH content of nanofiltration product water in the nanofiltration product water tank is 118.39g/L, SO42-The content is less than 50mg/L, Si, the content is less than 9.0mg/L, Ca, the content is less than 16.0mg/L, SS, and the content is less than 1.0 mg/L.
5. The process for removing impurities from lithium hydroxide heavy solution according to claim 1, wherein the precise filtration system adopts a titanium-based membrane filtration element, the primary nanofiltration system and the secondary nanofiltration system both adopt an alkali-resistant nanofiltration membrane element, and the alkali-resistant nanofiltration membrane element is resistant to alkali sodium hydroxide with a concentration of 20%, pressure resistance of 600psi and temperature resistance of 70 ℃.
6. The lithium hydroxide heavy solution impurity removal process according to claim 1, wherein the precise filtration systemThe water production flux is 500L/m2H, the precise filtering system comprises a plurality of precise filters connected in parallel, and the water yield of a single precise filter is 31.58m3The filtration precision is 0.1-0.2 μm.
7. The lithium hydroxide heavy solution impurity removal process according to claim 1, wherein the water yield of the primary nanofiltration system is 15L/m2H, the primary nanofiltration system comprises a plurality of primary nanofiltration devices connected in parallel, and the water yield of a single primary nanofiltration device is 20.99m3/h。
8. The lithium hydroxide heavy solution impurity removal process according to claim 1, wherein the water yield of the secondary nanofiltration system is 10L/m2H, the secondary nanofiltration system comprises a plurality of secondary nanofiltration devices connected in parallel, and the water yield of a single secondary nanofiltration device is 9.41m3/h。
9. The lithium hydroxide heavy solution impurity removal process according to claim 1, wherein a backwashing system is connected to the precise filtration system, the backwashing system comprises a backwashing pump and a backwashing water tank, and concentrated water obtained by precise filtration backwashing is stored in a slag liquid tank.
10. The lithium hydroxide heavy-solution impurity removal process according to claim 1, wherein a precise filtration chemical cleaning system is connected with the precise filtration system, and the precise filtration chemical cleaning system comprises a cleaning water pump and an acid/alkali dosing pump.
CN202110131231.6A 2021-01-30 2021-01-30 Impurity removal process for lithium hydroxide heavy solution Pending CN112777616A (en)

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