CN111689605A - Method for treating wastewater containing tungsten and vanadium in regeneration process of waste SCR catalyst - Google Patents

Method for treating wastewater containing tungsten and vanadium in regeneration process of waste SCR catalyst Download PDF

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Publication number
CN111689605A
CN111689605A CN202010271499.5A CN202010271499A CN111689605A CN 111689605 A CN111689605 A CN 111689605A CN 202010271499 A CN202010271499 A CN 202010271499A CN 111689605 A CN111689605 A CN 111689605A
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wastewater
vanadium
value
stirring
calcium hydroxide
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CN202010271499.5A
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武乐
陈大伟
王梦雪
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Anhui Scr Environmental Technology Co ltd
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Anhui Scr Environmental Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/20Obtaining niobium, tantalum or vanadium
    • C22B34/22Obtaining vanadium
    • C22B34/225Obtaining vanadium from spent catalysts
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/30Obtaining chromium, molybdenum or tungsten
    • C22B34/36Obtaining tungsten
    • C22B34/365Obtaining tungsten from spent catalysts
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a method for treating waste water containing tungsten and vanadium in the regeneration process of a waste SCR catalyst, which comprises the following steps: firstly, standing and precipitating wastewater in a wastewater pool, filtering to obtain clear filtrate after standing and precipitating, then adding lime into the clear filtrate, stirring, adjusting the pH value of the filtrate to 8-9, and then filtering to obtain treated water and tungsten vanadium precipitate; after the waste water containing tungsten and vanadium regenerated by the waste SCR catalyst is kept stand and precipitated, lime is slowly added while stirring, when the pH value is 8-9, the tungsten and vanadium elements are precipitated, and simultaneously, the color of the waste water is changed from light yellow to colorless and transparent.

Description

Method for treating wastewater containing tungsten and vanadium in regeneration process of waste SCR catalyst
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating tungsten-vanadium-containing wastewater in the regeneration process of a waste SCR catalyst.
Background
At present, the regeneration of the waste SCR catalyst is industrialized, and the waste water contains tungsten, vanadium, arsenic and other heavy metals with certain concentration in the regeneration process, and the metals have toxic action on human bodies and harm on the environment. For the wastewater containing heavy metals, a neutralization flocculation precipitation method, a ferrite method, a sodium sulfide method, an ion exchange resin method and the like are generally adopted. These methods have disadvantages in that the removal effect, the process complexity, and the investment and operation costs are comprehensively considered. Therefore, it is important to solve such problems.
Disclosure of Invention
In order to solve the problems, the invention provides a method for treating waste water containing tungsten and vanadium in the regeneration process of a waste SCR catalyst, wherein after the waste water containing tungsten and vanadium in the regeneration process of the waste SCR catalyst is kept stand and precipitated, lime is slowly added while stirring, when the pH value is 8-9, the tungsten and vanadium element are precipitated, and meanwhile, the color of the waste water is changed from light yellow to colorless and transparent.
In order to realize the technical scheme, the invention provides a method for treating waste water containing tungsten and vanadium in the regeneration process of a waste SCR catalyst, which comprises the following steps: firstly, standing and precipitating wastewater in a wastewater pool, filtering to obtain clear filtrate after standing and precipitating, then adding lime into the clear filtrate, stirring, adjusting the pH value of the filtrate to 8-9, and then filtering to obtain treated water and tungsten vanadium precipitate.
The further improvement lies in that: the steps of taking sample wastewater from a wastewater tank for treatment are as follows:
the method comprises the following steps: preparation of wastewater and determination of tungsten and vanadium content in wastewater
Taking 5L of wastewater in production, wherein the wastewater is acidic, and the acidity is 5.3%; standing for precipitation, filtering to obtain clear filtrate, taking 15ml of wastewater from the filtrate, dropwise adding the wastewater into 5g of pure denitration titanium dioxide, and drying to detect the content by XRF; then taking 400g of wastewater from the wastewater tank, pouring the wastewater into a beaker, placing the beaker on a magnetic stirrer, and placing the beaker into a stirring rotor;
step two: adjusting different pH values by adding calcium hydroxide
The method comprises the following steps: firstly adding a small amount of calcium hydroxide, starting a stirrer, then adding the calcium hydroxide while stirring, changing the solution into a milky turbid solution with the increase of the addition amount, wherein the pH value is 2-3, changing the solution color into light yellow instantly when continuously adding and adjusting the pH value to 5-6, wherein the bottom of the solution is white precipitate, the total amount of the calcium hydroxide is 20.10g, the pH value is adjusted, and after stirring for 1h, placing a beaker while standing;
secondly, the step of: after the pH value is adjusted to 5-6 according to the first step, calcium hydroxide is continuously added while stirring, the light yellow of the solution gradually disappears and becomes light along with the increase of the addition amount, the color of the solution becomes colorless and transparent when the pH value is continuously added and adjusted to 8-9, white precipitate is at the bottom, the total dosage of the calcium hydroxide is 22.36g, the pH value is adjusted, and after stirring for 1h, the beaker is placed and kept stand;
step three: carrying out suction filtration on a sample, and carrying out adsorption measurement on supernatant fluid to obtain XRF
After the sample is kept stand for about 1 hour, 15ml of supernate is taken and dripped into 5g of pure denitration titanium dioxide, and the content is detected by XRF after the supernate is dried; after suction filtration, the filter cake was dried and the content was measured by XRF.
The further improvement lies in that: standing for precipitation, and filtering to obtain clear filtrate and filter residue, wherein the filter residue is cleaned and removed by workers.
The invention has the beneficial effects that: after the waste water containing tungsten and vanadium regenerated by the waste SCR catalyst is kept stand and precipitated, lime is slowly added while stirring, when the pH value is 8-9, the tungsten and vanadium elements can be precipitated, and the color of the waste water can be changed from light yellow to colorless and transparent.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
In order to further understand the present invention, the following detailed description will be made with reference to the following examples, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
Example one
Taking 5L of wastewater in production, wherein the wastewater is acidic, and the acidity is 5.3%; standing for precipitation, filtering to obtain clear filtrate, taking 15ml of wastewater from the filtrate, dropwise adding the wastewater into 5g of pure denitration titanium dioxide, and drying to detect the content by XRF; then taking 400g of wastewater from the wastewater tank, pouring the wastewater into a beaker, placing the beaker on a magnetic stirrer, and placing the beaker into a stirring rotor;
firstly adding a small amount of calcium hydroxide, starting a stirrer, then adding the calcium hydroxide while stirring, changing the solution into a milky turbid solution with the increase of the addition amount, wherein the pH value is 2-3, changing the solution color into light yellow instantly when continuously adding and adjusting the pH value to 5-6, wherein the bottom of the solution is white precipitate, the total amount of the calcium hydroxide is 20.10g, the pH value is adjusted, and after stirring for 1h, placing a beaker while standing;
after the sample is kept stand for about 1 hour, 15ml of supernate is taken and dripped into 5g of pure denitration titanium dioxide, and the content is detected by XRF after the supernate is dried; after suction filtration, the filter cake was dried and the content was measured by XRF.
Example two
Taking 5L of wastewater in production, wherein the wastewater is acidic, and the acidity is 5.3%; standing for precipitation, filtering to obtain clear filtrate, taking 15ml of wastewater from the filtrate, dropwise adding the wastewater into 5g of pure denitration titanium dioxide, and drying to detect the content by XRF; then taking 400g of wastewater from the wastewater tank, pouring the wastewater into a beaker, placing the beaker on a magnetic stirrer, and placing the beaker into a stirring rotor;
firstly adding a small amount of calcium hydroxide, starting a stirrer, then adding the calcium hydroxide while stirring, changing the solution into a milky turbid solution with the increase of the addition amount, wherein the pH value is 2-3, and when continuously adding and adjusting the pH value to 5-6, the solution is instantly changed into light yellow, and the bottom of the solution is white precipitate;
after the pH value of the charged solution is 5-6, continuously adding calcium hydroxide, stirring while adding calcium hydroxide, gradually fading and lightening the faint yellow of the solution along with the increase of the added amount, continuously adding and adjusting the pH value to be 8-9, enabling the color of the solution to be colorless and transparent, enabling the bottom to be white precipitate, enabling the total amount of calcium hydroxide to be 22.36g, completing the pH value adjustment, stirring for 1 hour, and then placing a beaker for standing;
after the sample is kept stand for about 1 hour, 15ml of supernate is taken and dripped into 5g of pure denitration titanium dioxide, and the content is detected by XRF after the supernate is dried; after suction filtration, the filter cake was dried and the content was measured by XRF.
EXAMPLE III
Taking 5L of wastewater in production, wherein the wastewater is acidic, and the acidity is 5.3%; standing for precipitation, filtering to obtain clear filtrate, taking 15ml of wastewater from the filtrate, dropwise adding the wastewater into 5g of pure denitration titanium dioxide, and drying to detect the content by XRF; then taking 400g of wastewater from the wastewater tank, pouring the wastewater into a beaker, placing the beaker on a magnetic stirrer, and placing the beaker into a stirring rotor;
firstly adding a small amount of calcium hydroxide, starting a stirrer, then adding the calcium hydroxide while stirring, changing the solution into a milky turbid solution with the increase of the addition amount, wherein the pH value is 2-3, and when continuously adding and adjusting the pH value to 5-6, the solution is instantly changed into light yellow, and the bottom of the solution is white precipitate;
after the pH value of the charged solution is 5-6, continuously adding calcium hydroxide, stirring while adding calcium hydroxide, gradually fading and lightening the faint yellow of the solution along with the increase of the added amount, continuously adding and adjusting the pH value to be 8-9, wherein the color of the solution is colorless and transparent, the bottom of the solution is white precipitate, and the total amount of the calcium hydroxide is 22.36 g;
after the pH value is adjusted to be 8-9, calcium hydroxide is continuously added, the solution is stirred and added, the solution is gradually changed into light yellow from colorless transparency along with the increase of the addition amount, when the pH value is continuously added and adjusted to be 10-11, the solution is light yellow, white precipitate is at the bottom, the total dosage of the calcium hydroxide is 30.08g, the pH value adjustment is finished, and after stirring for 1h, the beaker is placed aside and stands still.
After the sample is kept stand for about 1 hour, 15ml of supernate is taken and dripped into 5g of pure denitration titanium dioxide, and the content is detected by XRF after the supernate is dried; after suction filtration, the filter cake was dried and the content was measured by XRF.
The results of the tests of the above three examples are as follows:
the tungsten content in the raw liquor of the production wastewater is 0.62 percent, and the vanadium content in the raw liquor of the production wastewater is 0.51 percent
When the pH value of the calcium hydroxide is adjusted to 5-6, the tungsten content in the liquid is 0.31 percent, and the vanadium content in the liquid is 0.24 percent;
when the pH value of the calcium hydroxide is adjusted to 8-9, the tungsten content in the liquid is 0.06 percent, and the vanadium content in the liquid is 0.00 percent;
when the pH of the liquid is adjusted to 10-11 by calcium hydroxide, the tungsten content in the liquid is 0.12%, and the vanadium content in the liquid is 0.08%.
The experimental results show that for the waste SCR catalyst regeneration tungsten-vanadium-containing waste water, the pH value is adjusted by using calcium hydroxide, the tungsten-vanadium precipitation efficiency is the best when the pH value is 8-9, and the tungsten-vanadium precipitation rate can reach more than 90%.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (3)

1. A method for treating waste water containing tungsten and vanadium in the regeneration process of a waste SCR catalyst is characterized by comprising the following steps: firstly, standing and precipitating wastewater in a wastewater pool, filtering to obtain clear filtrate after standing and precipitating, then adding lime into the clear filtrate, stirring, adjusting the pH value of the filtrate to 8-9, and then filtering to obtain treated water and tungsten vanadium precipitate.
2. The method for treating the wastewater containing tungsten and vanadium in the regeneration process of the waste SCR catalyst according to claim 1, which is characterized in that: the steps of taking sample wastewater from a wastewater tank for treatment are as follows:
the method comprises the following steps: preparation of wastewater and determination of tungsten and vanadium content in wastewater
Taking 5L of wastewater in production, wherein the wastewater is acidic, and the acidity is 5.3%; standing for precipitation, filtering to obtain clear filtrate, taking 15ml of wastewater from the filtrate, dropwise adding the wastewater into 5g of pure denitration titanium dioxide, and drying to detect the content by XRF; then taking 400g of wastewater from the wastewater tank, pouring the wastewater into a beaker, placing the beaker on a magnetic stirrer, and placing the beaker into a stirring rotor;
step two: adjusting different pH values by adding calcium hydroxide
The method comprises the following steps: firstly adding a small amount of calcium hydroxide, starting a stirrer, then adding the calcium hydroxide while stirring, changing the solution into a milky turbid solution with the increase of the addition amount, wherein the pH value is 2-3, changing the solution color into light yellow instantly when continuously adding and adjusting the pH value to 5-6, wherein the bottom of the solution is white precipitate, the total amount of the calcium hydroxide is 20.10g, the pH value is adjusted, and after stirring for 1h, placing a beaker while standing;
secondly, the step of: after the pH value is adjusted to 5-6 according to the first step, calcium hydroxide is continuously added while stirring, the light yellow of the solution gradually disappears and becomes light along with the increase of the addition amount, the color of the solution becomes colorless and transparent when the pH value is continuously added and adjusted to 8-9, white precipitate is at the bottom, the total dosage of the calcium hydroxide is 22.36g, the pH value is adjusted, and after stirring for 1h, the beaker is placed and kept stand;
step three: carrying out suction filtration on a sample, and carrying out adsorption measurement on supernatant fluid to obtain XRF
After the sample is kept stand for about 1 hour, 15ml of supernate is taken and dripped into 5g of pure denitration titanium dioxide, and the content is detected by XRF after the supernate is dried; after suction filtration, the filter cake was dried and the content was measured by XRF.
3. The method for treating tungsten-containing vanadium in the regeneration process of the waste SCR catalyst according to claim 1, wherein the method comprises the following steps: standing for precipitation, and filtering to obtain clear filtrate and filter residue, wherein the filter residue is cleaned and removed by workers.
CN202010271499.5A 2020-04-09 2020-04-09 Method for treating wastewater containing tungsten and vanadium in regeneration process of waste SCR catalyst Withdrawn CN111689605A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112553469A (en) * 2021-02-26 2021-03-26 中国科学院过程工程研究所 Method for separating vanadium, tungsten and arsenic from sodium hydroxide waste liquid and application
CN113249595A (en) * 2021-06-01 2021-08-13 中国科学院过程工程研究所 Method for recovering tungsten from waste alkali liquor generated by regenerating waste SCR catalyst and application of method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112553469A (en) * 2021-02-26 2021-03-26 中国科学院过程工程研究所 Method for separating vanadium, tungsten and arsenic from sodium hydroxide waste liquid and application
CN112553469B (en) * 2021-02-26 2021-05-11 中国科学院过程工程研究所 Method for separating vanadium, tungsten and arsenic from sodium hydroxide waste liquid and application
CN113249595A (en) * 2021-06-01 2021-08-13 中国科学院过程工程研究所 Method for recovering tungsten from waste alkali liquor generated by regenerating waste SCR catalyst and application of method

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Application publication date: 20200922