CN112510282A - Method for preparing MOF-based nano material based on waste lithium ion battery leachate - Google Patents

Method for preparing MOF-based nano material based on waste lithium ion battery leachate Download PDF

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CN112510282A
CN112510282A CN202011383530.0A CN202011383530A CN112510282A CN 112510282 A CN112510282 A CN 112510282A CN 202011383530 A CN202011383530 A CN 202011383530A CN 112510282 A CN112510282 A CN 112510282A
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mof
lithium ion
ion battery
leachate
nano material
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CN112510282B (en
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范二莎
李丽
陈人杰
林娇
吴锋
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Beijing Institute of Technology BIT
Advanced Technology Research Institute of Beijing Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention provides a method for preparing an MOF-based nano material based on a waste lithium ion battery leachate, which comprises the following steps: (1) dissolving the anode material of the waste lithium ion battery in an acidic reagent to obtain the material containing Co2+、Li+The leachate of (2); (2) dispersing quantitative 2-methylimidazole into the leachate, and centrifuging to obtain an MOF nano material; (3) and roasting the MOF nano material to prepare the MOF-based derivative nano material. The method provided by the invention has the advantages of cheap and easily-obtained raw materials, simple preparation steps, mild and easily-controlled reaction conditions, regular shape and high purity of the prepared product, wide application prospect and important high-valued utilization of the waste lithium ion batteryThe significance of (1).

Description

Method for preparing MOF-based nano material based on waste lithium ion battery leachate
Technical Field
The invention relates to the field of resource recycling technology and chemical material preparation, in particular to the field of a method for preparing an MOF-based nano material based on a waste lithium ion battery leachate.
Background
The lithium ion battery has the advantages of high energy density, small self-discharge, light pollution, long cycle life and the like, and is widely applied to consumer electronics, new energy automobiles and large energy storage equipment, so that the consumption and the waste of the lithium ion battery are increased rapidly in the global scope, and the subsequent reasonable treatment of the lithium ion battery is an urgent problem to be solved after the lithium ion battery is in service. The waste lithium ion battery can cause resource waste due to improper disposal, and has great threat to the environment and human health. Under such circumstances, recycling of the used batteries has become an urgent task, because it not only minimizes the need for critical materials, but also solves the environmental and ecological pollution and impact thereof.
Due to coexistence of various metal ions, the prior waste lithium ion battery leachate is difficult to separate and extract, the process flow is long, the utilization rate of the leachate is low, the added value of the product is low, the purity of the leachate does not meet the commercial application requirement, and the morphology is uncontrollable. At present, MOF materials show good application prospects in the aspects of lithium ion batteries, supercapacitors, electrocatalysis, adsorbents and the like, but large-scale application of the MOF materials is limited due to the fact that raw materials required by preparation of the MOF materials are expensive.
Disclosure of Invention
The invention aims to provide a method for preparing an MOF-based nano material based on a waste lithium ion battery leachate, which realizes value-added utilization of valuable metal cobalt in a lithium ion battery anode material; meanwhile, the method is simple and convenient to operate, efficient and environment-friendly, and the prepared product is regular in shape.
The invention discloses a method for preparing an MOF-based nano material based on a waste lithium ion battery leachate, which comprises the following steps:
(1) cobalt leaching experiment
Mixing the anode material of the waste lithium ion battery with an acidic solution, and adding H2O2Stirring to obtain a mixture containing Li+，Co2+A solution of metal ions;
(2) preparation of MOF nanomaterials
Adjusting the concentration of cobalt ions to be 0.25-2 mol/L, adding a pH regulator, and controlling the pH of the leaching solution to be within 5-11; adding ethanol, and adjusting the volume ratio of the leaching solution to the ethanol to be 0.5: 1-5: 1; weighing 2-methylimidazole, slowly adding the 2-methylimidazole into the mixed solution, carrying out solvothermal reaction, and centrifuging to obtain the MOF-based nano material;
(3) preparation of MOF-based derivatized nanomaterials
And roasting the obtained MOF nano material to prepare the MOF-based derivative nano material.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As a preferable technical scheme of the invention, the lithium ion battery anode material in the step (1) is any one or a combination of at least two of a cobalt lithium battery anode material, a nickel cobalt aluminum lithium battery anode material or a nickel cobalt manganese lithium battery anode material.
As a preferred technical scheme of the invention, the acidic solvent in the step (1) is one or a combination of at least two of inorganic acid sulfuric acid, nitric acid, hydrochloric acid and organic acid acetic acid, maleic acid, lactic acid or carotic acid, and typical but non-limiting examples of the combination are as follows: sulfuric acid and nitric acid, sulfuric acid and hydrochloric acid, acetic acid and lactic acid, and nitric acid, acetic acid and lactic acid.
In a preferred embodiment of the present invention, the concentration of cobalt ions in step (2) is controlled to be 0.25 to 2mol/L, for example, 0.25mol/L, 0.5mol/L, 0.75mol/L, 1mol/L, 1.5mol/L, 2mol/L, etc., but the concentration is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, preferably 0.5 to 1 mol/L;
preferably, the pH regulator in the step (2) is any one or a combination of at least two of sodium hydroxide, ammonia water and potassium hydroxide, and is preferably ammonia water;
preferably, the PH of the leachate in step (2) is adjusted to 5 to 11, for example 6, 7, 8, 9, 10 or 11, but not limited to the values listed, and other values not listed within this range are equally applicable, preferably 6 to 8.
Preferably, the 2-methylimidazole in the step (2) is added according to the addition amount of the 2-methylimidazole and Co in the solution2+Metal ion molar ratio, 2-methylimidazole and Co in solution2+The molar ratio of the metal ions is 2:1 to 10:1, for example, 2:1, 4:1, 6:1, 8:1 or 10:1, but the ratio is not limited to the recited values, and other values not recited in the above range are also applicable, and preferably 4:1 to 8: 1.
Preferably, the solvothermal temperature in step (2) is 30 to 120 ℃, for example 30 ℃, 60 ℃, 90 ℃, 120 ℃ and the like, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable, preferably 30 to 90 ℃.
Preferably, the solvothermal reaction time in step (2) is 12-72h, such as 12h, 24h,36h,48h,72h, etc., but not limited to the recited values, and other values not recited in the range of values are also applicable, preferably 24-48 h.
As a preferable technical scheme of the invention, the roasting treatment in the step (3) is carried out under different atmosphere conditions.
Preferably, the atmosphere comprises any one or a combination of at least two of air, oxygen, nitrogen, neon, argon or argon, typical but non-limiting examples of which are: a combination of air and oxygen, a combination of oxygen and nitrogen, a combination of neon, argon and argon, a combination of air, nitrogen and argon, and the like.
Preferably, the roasting treatment in step (3) is performed under air or nitrogen.
Preferably, the additive in the step (3) is sulfur powder or selenium powder.
Preferably, the temperature of the baking treatment in step (3) is 100 to 1000 ℃, for example 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 1000 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 300 to 600 ℃.
Preferably, the time of the baking treatment in step (3) is 0.1 to 24 hours, such as 0.1 hour, 4 hours, 7 hours, 12 hours, 15 hours, 18 hours, 21 hours or 24 hours, but not limited to the recited values, and other values in the range are also applicable, preferably 1 to 12 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method provided by the invention can realize accurate regulation and control of the pH value of the leachate and the concentration of metal ions, thereby solving the technical problem of interference of other metal ions in the conventional technology and preparing the MOF material and the MOF material derivative which have complete crystal form, good crystallinity, high purity and uniform size.
(2) The preparation method provided by the invention has the advantages that the cost of the required raw materials is low, the recovery cost is saved, the prepared product has higher added value, and the excellent performance is expected to be applied to the fields of energy storage or catalysis and the like.
Drawings
Fig. 1 is a process flow diagram of a method of making MOF-based nanomaterials provided in the detailed description of the invention section.
FIG. 2 is a scanning electron micrograph of the MOF-derived nanomaterials of example 1.
Fig. 3 is a scanning electron micrograph of MOF derived nanomaterials from example 2.
Detailed Description
For better illustration of the present invention and to facilitate understanding of the technical solutions, the technical solutions of the present invention are described in detail below with reference to the accompanying drawings and examples. The specific flow is shown in figure 1. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1:
the embodiment provides a method for preparing an MOF-based nano material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste lithium cobalt oxide battery, and the method comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with 2mol/L acetic acid solution, and adding H with the volume of 3 percent of the acid solution2O2Stirring at 70 deg.C for 60min to obtain Li-containing solution+，Co2+A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 30g/L, and the stirring speed is 400 rpm.
(2) Controlling the concentration of cobalt ions to be 0.75mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 6; adding ethanol so that the volume ratio of the leaching solution to the ethanol is 0.5: 1; according to the molar ratio of the 2-methylimidazole to the cobalt ion concentration of 8:1, weighing 2-methylimidazole, slowly adding the 2-methylimidazole into the mixed solution, stirring at room temperature for 20min, standing in an oven at 30 ℃ for 24h, and centrifuging to obtain the MOF nano material.
(3) Roasting the obtained MOF-based nano material for 5 hours at 350 ℃ in the air to prepare MOF-based derived Co3O4And (3) nano materials.
In this example, the MOF derived nanomaterials were about 500nm in size and the morphology is shown in fig. 2. Analyzing by X-ray diffraction (XRD), the main phase of the MOF-based derived nano-materials in the step (3) is Co3O4And the purity thereof is 99.1%.
Example 2:
the embodiment provides a method for preparing an MOF-based nano material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste lithium cobalt oxide battery, and the method comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with 1mol/L nitric acid solution, and adding H with the volume of 0.5 percent of the volume of the acid solution2O2Stirring at 50 deg.C for 30min to obtain Li-containing solution+，Co2+A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 50g/L, and the stirring speed is 300 rpm.
(2) Controlling the concentration of cobalt ions to be 0.5mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 7; adding ethanol so that the volume ratio of the leachate to the ethanol is 3: 1; according to the mol ratio of the 2-methylimidazole to the cobalt ion concentration of 4:1, weighing 2-methylimidazole, slowly adding the 2-methylimidazole into the mixed solution, stirring at room temperature for 20min, standing in an oven at 60 ℃ for 36h, and centrifuging to obtain the MOF nano material.
(3) And roasting the obtained MOF-based nano material for 6 hours at 500 ℃ in the air to obtain the MOF-based derivative nano material.
In this example, the MOF derived nanomaterials were approximately 250nm in size and the morphology is shown in fig. 3. Analyzing by X-ray diffraction (XRD), the main phase of the MOF-based derived nano-materials in the step (3) is Co3O4And the purity thereof is 99.2%.
Example 3:
the embodiment provides a method for preparing an MOF-based nano material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste lithium cobalt oxide battery, and the method comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with 1.5mol/L lactic acid solution, and adding H with the volume of 0.5 percent of the volume of the acid solution2O2Stirring at 60 deg.C for 30min to obtain Li-containing solution+，Co2+A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 20g/L, and the stirring speed is 400 rpm.
(2) Controlling the concentration of cobalt ions to be 0.25mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 10; adding ethanol so that the volume ratio of the leachate to the ethanol is 1: 1; according to the molar ratio of the 2-methylimidazole to the cobalt ion concentration of 8:1, weighing 2-methylimidazole, slowly adding the 2-methylimidazole into the mixed solution, stirring at room temperature for 20min, standing in an oven at 60 ℃ for 24h, and centrifuging to obtain the MOF nano material.
(3) And placing a certain amount of sulfur powder on the upstream of the tubular furnace in the nitrogen atmosphere of the obtained MOF-based nano material, and roasting at 800 ℃ for 6 hours to obtain the MOF-based derivative nano material.
In this example, the main phase of the MOF-based derived nanomaterial of step (3) was CoS and its purity was 98.9% by X-ray diffraction (XRD) analysis.
Example 4:
the embodiment provides a method for preparing an MOF-based nano material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste nickel cobalt lithium manganate battery, and the method comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with 1.5mol/L carrot acid solution, and adding H with the volume of 0.5 percent of the acid solution2O2Stirring at 80 deg.C for 60min to obtain Li-containing material+，Co2+A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 25g/L, and the stirring speed is 400 rpm.
(2) Controlling the concentration of cobalt ions to be 1mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 11; adding ethanol so that the volume ratio of the leachate to the ethanol is 1: 1; weighing 2-methylimidazole according to the molar ratio of the 2-methylimidazole to the cobalt ion concentration of 6:1, slowly adding the 2-methylimidazole into the mixed solution, stirring at room temperature for 20min, standing in an oven at 80 ℃ for 24h, and centrifuging to obtain the MOF nano material.
(3) And placing a certain amount of selenium powder on the upstream of the tubular furnace in a nitrogen atmosphere of the obtained MOF-based nano material, and roasting at 750 ℃ for 10 hours to obtain the MOF-based derivative nano material.
In this example, the main phase of the MOF-based derived nanomaterial of step (3) was CoSe and its purity was 98.9% as analyzed by X-ray diffraction (XRD).
Example 5:
the embodiment provides a method for preparing an MOF-based nano material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste nickel cobalt lithium manganate battery, and the method comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with 1mol/L maleic acid solution, and adding H with the volume of 1 percent of the acid solution2O2Stirring at 60 deg.C for 90min to obtain Li-containing material+，Co2+A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 30g/L, and the stirring speed is 400 rpm.
(2) Controlling the concentration of cobalt ions to be 2mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 8; adding ethanol so that the volume ratio of the leachate to the ethanol is 1: 1; weighing 2-methylimidazole according to the molar ratio of the concentration of 2-methylimidazole to cobalt ions of 10:1, slowly adding the 2-methylimidazole into the mixed solution, stirring at room temperature for 20min, standing in an oven at 60 ℃ for 72h, and centrifuging to obtain the MOF nano material.
(3) And placing a certain amount of sulfur powder on the upstream of the tubular furnace in the nitrogen atmosphere of the obtained MOF nano material, and roasting at 750 ℃ for 8h to obtain the MOF-based derivative nano material.
In this example, the main phase of the MOF-based derived nanomaterial of step (3) was CoS and its purity was 99.2% by X-ray diffraction (XRD) analysis.
Example 6:
the embodiment provides a method for preparing an MOF-based nano material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste lithium cobalt oxide battery, and the method comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with 1mol/L maleic acid solution, and adding H with the volume of 1 percent of the acid solution2O2Stirring at 60 deg.C for 90min to obtain Li-containing material+，Co2+A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 30g/L, and the stirring speed is 400 rpm.
(2) Controlling the concentration of cobalt ions to be 1.5mol/L by evaporating the leaching solution; adding a proper amount of sodium hydroxide, and adjusting the pH value of the leaching solution to 9; adding ethanol so that the volume ratio of the leachate to the ethanol is 5: 1; and weighing 2-methylimidazole according to the molar ratio of 2:1 of the concentration of the 2-methylimidazole to the concentration of cobalt ions, slowly adding the 2-methylimidazole into the mixed solution, stirring at room temperature for 20min, standing in an oven at 60 ℃ for 72h, and centrifuging to obtain the MOF nano material.
(3) And placing a certain amount of sulfur powder at the upstream of the tubular furnace in a nitrogen atmosphere of the obtained MOF-based nano material, and roasting at 750 ℃ for 8h to obtain the MOF-based derivative nano material.
In this example, the main phase of the MOF-based derived nanomaterial of step (3) was CoS and its purity was 99.2% by X-ray diffraction (XRD) analysis.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modification, equivalent substitution of materials for the invention, addition of additional materials, selection of specific means, etc., which are apparent to those skilled in the art are intended to be within the scope and disclosure of the invention.

Claims (10)

1. A method for preparing MOF-based nano materials based on a waste lithium ion battery leachate is characterized by comprising the following steps:
(1) mixing the anode material of the waste lithium ion battery with an acidic solvent, and stirring to obtain the Li-containing material+，Co2+A solution of metal ions;
(2) adjusting the concentration of cobalt ions to 0.25-2 mol/L, adding a pH regulator, and controlling the pH of the leaching solution to be within 5-11; adding ethanol, and adjusting the volume ratio of the leaching solution to the ethanol to be 0.5: 1-5: 1; weighing 2-methylimidazole, slowly adding the 2-methylimidazole into the mixed solution, carrying out solvothermal reaction, and centrifuging to obtain the MOF-based nano material;
(3) roasting the MOF-based nano material obtained in the step (2) at 100-1000 ℃ for 0.1-24 h to prepare the MOF-based derivative nano material.
2. The method for preparing the MOF-based nano material based on the leachate of the waste lithium ion battery as claimed in claim 1, wherein the lithium ion battery cathode material in the step (1) is any one or more of a lithium cobalt oxide battery cathode material, a lithium nickel cobalt aluminate battery cathode material or a lithium nickel cobalt manganese oxide battery cathode material.
3. The method for preparing the MOF-based nano material based on the leachate of the waste lithium ion battery according to claim 1 or 2, wherein the acidic solvent in the step (1) is one or more of inorganic acid sulfuric acid, nitric acid, hydrochloric acid and organic acid acetic acid, maleic acid, lactic acid or carotic acid.
4. The method for preparing the MOF-based nano material based on the leachate of the waste lithium ion battery as claimed in claim 1 or 2, wherein the cobalt ion concentration in the step (2) is 0.75-1.5 mol/L.
5. The method for preparing the MOF-based nano material based on the leachate of the waste lithium ion battery as claimed in claim 1 or 2, wherein the pH regulator in the step (2) is any one or more of sodium hydroxide, ammonia water and potassium hydroxide.
6. The method for preparing the MOF-based nano material based on the waste lithium ion battery leachate according to claim 1 or 2, wherein the volume ratio of the leachate and ethanol in the step (2) is 1: 1-3: 1.
7. The method for preparing the MOF-based nano material based on the leachate of the waste lithium ion battery as claimed in claim 1 or 2, wherein the 2-methylimidazole is added in the step (2) according to the addition amount of the 2-methylimidazole and Co in the solution2+Adding metal ions at a molar ratio of 2: 1-10: 1;
the solvothermal reaction temperature is 30-120 ℃, and the reaction time is 12-72 h.
8. The method for preparing the MOF-based nano material based on the leachate of the waste lithium ion battery according to any one of claims 1 or 2, wherein the roasting treatment in the step (3) is carried out under vacuum or atmosphere conditions.
9. The method for preparing the MOF-based nanomaterial based on the leachate of the waste lithium ion battery according to any of the claims 8, wherein the atmosphere comprises any one or a combination of at least two of air, oxygen, nitrogen, neon, argon or argon.
10. The method for preparing the MOF-based nano material based on the leachate of the waste lithium ion battery according to any one of claims 1 or 2, wherein the additive for the roasting treatment in the step (3) is sulfur powder or selenium powder, and the temperature is 300-600 ℃;
and (4) the roasting treatment time in the step (3) is 1-12 h.
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