Mixed powder for oxygen reactant and oxygen reactant using the same

Abstract

Provided is a mixed powder for an oxygen reaction agent, which exhibits excellent reactivity with oxygen. This mixed powder for an oxygen reaction agent is a mixed powder containing: an iron-based powder (A) in which the ratio of oxygen atoms and iron atoms (O / Fe) is less than 0.30; and a powder (B) containing at least one of an iron oxide powder in which the O / Fe ratio is 0.30-1.90 and a coke powder in which the C content is 50 mass% or greater. The content of the powder (B) in the mixed powder is 0.05-70.00 mass%.

Description

[Technical Field]

[0001] The present invention relates to a mixed powder for an oxygen reactant and an oxygen reactant using the same. [Background technology]

[0002] Oxygen reactants that utilize the reaction between iron-based powder and oxygen are known to be used as oxygen scavengers or heat generating agents. For example, as an oxygen scavenger, an oxygen reactant can be sealed in a container together with preserved items such as food and medicine to create a low-oxygen state inside the container. Therefore, oxygen reactants are used to suppress quality deterioration of preserved items due to oxidation and mold growth. Oxygen reactants can also be used as heat generating agents and are widely used in disposable hand warmers to warm the human body, etc. Generally, these oxygen reactants contain activated carbon, sodium chloride, silica powder, wood powder, water, sulfur powder, etc. added to the iron-based powder to further promote the reaction between the iron-based powder and oxygen.

[0003] Furthermore, in both applications, the reaction rate between iron and oxygen is important, and as a means for controlling the reaction rate, the use of a conductive material other than iron in combination with the iron-based powder has been studied.

[0004] For example, Patent Document 1 proposes activated iron powder in which the surface of the iron powder is coated with a conductive carbonaceous material such as conductive graphite, carbon black, graphite, and activated carbon, and a body warmer using the same.

[0005] From a viewpoint other than improving reactivity, mixed powders containing iron-based powders that can be suitably used as oxygen reactants have also been investigated.

[0006] For example, Patent Document 2 proposes a composition for an oxygen scavenger in which iron powder and iron oxyhydroxide or iron (III) oxide are mixed in order to ensure fluidity while suppressing dust generation. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 6-248303 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-159271 Summary of the Invention [Problem to be solved by the invention]

[0008] As described in Patent Document 1, when iron powder and a carbon material are used, the iron powder acts as an anode and the carbon material acts as a cathode, thereby accelerating the oxidation reaction of iron. However, further improvement in reactivity has been desired.

[0009] Furthermore, even when the composition described in Patent Document 2 was used, the reactivity with oxygen was insufficient.

[0010] The present invention aims to solve the above-mentioned problems and to provide a mixed powder for an oxygen reactant which has excellent reactivity with oxygen, and an oxygen reactant using the same. [Means for solving the problem]

[0011] Generally, when comparing the oxidation reaction of carbon with that of iron, the standard electrode potential of carbon is higher, and carbonaceous powder is less susceptible to oxidation than iron. The carbonaceous powder referred to here includes graphite and coke powder, for example. Furthermore, as can be seen from the potential-pH diagram (Pourbaix diagram) for iron, when comparing the reaction in which iron oxide is further oxidized with the oxidation reaction of metallic iron, the standard electrode potential of iron oxide is higher.

[0012] When an iron-based powder comes into contact with a conductive powder having a higher potential than the iron-based powder in a corrosive environment such as an electrolyte, a local battery is formed. That is, a corrosion current flows from the powder with the higher potential to the iron-based powder with the lower potential, and then the corrosion current returns to the powder with the higher potential than the iron-based powder via the electrolyte, and then flows back to the iron-based powder.

[0013] It is also believed that the formation of the local battery described above promotes the reaction between the low-potential iron-based powder and oxygen. In particular, a powder containing iron oxide powder or coke powder has a higher potential than an iron-based powder with a low oxygen content relative to iron. When the iron-based powder is mixed with the above-mentioned powder with a higher potential, the reactivity of the iron-based powder with oxygen increases due to contact between the iron oxide powder and the iron-based powder, or the reactivity of the iron-based powder with oxygen increases due to contact between the coke powder and the iron-based powder.

[0014] Therefore, the inventors came up with the idea of ​​adding a powder containing at least one of iron oxide powder and coke powder to the iron-based powder and mixing it in order to promote the reaction between the iron-based powder and oxygen, and conducted extensive research. As a result, they found that a mixed powder obtained by mixing a plurality of powders in an appropriate ratio exhibits excellent reactivity with oxygen.

[0015] The present invention is based on the above findings and has the following gist and configuration.

[0016] 1. A mixed powder for an oxygen reactant, which is a mixture of an iron-based powder (A) having an oxygen to iron atomic ratio O / Fe of less than 0.30 and a powder (B) containing at least one of an iron oxide powder having an O / Fe ratio of 0.30 or more and 1.90 or less and a coke powder having a C content of 50 mass% or more, wherein the content of the powder (B) in the mixed powder is 0.05 mass% or more and 70.00 mass% or less.

[0017] 2. The mixed powder for an oxygen reactant according to 1, wherein the powder (B) contains a total of 0.30 mass% or more and 100.00 mass% or less of the iron oxide powder having an O / Fe ratio of 0.30 or more and 1.90 or less and the coke powder having a C content of 50 mass% or more.

[0018] 3. An oxygen reactant using the mixed powder for an oxygen reactant according to 1 or 2 above. [Effects of the Invention]

[0019] According to the present invention, a mixed powder for an oxygen reactant having excellent reactivity with oxygen and an oxygen reactant using the same can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0020] First, an outline of the present invention will be described.

[0021] The mixed powder for an oxygen reactant according to the present invention is a mixed powder of iron-based powder (A) and powder (B). When the mixed powder is used, powder (B) comes into contact with iron-based powder (A), generating a corrosion current and promoting the reaction of iron with oxygen. The mixed powder for an oxygen reactant according to the present invention has excellent reactivity with oxygen and is suitable for use in the oxygen reactant of the present invention.

[0022] Hereinafter, embodiments of the present invention will be described. Note that the following embodiments are merely examples for explaining the present invention, and the present invention is not limited to these embodiments.

[0023] The mixed powder for an oxygen reactant according to the present invention is a mixed powder of an iron-based powder (A) and a powder (B). Here, the iron-based powder (A) has an oxygen to iron atomic ratio (hereinafter also referred to as "O / Fe") of less than 0.30. Furthermore, the powder (B) contains at least one of an iron oxide powder having an O / Fe ratio of 0.30 or more and 1.90 or less, and a coke powder having a C content of 50 mass% or more. Each component will be explained below.

[0024] In the present invention, the O / Fe ratio of the iron-based powder (A) must be less than 0.30. Iron-based powders, such as iron powder, generally have oxidized surfaces. When the surface of the iron-based powder is oxidized, the metallic iron contained in the iron-based powder is less likely to convert to iron ions and release electrons. Therefore, when using a typical iron-based powder, it is difficult to promote the oxidation reaction of iron by using the iron-based powder as the anode and a carbonaceous material as the cathode. However, if the O / Fe ratio is reduced to less than 0.30, a sufficient amount of corrosion current is generated in the presence of an electrolyte due to the potential difference between the iron-based powder (A) and the powder (B). In other words, when used as an oxygen reactant, the iron-based powder (A) should be as oxidized as possible to obtain a larger corrosion current. Therefore, in the present invention, the O / Fe ratio of the iron-based powder (A) is set to less than 0.30. The lower limit of the O / Fe ratio is not particularly limited and may be 0. However, from the viewpoint of ease of production, a ratio of 0.15 or more is preferable.

[0025] The O / Fe ratio of the iron-based powder (A) in the present invention is measured as follows.

[0026] First, X-ray diffraction measurement is performed on the iron-based powder (A), and the obtained diffraction data is used to perform Rietveld analysis to determine the contents of elemental Fe, compounds of Fe and O, and other compounds in the powder. The numbers of Fe and O atoms are determined from the contents, and the O / Fe value is calculated.

[0027] The iron-based powder (A) is not particularly limited and any iron-based powder can be used. Examples of the iron-based powder (A) include iron powder and iron-based alloy powder. The term "iron-based powder" refers to a metal powder containing 50.00% by mass or more of Fe, and the term "iron-based alloy powder" refers to an alloy powder containing 50.00% by mass or more of Fe. The term "iron powder" refers to a powder consisting of Fe and inevitable impurities, and is generally referred to as "pure iron powder" in the technical field. When the iron-based powder (A) is an iron-based alloy powder, the iron-based alloy powder may further contain any element, such as C, S, N, Si, Na, Mg, or Ca, in addition to Fe and O. On the other hand, when the iron-based powder (A) is an iron powder, the iron powder may contain any element, such as C, S, O, N, Si, Na, Mg, or Ca, as an inevitable impurity.

[0028] The iron oxide powder according to the present invention has an O / Fe ratio of 0.30 or more and 1.90 or less. If the O / Fe ratio is less than 0.30, the potential difference with the iron-based powder (A) is small, resulting in a small corrosion current flowing between the iron-based powder (A) and the iron oxide powder. Therefore, the O / Fe ratio of the iron oxide powder is set to 0.30 or more. On the other hand, if the O / Fe ratio exceeds 1.90, the conductivity of the powder (B) decreases, making it difficult for a corrosion current to flow between the iron-based powder (A) and the powder (B). Therefore, the O / Fe ratio of the iron oxide powder is set to 1.90 or less. The O / Fe value can be measured in the same manner as for the iron-based powder (A). The sample used for measuring the O / Fe ratio may contain components other than the iron oxide powder as long as they do not affect the calculation of the O / Fe ratio.

[0029] The coke breeze according to the present invention has a C content of 50% by mass or more. If the C content is less than 50% by mass, a corrosion current does not sufficiently flow between the iron-based powder (A) and the coke breeze. On the other hand, the upper limit of the C content of the coke breeze is not particularly limited and may be 100% by mass.

[0030] The C content of the coke breeze is measured by the method specified in JIS M 8813 "Coals and cokes - Elemental analysis method." More specifically, it can be measured by the method described in the examples.

[0031] Powder (B) contains at least one of the iron oxide powder and the coke breeze. Powder (B) may contain either the iron oxide powder or the coke breeze. However, powder (B) preferably contains the iron oxide powder and the coke breeze. When powder (B) contains the iron oxide powder and the coke breeze, both phenomena occur simultaneously: the reactivity of iron with oxygen is improved by contact between the iron oxide powder and the iron-based powder (A), and the reactivity of iron with oxygen is improved by contact between the coke breeze and the iron-based powder (A). This results in a higher reactivity with oxygen than when a mixed powder containing only one of the iron oxide powder and the coke breeze is used.

[0032] The powder (B) may contain any powder other than the iron oxide powder and the coke breeze. Specific examples of such powders include Al2O3, SiO2, and CaO. The powder (B) may also consist of the iron oxide powder, the coke breeze, and the remainder consisting of inevitable impurities. Examples of the inevitable impurities include at least one of P, S, Si, Al, Ca, Mn, Ti, Cu, Ni, Mo, Mg, Cr, Zn, and oxides thereof.

[0033] The powder (B) is preferably dust, particularly iron-making dust. The use of dust enables the reuse of waste materials and further reduces production costs. The iron-making dust includes dust generated in blast furnaces (blast furnace dust) and dust generated in converters (converter dust) in steelworks.

[0034] The powder (B) preferably contains the iron oxide powder and the coke powder in a total amount of 0.30% by mass or more and 100.00% by mass or less. By setting the total amount to 0.30% by mass or more, the content of powders other than the iron oxide powder and the coke powder (e.g., powders of Al2O3, SiO2, CaO, etc.) can be reduced, thereby improving reactivity. Furthermore, powders other than the iron oxide powder and the coke powder have effects such as reducing the contact between the iron-based powder (A) and the iron oxide powder or the coke powder, and absorbing moisture necessary for the oxidation of the iron-based powder (A). Therefore, a lower content of these powders further improves the heat generation property of the mixed powder. Therefore, the total amount is preferably 0.30% by mass or more. The upper limit of the total amount is not particularly limited and can be 100.00% by mass.

[0035] The upper limit of the proportion of the iron oxide powder in powder (B) is not limited, and may be 100% by mass or less, or may be 60.00% by mass or less. Here, for example, the proportion of iron oxide powder in blast furnace dust can take any value depending on the operating conditions, but when a blast furnace is operated under typical operating conditions, it is generally 60.00% by mass or less. The lower limit of the proportion of the iron oxide powder in powder (B) is not limited, and may be 0% by mass.

[0036] The upper limit of the proportion of the coke breeze in the powder (B) is not limited, and may be 100% by mass or less, or 40.00% by mass or less. Here, for example, the proportion of coke breeze in blast furnace dust can take any value depending on the operating conditions, but when a blast furnace is operated under general operating conditions, it is generally 40.00% by mass or less. The lower limit of the proportion of the coke breeze in the powder (B) is not limited, and may be 0% by mass.

[0037] The mixed powder for an oxygen reactant according to the present invention is a mixed powder of the iron-based powder (A) and the powder (B). The mixed powder for an oxygen reactant according to the present invention preferably consists of the iron-based powder (A) and the powder (B).

[0038] The reason why the mixed powder for an oxygen reactant of the present invention exhibits excellent reactivity with oxygen is presumed to be as follows: Since both the iron oxide powder and the coke powder have a higher potential than the iron-based powder (A), when the iron-based powder (A) and the powder (B) come into contact with each other in the presence of an electrolyte, a corrosion current is generated, accelerating the oxidation reaction of iron.

[0039] In the present invention, the mixed powder for an oxygen reactant contains powder (B) in an amount of 0.05% by mass or more and 70.00% by mass or less. If the content of powder (B) is less than 0.05% by mass, the corrosion current is small and the reaction of iron with oxygen cannot be promoted. Therefore, the content of powder (B) is set to 0.05% by mass or more. On the other hand, powder (B) itself hardly oxidizes, so it reacts with oxygen in a smaller amount than iron-based powder (A). Therefore, if the content of powder (B) is more than 70.00% by mass, the amount of reaction of the mixed powder with oxygen becomes too low, falling below the amount of reaction of iron-based powder (A) alone with oxygen. Therefore, the content of powder (B) is set to 70.00% by mass or less.

[0040] The particle size of the mixed powder is not particularly limited as long as it is a particle size that does not cause problems in handling. 50 (the median value of particle diameter calculated from the volume-based particle size distribution) is preferably 1000 μm or less, more preferably 400 μm or less, and even more preferably 200 μm or less. 50 There is no particular restriction on the lower limit of D of the mixed powder from the viewpoint of ease of handling. 50 It is preferable to set the thickness to 5 μm or more.

[0041] Median diameter D 50 is measured by a laser diffraction / scattering method. The specific measurement method is as follows: The powder to be measured is placed in a solvent (e.g., ethanol) and dispersed by ultrasonic vibration for 30 seconds or more, and the volume-based particle size distribution of the powder is measured using a laser diffraction particle size distribution analyzer. The cumulative particle size distribution is calculated from the obtained particle size distribution, and the particle size of the particles corresponding to 50% of the total volume of all particles is taken as the median D 50 The median D 50can be used as a representative value of the particle size of the mixed powder.

[0042] [Production of iron-based powder (A)] The iron-based powder (A) can be produced by any method. For example, the iron-based powder (A) can be produced by techniques such as atomization, reduction, or pulverization. The atomization method is a method in which water or gas is sprayed onto a molten metal, pulverized, and then cooled and solidified, and either water atomization or gas atomization can be used. The reduction method is, for example, a method in which iron oxide (mill scale) or iron ore powder generated on the surface of a steel sheet during hot rolling of the steel material is reduced. The pulverization method is a method in which small metal pieces are pulverized using a pulverizer. Furthermore, the powder produced by the above methods may be classified or mixed. The classification and mixing can be performed by any method.

[0043] To remove oxygen so that the O / Fe ratio of the iron-based powder (A) is 0.30 or less, the iron-based powder (A) may be subjected to a heat treatment (deoxidation treatment) using carbon such as coke or graphite or hydrogen gas at a maximum temperature of 750°C or higher.

[0044] [Production of powder containing iron oxide powder] The powder (B) can be produced by any method. For example, when a powder containing the iron oxide powder is used as the powder (B), the powder (B) is preferably an atomized powder (a powder produced by the atomization method described above), a mill scale powder, or an iron ore powder. In this case, the powder (B) is more preferably a powder before reduction. Furthermore, the above-mentioned powders may be classified or mixed. The classification and mixing can be performed by any method.

[0045] [Production of powder containing coke powder] When a powder containing the coke powder is used as the powder (B), the powder (B) is preferably a powder obtained by crushing and classifying coke. The powder (B) is also preferably a powder obtained by collecting dust when coke immediately after production in a coke oven is transported to a coke dry quenching facility, or a powder obtained by collecting dust in the coke dry quenching facility.

[0046] [Production of powder containing iron oxide powder and coke powder] When a powder containing the iron oxide powder and the coke fines is used as the powder (B), as described above, the powder (B) is preferably dust, particularly ironworks dust. The ironworks dust includes dust generated in blast furnaces (blast furnace dust) and dust generated in converters (converter dust) in steelworks. For example, blast furnace dust is generated by the impact of dropping iron ore and coke when they are charged into a blast furnace from the top of the furnace. The blast furnace dust is generally discharged outside the blast furnace together with the furnace gas rising from the bottom of the blast furnace and collected when the furnace gas is purified with water. The dust is, for example, dried to form a solid and then pulverized to obtain the powder (B). The pulverized powder obtained by pulverizing the blast furnace dust contains, as main components, the iron oxide powder derived from the iron ore and the coke fines derived from the coke.

[0047] [Mixed powder manufacturing] In producing the mixed powder for the oxygen reactant, it is necessary to mix the iron-based powder (A) with the powder (B). To mix them uniformly, it is preferable to use a mixing device such as a V-type mixer, a double cone mixer, or a conical blender.

[0048] The above-mentioned apparatus and mixing conditions may be those known in the art.

[0049] [Oxygen reactant] In one embodiment of the present invention, an oxygen reactant can be produced using the mixed powder for an oxygen reactant described above. In other words, the oxygen reactant according to one embodiment of the present invention is an oxygen reactant using the mixed powder for an oxygen reactant described above. The mixed powder for an oxygen reactant of the present invention has excellent reactivity with oxygen and is therefore suitable for use as the oxygen reactant. Therefore, the oxygen reactant exhibits the same effects as the mixed powder for an oxygen reactant of the present invention.

[0050] The components constituting the oxygen reactant other than the oxygen reactant mixed powder are not particularly limited, and conventionally known components used in oxygen reactants can be used. For example, an additive may be added to the mixed powder. Examples of such additives include activated carbon and salt water. The oxygen reactant may also be enclosed in a bag made of breathable packaging material. Examples of such bags include a bag made by layering nonwoven fabric and perforated polyethylene, or a bag made by layering paper and perforated polyethylene. The oxygen reactant may consist of the oxygen reactant mixed powder. [Example]

[0051] The mixed powder used in this example was prepared by the following procedure.

[0052] As the iron-based powder (A) shown in Table 1, various iron-based powders were obtained by adjusting the O / Fe ratio by reducing mill scale with coke in the temperature range of 800 to 1000°C.

[0053] The O / Fe ratio of the iron-based powder (A) was calculated by measuring the contents of simple Fe, compounds of Fe and O, and other compounds in the iron-based powder using an X-ray diffractometer (SmartLab, manufactured by Rigaku Corporation).

[0054] Furthermore, among the powders (B) listed in Table 1 containing iron oxide powder and coke powder, simulated blast furnace dust (powder simulating blast furnace dust) was used, which was a mixture of iron oxide powder, coke powder, and ash in a specific ratio. Here, the iron oxide powder used was a powder that did not contain oxides of metals other than Fe, and the coke powder and ash used were powders that did not contain Fe. The simulated blast furnace dusts with different components were pulverized using a Braun horizontal pulverizer (Yoshida Seisakusho Co., Ltd., 1025-A) to obtain pulverized powders of the simulated blast furnace dust.

[0055] The O / Fe ratio of the iron oxide powder was calculated by measuring the contents of elemental Fe, Fe-O compounds, and other compounds in powder (B) using an X-ray diffractometer, as in the case of iron-based powder (A). Taking into account the component composition of the raw material for the simulated blast furnace dust, the number of O atoms in Fe-O compounds and the number of Fe atoms in elemental Fe and Fe compounds were determined from the measurement results of powder (B). The ratio of the number of O atoms to the number of Fe atoms was defined as the O / Fe ratio of the iron oxide powder. The carbon content of the coke powder was determined by measuring the carbon content of the coke powder used as the raw material for the simulated blast furnace dust according to the method specified in JIS M 8813, "Coals and cokes - Elemental analysis method," and the carbon content in an anhydrous state was used as the carbon content.

[0056] Among the powders (B) listed in Table 1, those not containing coke powder were obtained by reducing mill scale powder to a predetermined O / Fe ratio. The O / Fe ratio of the iron oxide powder was determined in the same manner as for the pulverized powder of simulated blast furnace dust.

[0057] Among the powders (B) listed in Table 1, those not containing iron oxide powder were obtained by collecting dust from coke immediately after production in a coke oven when it was transported to a coke dry quenching facility. The C content of the coke powder was determined in the same manner as for the pulverized powder of the simulated blast furnace dust.

[0058] The obtained iron-based powder (A) and powder (B) were mixed to obtain a mixed powder for an oxygen reactant according to the present invention.

[0059] In the present example, the reactivity of the obtained mixed powder for oxygen reactant with oxygen was evaluated as follows.

[0060] A sample was obtained by adding 2 g of an 8% by mass aqueous sodium chloride solution to 20 g of the oxygen reactant mixed powder. The resulting sample was then sealed in a gas barrier zipper bag (HSC160-ST, manufactured by AS ONE Corporation) with oxygen gas barrier properties and left to stand at 25°C for 1 hour to allow the sample to return to room temperature. The sample was then placed in a paper cup (SD-729, manufactured by STRIX DESIGN, Inc.), and a temperature sensor connected to a data logger (TR-71wf, manufactured by T&D Corporation) was inserted into the center of the sample. After the temperature sensor was inserted, the temperature was measured using the temperature sensor at 1-minute intervals to determine the elapsed time until the temperature reached 40°C and the maximum temperature reached by the sample.

[0061] In addition, the D of each powder according to the example was measured by the above-mentioned method. 50 asked for.

[0062] Table 1 shows the temperature measurement results and D 50 are listed together respectively.

[0063] [Table 1]

[0064] As shown in Table 1, the mixed powders for oxygen reactant of Examples 1 to 13 of the invention shortened the time required to reach 40°C and increased the maximum temperature reached, compared to the powders of Comparative Examples 1 to 18. This shows that the mixed powders of the invention examples have good reactivity with oxygen.

[0065] The mixed powders for oxygen reactant of Examples 1 to 13 are examples that satisfy all of the requirements of the present invention, while the mixed powders of Comparative Examples 1 to 18 are examples that do not satisfy any of the requirements of the present invention.

[0066] Among them, in Examples 5 to 13 of the present invention, in which powder (B) having a total content of the iron oxide powder and coke powder of 0.30 mass% or more and 100.00 mass% or less was mixed, the time to reach 40°C was further shortened and the maximum temperature reached was 55°C or more.

[0067] In addition, in Examples 9 to 13, the D of the mixed powder 50 By setting the thickness to 400 μm or less, the time required to reach 40°C was further shortened, and the maximum temperature reached was 60°C or higher.

[0068] Furthermore, in Examples 11 to 13, the D of the mixed powder 50 By setting the thickness to 200 μm or less, the time required to reach 40°C was further shortened, and the maximum temperature reached was 65°C or higher.

[0069] In contrast to this, in Comparative Examples 1 to 18, it took a long time to reach 40°C, and the maximum temperature reached was 50°C or lower.

Claims

1. an iron-based powder (A) having an oxygen to iron atomic ratio O / Fe of less than 0.30; Coke powder having a C content of 50 mass% or more, or powder (B) containing iron oxide powder and the coke powder having an O / Fe ratio of 0.30 to 1.90; A mixed powder comprising: a powder (B) having a content of 0.05% by mass or more and 70.00% by mass or less; The iron-based powder (A) is a mixed powder for an oxygen reactant containing Fe and O, with the remainder being unavoidable impurities.

2. 2. The mixed powder for an oxygen reactant according to claim 1, wherein the powder (B) contains a total of 0.30 mass% or more and 100.00 mass% or less of the iron oxide powder having an O / Fe ratio of 0.30 to 1.90 and the coke powder having a C content of 50 mass% or more.

3. An oxygen reactant using the mixed powder for an oxygen reactant according to claim 1 or 2.

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