Granular ozone catalyst based on algae biomass and preparation method thereof

Abstract

The invention discloses a preparation method of a granular ozone catalyst based on algae biomass, which comprises the following steps: grinding silicon-aluminum-based mineral powder to 200-1200 meshes, and then drying for later use; uniformly mixing the algae biomass with the water content of less than 5% and the silicon-aluminum-based mineral powder according to the mass ratio of 1: 5-1: 20 to obtain a mixed material; metal active components are introduced into the mixed material through a mixing method, a roasting method or a mixing-roasting method, and a particle material is obtained; and drying and roasting the granular material to obtain the catalyst. According to the ozone catalyst prepared by the method disclosed by the invention, algae biomass is taken as a raw material to introduce a high-activity carbon catalytic matrix and active catalytic sites of nitrogen and phosphorus atoms, so that a good way for realizing resource utilization of solid wastes is provided; meanwhile, alumina powder, natural zeolite powder and the like which are low in price and easy to obtain are used for achieving granulation of the catalyst form and stable recovery in application, and metal components are introduced to provide metal active sites; the preparation method is novel, simple and easy to popularize.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst preparation, and in particular to a granular ozone catalyst based on algae biomass and a preparation method thereof. Background Art

[0002] As my country's environmental management requirements continue to improve, the requirements for wastewater treatment efficiency and green and low-carbon levels are constantly increasing. Ozone catalytic oxidation is one of the most widely used sewage deep treatment technologies, and the performance of the ozone catalyst directly determines the treatment efficiency of the technology.

[0003] Currently, commonly used ozone catalysts are mainly composed of a matrix (carrier) and active components. The commonly used raw materials of the matrix (carrier) are alumina, zeolite, diatomaceous earth, etc. The active components mainly come from metals or carbon materials, etc. In addition, the introduction of elements such as nitrogen and phosphorus is also conducive to the formation of high catalytic activity sites. With the continuous promotion of ozone catalytic oxidation technology, the demand for high-activity, low-cost, widely available catalyst preparation raw materials is increasing.

[0004] Algae are common autotrophic organisms in aquatic environments and play an important role as producers in aquatic ecosystems. Algae cells absorb nutrients such as nitrogen and phosphorus in water and carbon dioxide in the air to synthesize cell substances. They naturally have carbon, nitrogen, and phosphorus elements and a specific cell structure.

[0005] The sources of algae biomass are very wide. Every year, my country collects a large amount of algae biomass from water bodies with algal blooms. In order to avoid the outbreak of algal blooms, the nitrogen and phosphorus in the water can be removed in advance through algae pre-cultivation pools. In addition to naturally obtaining algae biomass, the scale and prospects of artificial cultivation of algae are also expanding. For example, in the energy production or food processing industry, algae are used to produce biomass energy products such as biodiesel, or high-value health products such as algae protein and astaxanthin. After the production and extraction of these products, a large amount of algae residue will remain. Direct discharge of algae residue into the environment will have an impact on the ecological environment. How to achieve the recycling of algae blooms and industrial algae residue is also a problem that needs to be solved.

[0006] Although the direct sintering of algae cells to prepare powdered ozone catalysts can achieve excellent catalytic effects, the powdered catalysts are not convenient to recycle and are difficult to apply in actual projects. How to ensure the catalytic effect while making the ozone catalysts prepared from algae biomass have reliable structural performance and mechanical strength is the basic prerequisite for realizing engineering applications. Summary of the invention

[0007] The purpose of the present invention is to provide a particulate ozone catalyst based on algae biomass and a preparation method thereof, utilizing algae biomass to provide a highly active carbon catalytic matrix and active catalytic sites of nitrogen and phosphorus atoms, adding alumina or zeolite to provide an aluminum or silicon / aluminum matrix, and introducing metal active components through a mixing method, a roasting method or a mixing-roasting method to prepare a new type of high-efficiency ozone catalyst.

[0008] In order to achieve the above object, the present invention is specifically implemented through the following technical solutions:

[0009] A method for preparing a particulate ozone catalyst based on algae biomass comprises the following steps:

[0010] S1, grinding the silicon-aluminum-based mineral powder to 200-1200 mesh, and then drying at 105-120° C. for standby use;

[0011] S2, mixing algae biomass having a moisture content of less than 5% and silicon-aluminum-based mineral powder in a mass ratio of 1:5 to 1:20 to obtain a mixed material;

[0012] S3, introducing metal active components into the mixed material by mixing, roasting or mixing-roasting, wherein the amount of the metal active components added is 0.25 to 1 mol / kg, to obtain a granular material;

[0013] S4, drying the granular material obtained in step S3 at 60-80° C. for at least 12 h, and then calcining at 500-800° C. in a nitrogen, argon or vacuum atmosphere for at least 3 h.

[0014] Based on the above technical solution, the algae biomass comes from natural water bodies or artificially cultured blue algae, green algae, diatoms and other organisms.

[0015] Based on the above technical solution, the algae biomass comes from the algae residue left after extracting some components from algae, such as extracting oil, protein or other biological products, and the moisture content is less than 5%. When using the algae residue left after extracting oil, protein or other biological products, if the moisture content of the algae residue is sufficiently lower than 5%, dehydration and drying can be omitted, and the moisture content can be ensured to be below 5%.

[0016] Based on the above technical solution, the silicon-aluminum-based mineral powder is one or more of alumina powder, natural zeolite and activated diatomaceous earth.

[0017] Based on the above technical solution, the activation method of the activated diatomite is that the diatomite is fully alkalized in a sodium hydroxide solution, filtered and washed with clean water, and then calcined for activation. The diatomite is activated after being treated with alkali to change its surface chemical properties and pore structure, improve adsorption performance, etc.

[0018] Based on the above technical solution, the metal active component is an oxide or nitrate of an active metal; the active metal is one or more of titanium, copper, calcium, manganese, iron, magnesium, zinc, nickel and cerium.

[0019] Based on the above technical solution, in step S3, the mixing method is to fully mix the algae biomass, the silicon-aluminum-based mineral powder and the metal oxide powder, and then perform ball granulation;

[0020] The impregnation method comprises rolling a mixture of algae biomass and silicon-aluminum-based mineral powders into granules, and transferring the prepared granules into a metal nitrate solution for full impregnation;

[0021] The mixing-impregnation method comprises firstly fully mixing algae biomass, silicon-aluminum-based mineral powder and metal oxide powder, rolling balls for granulation, and then transferring the prepared balls to a metal nitrate solution for full immersion.

[0022] Based on the above technical scheme, in the impregnation method and the mixed-impregnation method, when there are two or more active metal nitrates, after being fully impregnated in one active metal nitrate solution and dried and calcined in step S5, it is then fully impregnated in the next active metal nitrate solution, and dried and calcined in step S5.

[0023] Based on the above technical solution, the drying time is 12 to 24 hours; the roasting time is 3 to 5 hours.

[0024] The present invention also provides an algae biomass-based particulate ozone catalyst prepared by the above-mentioned method for preparing the algae biomass-based particulate ozone catalyst.

[0025] The ozone catalyst prepared by the method of the present invention uses algae biomass as a raw material to introduce a highly active carbon catalytic matrix and active catalytic sites of nitrogen and phosphorus atoms. The algae residue raw material used can come from water bloom algae, or from algae biomass diesel and algae residue remaining after the extraction of high-value biomass products. While obtaining the algae biomass raw materials through these approaches, the treatment and protection of the water environment is also achieved, and it is also a good way to realize the resource utilization of solid waste. At the same time, cheap and easily available alumina powder, natural zeolite powder, etc. are used to realize the granulation of the catalyst form and stable recovery in application, and metal components are introduced to provide metal active sites. The preparation method is novel and simple, and easy to promote.

[0026] While using algae biomass as raw material, metal oxides or salt solutions are added to provide metal active components. Combined with silicon / aluminum-based materials such as alumina, zeolite, and diatomaceous earth, a particle shape that is easy to recycle, a porous structure with a high specific surface area, and reliable mechanical strength are provided, which can further form an ozone catalyst with excellent performance, stable structure, and a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a comparison chart of TOC removal effect between the embodiment of the present invention and the comparative example. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below in conjunction with the accompanying drawings and embodiments.

[0029] The present invention provides a method for preparing a particulate ozone catalyst based on algae biomass, comprising the following steps:

[0030] S1. Grind the silicon-aluminum-based mineral powder to 200-1200 mesh, and then dry it at 105-120° C. for more than 24 hours for standby use; in this step, the silicon-aluminum-based mineral powder is preferably alumina powder or natural zeolite powder.

[0031] S2. Evenly mix algae biomass with a moisture content of less than 5% and silicon-aluminum-based mineral powder in a mass ratio of 1:5 to 1:20 to obtain a mixed material; the algae biomass comes from organisms such as natural water bodies or artificially cultivated blue algae, green algae, diatoms, etc., or residual algae residue after extraction of some components, and the moisture content is ensured to be below 5%.

[0032] S3. Introduce metal active components into the mixed material by mixing, roasting or mixing-roasting, with the metal active component added in an amount of 0.25 to 1 mol / kg to obtain a granular material; preferably, in this step, the metal active component is an oxide or nitrate of an active metal; the active metal is one or more of titanium, copper, calcium, manganese, iron, magnesium, zinc, nickel and cerium.

[0033] S4, drying the granular material obtained in step S3 at 60-80° C. for at least 12 h, and then calcining at 500-800° C. in a nitrogen, argon or vacuum atmosphere for at least 3 h.

[0034] In the impregnation method and mixed-impregnation method, when there are two or more active metal nitrates, after fully impregnating in one active metal nitrate solution and drying and roasting in step S5, enter the next active metal nitrate solution for full impregnation, drying and roasting in step S5. Full impregnation generally adopts excessive impregnation method, and the time is more than 12 hours. The conditions of the above-mentioned separate treatments do not have to be completely consistent, and can be within the range of the above-mentioned step S4.

[0035] Example 1

[0036] The preparation method of the granular ozone catalyst of the present invention comprises raw materials including: bloom algae (mainly cyanobacteria, including green algae, Chlamydomonas, etc.), alumina powder and copper nitrate. The preparation method is as follows:

[0037] S1. Dehydrating and drying the algae biomass salvaged from the water body of the algae bloom to reduce its moisture content to less than 5%;

[0038] S2, drying the alumina powder ground to 200-1200 mesh at 105-120°C for later use;

[0039] S3, mixing the algae biomass processed in step S1 and the alumina powder in step S2 in a mass ratio of 1:5, and granulating by rolling balls;

[0040] S4, transferring the small balls prepared in S3 to a copper nitrate solution for full immersion, wherein the amount of copper nitrate used is 1 mol / kg, to obtain a granular material;

[0041] S5. Dry the granular material at 60° C. for 24 h, and then calcine at 500° C. in a nitrogen, argon or vacuum atmosphere for 5 h.

[0042] Example 2

[0043] The preparation method of the granular ozone catalyst of the present invention comprises raw materials including: chlorella, natural zeolite powder, and copper oxide powder. The preparation method is as follows:

[0044] S1. Dehydrating and drying the chlorella to reduce its moisture content to below 5%;

[0045] S2, grinding the natural zeolite powder to 200-1200 mesh and drying it at 105-120°C for later use;

[0046] S3, fully and uniformly mixing algae biomass, natural zeolite powder and copper oxide powder, wherein the mixing mass ratio of algae biomass to natural zeolite powder is 1:12, the amount of copper oxide is 0.5 mol / kg, and granulating by rolling ball to obtain granular material;

[0047] S4. Dry the prepared granular material at 80°C for 12 hours, and then calcine at 800°C in nitrogen, argon or vacuum atmosphere for 3 hours.

[0048] Example 3

[0049] The preparation method of the granular ozone catalyst of the present invention comprises the following raw materials: algae biomass, mixed algae from algae culture ponds for deep treatment of nitrogen and phosphorus removal in sewage treatment plants, including Scenedesmus, Chlorella, etc.; alumina powder, natural zeolite powder; and metal active components using manganese nitrate solution and copper nitrate solution. The preparation method is as follows:

[0050] S1. Use sludge dewatering facilities on site at the sewage treatment plant to filter-filter dehydrate and dry the algae biomass to reduce its moisture content to less than 5%;

[0051] S2, grinding the alumina powder and natural zeolite powder to 200-1200 mesh and drying them at 105-120° C. for later use;

[0052] S3, mixing algae biomass, alumina powder and natural zeolite powder evenly (mixing mass ratio is 1:5:4), and granulating by rolling ball;

[0053] S4, transferring the prepared pellets to a manganese nitrate solution for full immersion, with a manganese nitrate dosage of 0.5 mol / kg, then washing with deionized water, drying at 65°C for 10 h, and calcining at 800°C in nitrogen, argon or vacuum atmosphere for 3 h;

[0054] S5. Transfer the small balls prepared in S4 to a copper nitrate solution for full immersion, with the amount of copper nitrate being 0.5 mol / kg; then wash with deionized water, dry at 65°C for 10 h, and calcine at 800°C in nitrogen, argon or vacuum atmosphere for 3 h.

[0055] Example 4

[0056] The preparation method of the granular ozone catalyst of the present invention comprises the following raw materials: algae biomass, mixed algae from algae culture ponds for deep treatment of nitrogen and phosphorus removal in sewage treatment plants, including Scenedesmus, Chlorella, etc.; alumina powder, diatomaceous earth; copper oxide powder, manganese oxide powder, and cerium oxide powder. The preparation method is as follows:

[0057] S1. Use sludge dewatering facilities on site at the sewage treatment plant to filter-filter dehydrate and dry the algae biomass to reduce its moisture content to less than 5%;

[0058] S2, fully grinding the aluminum oxide powder to 200-1200 mesh, and drying at 105-120° C. for standby use;

[0059] S3, fully alkalize the diatomaceous earth in a sodium hydroxide solution, filter it, wash it with clean water, and then roast it for activation;

[0060] S4, fully and uniformly mixing algae biomass, alumina powder, natural zeolite powder, copper oxide powder, manganese oxide powder and cerium oxide powder, wherein the mixing mass ratio of algae biomass, alumina powder and natural zeolite powder is 1:3:6, and the addition amount of copper oxide powder, manganese oxide powder and cerium oxide powder is 0.25 mol / kg, and rolling ball granulation is performed to obtain granular material;

[0061] S5. Dry the prepared granular material at 80° C. for 10 h, and then calcine at 800° C. in a nitrogen, argon or vacuum atmosphere for 5 h.

[0062] Example 5

[0063] The preparation method of the granular ozone catalyst of the present invention comprises the following raw materials: algae biomass, algae residue (water content less than 5%) after oil is extracted from Chlorella vulgaris; aluminum oxide powder; copper oxide powder, manganese oxide powder, cerium oxide powder; zinc nitrate solution, magnesium nitrate solution. The preparation method is as follows:

[0064] S1, drying the 200-1200 mesh ground alumina powder at 105-120°C for later use;

[0065] S2, the chlorella algae residue, aluminum oxide powder, copper oxide powder, manganese oxide powder, cerium oxide powder are fully mixed, wherein the chlorella algae residue and aluminum oxide powder are mixed in a mass ratio of 1:12, and the addition amount of copper oxide powder, manganese oxide powder, and cerium oxide powder is 0.2 mol / kg), and ball granulation is performed;

[0066] S3, transfer the pellets treated in S2 to a zinc nitrate solution for full immersion, the amount of zinc nitrate used is 0.2 mol / kg, then wash with deionized water, dry at 75°C for 15h, and calcine at 650°C in nitrogen, argon or vacuum atmosphere for 4h;

[0067] S4. Transfer the small balls treated with S3 to a magnesium nitrate solution for full immersion, with the amount of magnesium nitrate being 0.2 mol / kg; then wash with deionized water, dry at 75°C for 15 hours, and calcine at 650°C in a nitrogen, argon or vacuum atmosphere for 4 hours.

[0068] Example 6

[0069] The preparation method of the granular ozone catalyst of the present invention comprises raw materials including: spirulina residue (water content less than 5%) after water extraction of phycocyanin; aluminum oxide powder; copper oxide powder and manganese oxide powder. The preparation method is as follows:

[0070] S1, grinding the alumina powder to 200-1200 mesh and drying it at 105-120°C for later use;

[0071] S2, the spirulina residue, aluminum oxide powder, copper oxide powder and manganese oxide powder are fully mixed (the mixing mass ratio of spirulina residue and aluminum oxide powder is 1:15, and the addition amount of copper oxide powder and manganese oxide powder is 0.5 mol / kg), and granulated by rolling ball to obtain granular material;

[0072] S3. Dry the prepared granular material at 80°C for 12 hours, and then calcine at 500°C in nitrogen, argon or vacuum atmosphere for 5 hours.

[0073] Example 7

[0074] The preparation method of the granular ozone catalyst of the present invention comprises raw materials including: algae residue (water content less than 5%) after astaxanthin is extracted from Haematococcus pluvialis, natural zeolite powder, manganese nitrate solution, copper nitrate solution and zinc nitrate solution.

[0075] The preparation method is as follows:

[0076] S1, drying the ground (200-1200 mesh) natural zeolite powder at 105-120°C for later use;

[0077] S2, mixing the Haematococcus pluvialis residue and natural zeolite powder in a mass ratio of 1:8, and granulating by rolling;

[0078] S3, transferring the pellets treated in S2 to a manganese nitrate solution for full immersion, with a manganese nitrate dosage of 0.25 mol / kg, then washing with deionized water, drying at 60°C for 24 hours, and then calcining at 550°C in nitrogen, argon or vacuum atmosphere for 5 hours;

[0079] S4, transfer the pellets treated in S3 to a copper nitrate solution for full immersion, with the copper nitrate dosage being 0.25 mol / kg, then wash with deionized water, dry at 60°C for 24 hours, and then calcine at 550°C in nitrogen, argon or vacuum atmosphere for 5 hours;

[0080] S5. Transfer the pellets treated with S4 to a zinc nitrate solution for full immersion, with the amount of zinc nitrate being 0.25 mol / kg; then wash with deionized water, dry at 60°C for 24 hours, and then calcine at 550°C in a nitrogen, argon or vacuum atmosphere for 5 hours.

[0081] Example 8

[0082] The preparation method of the granular ozone catalyst of the present invention comprises raw materials including: bloom algae (mainly cyanobacteria, including green algae, Chlamydomonas, etc.), algae residue after oil is extracted from Chlorella (water content is less than 5%); aluminum oxide powder, natural zeolite powder; manganese oxide powder, cerium oxide powder; copper nitrate solution, zinc nitrate solution.

[0083] The preparation method is as follows:

[0084] S1. Dehydrating and drying the algae biomass salvaged from the water body of the algae bloom to reduce its moisture content to less than 5%;

[0085] S2, drying the ground (200-1200 mesh) alumina powder and natural zeolite powder at 105-120°C for later use;

[0086] S3, the bloom algae powder, chlorella algae residue, alumina powder, natural zeolite powder, manganese oxide powder, cerium oxide powder are fully mixed (the mixing ratio of bloom algae powder, chlorella algae residue, alumina powder, natural zeolite powder is 1:1:10:10, and the addition amount of manganese oxide powder and cerium oxide powder is 0.25 mol / kg), and granulation is performed by rolling ball;

[0087] S4, transfer the prepared pellets to a copper nitrate solution for full immersion, the copper nitrate dosage is 0.25 mol / kg, then wash with deionized water, dry at 65°C for 20 h, and then calcine at 600°C in nitrogen, argon or vacuum atmosphere for 4 h;

[0088] S5. Transfer the above-mentioned small balls to a zinc nitrate solution for full immersion, with the amount of zinc nitrate being 0.25 mol / kg; then wash with deionized water, dry at 65°C for 20 hours, and then calcine at 600°C in a nitrogen, argon or vacuum atmosphere for 4 hours.

[0089] Comparative Example 1

[0090] Existing commercial ozone catalysts are supported by alumina and have metals as active components.

[0091] Comparative Example 2

[0092] A metal-based ozone catalyst, the catalyst raw materials include: 94% aluminum oxide powder and 6% manganese oxide. The preparation method is as follows:

[0093] S1, mixing the ground and dried catalyst carrier and active components uniformly;

[0094] S2, placing in a granulator for granulation, adding acetic acid of a certain volume concentration until particles with a uniform particle size of 3 to 4 mm are formed;

[0095] S3. Dry the prepared particles at 120° C. for 12 h, and then calcine at 500° C. in air atmosphere for 3 h.

[0096] Comparative test:

[0097] The above catalyst (Examples 1 to 8, Comparative Examples 1 to 2) was used to deeply treat a certain petrochemical wastewater by ozone catalytic oxidation. The ozone concentration was 3 mg / L, the flow rate was 100 ml / min, the oxidation time was 30 min, the influent TOC concentration was 14.35 mg / L, and the TOC removal rate was as follows: Figure 1 shown.

[0098] Under the same conditions, the TOC removal rate of the ozone catalyst of the present invention is above 50% compared with the raw water. The removal rates of Comparative Examples 1 and 2 are up to 36%, especially Comparative Example 2 is an ozone catalyst without adding algae biomass. It can be seen that the performance of the ozone catalyst based on algae biomass in wastewater treatment of the present invention is significantly improved compared with the comparative example, indicating that the product has good activity and good effect in ozone catalytic oxidation.

[0099] The specific embodiments of the present invention are merely explanations of the present invention and are not limitations of the present invention. After reading this specification, those skilled in the art may make modifications to the embodiments without any creative contribution as needed. However, such modifications are protected by the patent law as long as they are within the scope of the claims of the present invention.

Claims

1. A method for preparing a particulate ozone catalyst based on algae biomass, characterized in that: The following steps are involved: S1. Grind the silicon-aluminum-based mineral powder to 200-1200 mesh, and then dry it at 105-120° C. for more than 24 hours for standby use; S2, mixing algae biomass having a moisture content of less than 5% and silicon-aluminum-based mineral powder in a mass ratio of 1:5 to 1:20 to obtain a mixed material; S3, introducing metal active components into the mixed material by mixing, roasting or mixing-roasting, wherein the amount of the metal active components added is 0.25 to 1 mol / kg, to obtain a granular material; S4, drying the granular material obtained in step S3 at 60-80° C. for at least 12 h, and then calcining at 500-800° C. in a nitrogen, argon or vacuum atmosphere for at least 3 h.

2. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 1, characterized in that: The algae biomass comes from natural water bodies or artificially cultivated blue algae, green algae, diatoms and other organisms, and is dehydrated and dried to a moisture content of less than 5%.

3. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 1, characterized in that: The algae biomass comes from the remaining algae residue after extracting some components from algae, and has a water content of less than 5%.

4. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 1, characterized in that: The silicon-aluminum-based mineral powder is one or more of aluminum oxide powder, natural zeolite and activated diatomaceous earth.

5. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 4, characterized in that: The activation method of the activated diatomite is that the diatomite is fully alkalized in a sodium hydroxide solution, filtered, washed with clean water, and then calcined for activation.

6. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 1, characterized in that: The metal active component is an oxide or nitrate of an active metal; the active metal is one or more of titanium, copper, calcium, manganese, iron, magnesium, zinc, nickel and cerium.

7. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 1, characterized in that: In step S3: The mixing method comprises fully mixing algae biomass, silicon-aluminum-based mineral powder and active metal oxide powder, and then rolling granulation; The impregnation method comprises rolling a mixture of algae biomass and silicon-aluminum-based mineral powders into granules, and transferring the prepared granules into an active metal nitrate solution for full impregnation; The mixing-impregnation method comprises firstly fully mixing algae biomass, silicon-aluminum-based mineral powder and active metal oxide powder, rolling balls for granulation, and then transferring the prepared balls to an active metal nitrate solution for full immersion.

8. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 7, characterized in that: In the impregnation method and mixed-impregnation method, when there are two or more active metal nitrates, after being fully impregnated in one active metal nitrate solution and dried and calcined in step S5, the active metal nitrate solution is then fully impregnated in the next active metal nitrate solution and dried and calcined in step S5.

9. The algae biomass-based particulate ozone catalyst and its preparation method according to claim 8, characterized in that: The drying time is 12 to 24 hours; the roasting time is 3 to 5 hours.

10. A particulate ozone catalyst based on algae biomass prepared by the preparation method of the particulate ozone catalyst based on algae biomass according to claims 1-9.

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