NL2024660B1 - Sepiolite derived catalyst with spinel structure, and preparation method and application thereof - Google Patents
Sepiolite derived catalyst with spinel structure, and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention discloses a sepiolite derived catalyst With a spinel structure, and a preparation method and application thereof. The catalyst includes sepiolite used as a carrier and Co (cobalt) loaded on the sepiolite and used as an active ingredient, wherein a part of Co exists in a CoAle4spinel structure form, and the other part of Co exists in a C03O4oxide structure form. In the catalyst, the metallic Co is highly scattered and stably anchored onto a surface of the carrier in a Co—Al spinel form, so that activity and stability of the catalyst are greatly improved, serious sintering and carbon deposition coverage of metal active sites in a reforming process can be avoided, and a service life of the catalyst is further prolonged.
Description
BACKGROUND Technical Field The present invention relates to the field of hydrogen preparation through bio-oil reforming, in particular to a sepiolite derived catalyst with a spinel structure, and a preparation method and application thereof. Related Art As a giant in renewable energy sources, biomass has the characteristics of carbon neutral performance and renewability. In order to improve the utilization efficiency, a bio-oil and bio-oil derivative catalysis steam reforming hydrogen preparation technology becomes the most effective and practical technical path, and conforms to concepts of biomass comprehensive refining, renewable hydrogen energy and the like. The bio-oil and bio-oil derivative steam reforming hydrogen preparation, as a strong heat absorption process, has an ideal reaction shown as follows: C4HmOs + (2n-k) HO = nCO:+ (2n + m/2-k) Hb Bio-oil and bio-oil derivative steam reforming, as a surface structure sensitive gas-solid interface catalysis reaction, belongs to a complicated reaction network including a great number of side reactions. In order to realize a high conversion rate and a high hydrogen gas production rate, a high-performance catalyst is a core of a reforming reaction.
A Chinese patent application with a publication number of 201711377622.6 discloses a Co/sepiolite catalyst which has good performance but is only applicable to catalytic degradation of lignin.
SUMMARY The technical problem to be solved by the present invention is to provide a sepiolite derived catalyst with a spinel structure and with advantages of a high conversion rate, a high hydrogen gas production rate, a stable structure and along service life, and a preparation method and application thereof.
In order to solve the technical problem, the present invention has the following technical scheme that the sepiolite derived catalyst with the spinel structure includes sepiolite used as a carrier and Co (cobalt) loaded on the sepiolite and used as an active ingredient, wherein a part of Co exists in a CoAl204spinel structure form, and the other part of Co exists in a Co;O40xide structure form.
The terms “part” or “the other part”, as used herein, mean that at least one Co atom exists in a corresponding structure form.
A Co-based catalyst is widely studied and applied due to low-temperature reforming and water steam shift reaction activity, low CO/CH: selectivity and mild sintering carbon deposition tendency thereof. Surface metallic Co sites with high stability, homodisperse performance and asmall nanometer dimension are key factors of the catalyst having excellent catalysis reforming activity, good anti-sintering capability and good anti-carbon-deposition capability. The sepiolite contains an impurity Al (aluminum). In the catalyst of the present invention, a part of Co forms a Co-Al spinel phase, and is loaded onto the carrier in a strong metal-carrier interaction form, so that the homodisperse and stable anchoring load effects can be achieved. A part of Co with weak interaction with the carrier exists in a Co3Osform, the reduction is easier, and necessary catalysis activity sites are provided for an initial stage of a reforming reaction.
Further, a content of Co is 2 to 15 wt.%, and the balance is sepiolite. In an implementation process of the present invention, an inventor discovers that by using such a proportioning ratio, an obtained catalyst has a high catalysis conversion rate, a high hydrogen gas production rate and a long service life.
Further, the Co existing in a CoAl:0; spinel structure form accounts for 60 to 90% of a total quantity of the Co. In the implementation process of the present invention, the inventor discovers that if a content of the Co existing in the CoAl,Os spinel structure form is within this range, the catalyst has strong metal-carrier interaction, and a great number of homogeneous-phase and monodisperse stable metallic Co sites are produced after the reduction.
A preparation method of the sepiolite derived catalyst with the spinel structure provided by the present invention includes the following steps of: adding purified sepiolite into a water solution of Co precursor salts and urea; performing a hydrothermal reaction after uniform stirring to obtain a reaction mixed solution; performing cooling and still standing on the reaction mixed solution; then, performing filtration treatment to obtain a filter cake; performing washing and drying treatment on the filter cake; calcining the filter cake sequentially in an air atmosphere and a reducing atmosphere;
and obtaining the sepiolite derived catalyst with the spinel structure.
According to the preparation method provided by the present invention, through a hydrothermal synthesis reaction, metallic Co is partially doped into a sepiolite crystal structure and forms an aluminum cobalt silicate species with framework Al atoms in the sepiolite crystal structure; and then, through high-temperature calcination, a Co-Al spinel phase is produced. Because the surface/body phase framework Al atom content is limited, a little Co3O:can be separated out. In addition, the urea is used as a precipitating agent, and alkaline species such as NH*/HCO;/OH are obtained through slow homogeneous decomposition under a hydrothermal condition. A phenomenon of a locally excessively high concentration or a concentration gradient cannot occur, the generation of homogeneous precipitation is facilitated, the metal dispersion is further improved, and the metal-carrier interaction is regulated and controlled.
Further, in the water solution of the Co precursor salts and the urea, a mol ratio of the urea to Co ions is 2 to 4. In an implementation process of the present invention, the inventor discovers that by using such a proportioning ratio, the Co loading can be effectively ensured, and controllability, safety and economical performance of operation can be influenced by too low or too high concentration of the precipitating agent.
Further, the Co precursor salts are any one of or a mixture obtained by mixing two and more of cobaltous nitrate hexahydrate, cobaltous chloride and cobalt (II) acetate tetrahydrate according to any proportion.
Further, the hydrothermal reaction should be performed for 2 to 6 h at a temperature being 160 to 200 °C and a pressure being 1 to 3 Mpa. In the implementation process of the present invention, the inventor discovers that by using the reaction conditions, the formation of a required structure can be ensured, and economical performance, effectiveness, safety and controllability are realized.
Further, the calcination in the air atmosphere is performed at a temperature of 600 to 800 °C for 2 to 4 h, and the calcination in the reducing atmosphere is performed at a temperature of 600 to 800 °C for 2 to 4 h. In the implementation process of the present invention, the inventor discovers that by using the above-mentioned conditions, the Co loading is facilitated, and the service life of the obtained catalyst is longer.
Further, the reducing atmosphere is a mixed gas of a hydrogen gas and a nitrogen gas with a hydrogen gas volume fraction being 10%. In the implementation process of the present invention, the inventor discovers that by using the above-mentioned condition, the Co reduction is facilitated, and the service life of the obtained catalyst is longer.
Further, the cooling is natural cooling to a room temperature, the time of still standing is 12 to 24 h, and sufficient crystallization can be ensured.
Further, a suction filtration mode is used in filtration, and specifically, a circulation water vacuum suction filtering pump can be used for separating a solid filter cake from turbid liquid formed after still standing.
Further, washing treatment refers to washing filtration for 5 to 10 times by deionized water.
Further, drying treatment refers to drying for 12 to 24 h under the conditions of a normal pressure and 105 °C.
Further, a preparation method of the purified sepiolite includes following step of performing acidification and calcination treatment on sepiolite clay minerals, wherein the acidification refers to normal temperature acidification treatment using 5 to 15 mol/L inorganic acid, and the inorganic acid includes one of hydrochloric acid, nitric acid or sulfuric acid; and the calcination is performed at 600 to 800 °C in an air atmosphere.
According to a concrete process, sepiolite raw materials are added into a 5 to 15 mol/L nitric acid solution; magnetic stirring is performed for 2 to 4 h under a water bath condition; then, suction filtration, washing, drying and mechanical crushing are performed; calcination is performed in a tubular furnace at 600 to 800 °C in the air atmosphere; and the purified sepiolite is obtained.
The application provided by the present invention is application of the sepiolite derived catalyst with the spinel structure to bio-oil and bio-oil derivative catalysis steam reforming hydrogen preparation. According to the application, a catalysis steam reforming hydrogen preparation method is provided and includes the following steps of: adding raw materials and the sepiolite derived catalyst with the spinel structure into a reaction vessel, and performing a reaction at a temperature of 500 °C to 700 °C.
Further, a consumption of the sepiolite derived catalyst with the spinel structure is
0.5to 1.5 g, a feeding quantity of the raw materials is 5 to 15 g/h, and a water-to-carbon mol ratio of the raw materials is 1.5 to 6.In an implementation process of the present invention, the inventor discovers that by using the above-mentioned conditions, a hydrogen preparation reaction is facilitated, and a conversion rate and a hydrogen gas production rate are higher.
The bio-oil is prepared from pine sawdust through pyrolysis under anoxic 5 conditions, and bio-oil derivatives are representative ingredients of ethyl alcohol, acetic acid, acetone and phenol in the bio-oil.
Further, by starting from the balance between feasibility and economical efficiency of a reforming hydrogen preparation reaction, the raw materials are a mixture of the bio-oil, the bio-oil derivatives and water according to a specific mol ratio (1.5 to 6).
The present invention has the following beneficial effects.
1. Metallic Co in the catalyst of the present invention is highly dispersed and stably anchored onto a surface of the carrier in a Co-Al spinel form, so that activity and stability of the catalyst are greatly improved, serious sintering and carbon deposition coverage of metal active sites in a reforming process can be avoided, and the service life of the catalyst is further prolonged.
2. When the catalyst of the present invention is applied to bio-oil and bio-oil derivative reforming hydrogen preparation, under proper conditions, the goals that the raw material conversion rate is 91% or higher, the hydrogen gas production rate is 75% or higher, and the service life 1s 200 h or longer can be achieved. The characteristics of high reforming activity, stable hydrogen gas production rate, long service life, low price and easy preparation are realized. The scale production requirements of the bio-oil and bio-oil derivative catalytic reforming hydrogen preparation can be met.
3. According to the preparation method of the catalyst provided by the present invention, in hydrothermal reaction and calcination processes, the Co and the carrier generate strong interaction to produce a Co-Al spinel phase, raw materials can be easily obtained, the method is simple, and the scale production is easy to realize.
4. According to the preparation method of the catalyst provided by the present invention, the urea is used as the precipitating agent. Compared with a conventional coprecipitation method, the preparation method has the advantages that by using the urea, alkaline species are obtained through slow homogeneous and thorough decomposition under the hydrothermal conditions, practicability, economical performance and process controllability are realized, and metal species agglomeration and inhomogeneous precipitation due to locally excessively high concentration are avoided. Metal dispersity and surface available active site quantity of the catalyst are further improved. The metal-carrier interaction is regulated and controlled. The reforming performance of the catalyst is enhanced. The service life of the catalyst is prolonged.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an X-ray diffraction pattern of a catalyst prepared in Embodiments 1 to 5 of the present invention. Fig. 2 is an X-ray diffraction pattern of a catalyst prepared in Embodiments 1 and 3 of a Chinese patent application with a publication number of 201711377622.6 in the prior art. Fig. 3 is a pine sawdust pyrolysis oil steam reforming hydrogen preparation 200 h activity test of a catalyst prepared in Embodiment 4 of the present invention. Fig. 4 is a pine sawdust pyrolysis oil steam reforming hydrogen preparation 200 h activity test of a catalyst prepared in Embodiment 3 of the Chinese patent application with the publication number of201711377622.6 in the prior art.
DETAILED DESCRIPTION The present invention is further described with reference to embodiments hereafter. Various raw materials used in following embodiments, unless otherwise specified, are all products sold in markets and well known in this field, wherein sepiolite is bought from Xiangtan Yuanyuan Sepiolite New Material Co., Ltd.. Embodiment 1 Preparation of a sepiolite derived catalyst with a spinel structure A content of an active ingredient Co in the sepiolite derived catalyst with the spinel structure prepared in the present embodiment is 2 wt.%, and other ingredients are sepiolite clay. A preparation method includes the following steps of: taking and adding 10.00 g of sepiolite raw materials into 5 mol/L nitric acid; performing magnetic stirring for 2 h under the condition of 80 °C constant temperature water bath; then, performing suction filtration, washing, drying and mechanical crushing to obtain solid powder I; putting the solid powder I into a tubular furnace; heating to 600 °C at a temperature rise speed of 2 °C/min; then, performing calcination for 4 h in an air atmosphere to obtain purified sepiolite; weighing and putting 0.5067 g of Co(NO:3)2:6H:Oand 0.2092 g of urea (a mol ratio of the urea to metal ions Urea/M 1s 2) into a 250 mL round bottom beaker; adding the mixture into 70 mL of deionized water for complete dissolution to obtain a solution I; weighing and adding 5 g of the purified sepiolite into the solution I; putting the material into a water bath pot; performing 40 °C constant temperature stirring for 4 h to form turbid liquid I; adding the turbid liquid I into a high-pressure reaction kettle to perform a hydrothermal reaction; regulating the temperature of the high-pressure reaction kettle to 160 °C, the pressure to 1 Mpa, the rotating speed to 100 r/min and the reaction time to 2 h; after the reaction is completed, performing natural cooling on the high-pressure reaction kettle to a room temperature; performing aging and still standing for 12 h to form a solid-liquid mixture I, performing suction filtration, washing, drying and sieving on the solid-liquid mixture I to obtain solid powder II; putting the solid powder II into the tubular furnace; raising the temperature from the room temperature to 600 °C at a temperature rise speed of 2 °C/min in the air atmosphere; performing constant temperature calcination for 4 h; then, cooling the materials to the room temperature; next, introducing a mixed gas of a hydrogen gas and a nitrogen gas with a hydrogen gas volume fraction being 10%; raising the temperature from the room temperature to 600 °C at a temperature rise speed of 2 °C/min; cooling the materials to the room temperature after the constant temperature calcinations is performed for 4 h; and obtaining the sepiolite derived catalyst with the spinel structure and with a serial number being 1.
According to the present embodiment, through characterization detection calculation, Co existing in a CoAl2O4 spinel structure form accounts for 90.3% of the total quantity of the Co, and Co existing in a Co;04 oxide structure form accounts for
7.8% of the total quantity of the Co.
Embodiment 2 Preparation of a sepiolite derived catalyst with a spinel structure A content of an active ingredient Co in the sepiolite derived catalyst with the spinel structure prepared in the present embodiment is 5 wt.%, and other ingredients are sepiolite clay. A preparation method includes the following steps of: taking and adding 10.00g of sepiolite raw materials into 10 mol/L nitric acid; performing magnetic stirring for 3 h under the condition of 60 °C constant temperature water bath; then, performing suction filtration, washing, drying and mechanical crushing to obtain solid powder I, putting the solid powder I into a tubular furnace; heating to 650 °C at a temperature rise speed of 3 °C/min; then, performing calcination for 4 h in an air atmosphere to obtain purified sepiolite; weighing and putting 1.0777 g of CoCl::6H;Oand 0.5411 g of urea (a mol ratio of the urea to metal ions Urea/M is 2) into a 250 mL round bottom beaker; adding the mixture into 70 mL of deionized water for complete dissolution to obtain a solution I; weighing and adding 5 g of the purified sepiolite into the solution I; putting the material into a water bath pot; performing 40 °C constant temperature stirring for 2 h to form turbid liquid I; adding the turbid liquid I into a high-pressure reaction kettle to perform a hydrothermal reaction; regulating the temperature of the high-pressure reaction kettle to 170 °C, the pressure to 2 Mpa, the rotating speed to 120 r/min and the reaction time to 3 h; after the reaction is completed, performing natural cooling on the high-pressure reaction kettle to a room temperature; performing aging and still standing for 14 h to form a solid-liquid mixture I; performing suction filtration, washing, drying and sieving on the solid-liquid mixture I to obtain solid powder II; putting the solid powder II into the tubular furnace; raising the temperature from the room temperature to 650 °C at a temperature rise speed of 3 °C/min in the air atmosphere; performing constant temperature calcination for 3 h; then, cooling the materials to the room temperature; next, introducing a mixed gas of a hydrogen gas and a nitrogen gas with a hydrogen gas volume fraction being 10%; raising the temperature from the room temperature to 650 °C at a temperature rise speed of 3 °C/min; cooling the materials to the room temperature after the constant temperature calcination for is performed for3 h; and obtaining the sepiolite derived catalyst with the spinel structure and with a serial number being 2.
According to the present embodiment, through characterization detection calculation, Co existing in a CoAl:O, spinel structure form accounts for 87.8% of the total quantity of the Co, and Co existing in a Coz0s4 oxide structure form accounts for
9.4% of the total quantity of the Co.
Embodiment 3 Preparation of a sepiolite derived catalyst with a spinel structure A content of an active ingredient Co in the sepiolite derived catalyst with the spinel structure prepared in the present embodiment is 8 wt.%, and other ingredients are sepiolite clay. A preparation method includes the following steps of: taking and adding 10.00g of sepiolite raw materials into 15 mol/L nitric acid; performing magnetic stirring for 2 h under the condition of 40 °C constant temperature water bath; then, performing suction filtration, washing, drying and mechanical crushing to obtain solid powder I, putting the solid powder I into a tubular furnace; heating to 700 °C at a temperature rise speed of 4 °C/min; then, performing calcination for 2 h in an air atmosphere to obtain purified sepiolite; weighing and putting 1.8818 g of CH;COOCo-4H;0and 1.3613 g of urea (a mol ratio of the urea to metal ions Urea/M is 3) into a 250 mL round bottom beaker; adding the mixture into 70 mL of deionized water for complete dissolution to obtain a solution I; weighing and adding 5 g of the purified sepiolite into the solution I; putting the material into a water bath pot; performing 40 °C constant temperature stirring for 3 h to form turbid liquid I; adding the turbid liquid I into a high-pressure reaction kettle to perform a hydrothermal reaction; regulating the temperature of the high-pressure reaction kettle to 180 °C, the pressure to 3 Mpa, the rotating speed to 150 r/min and the reaction time to 3 h; after the reaction is completed, performing natural cooling on the high-pressure reaction kettle to a room temperature; performing aging and still standing for 16 h to form a solid-liquid mixture I, performing suction filtration, washing, drying and sieving on the solid-liquid mixture I to obtain solid powder II; putting the solid powder II into the tubular furnace; raising the temperature from the room temperature to 700 °C at a temperature rise speed of 4 °C/min in the air atmosphere; performing constant temperature calcination for 2 h; then, cooling the materials to the room temperature; next, introducing a mixed gas of a hydrogen gas and a nitrogen gas with a hydrogen gas volume fraction being 10%; raising the temperature from the room temperature to 700 °C at a temperature rise speed of 4 °C/min; cooling the materials to the room temperature after the constant temperature calcination is performed for 2 h; and obtaining the sepiolite derived catalyst with the spinel structure and with a serial number being 3. According to the present embodiment, through characterization detection calculation, Co existing in a CoAl,Osspinel structure form accounts for 85.6% of the total quantity of the Co, and Co existing in a Co3;O4 oxide structure form accounts for
13.6% of the total quantity of the Co. Embodiment 4
Preparation of a sepiolite derived catalyst with a spinel structure A content of an active ingredient Co in the sepiolite derived catalyst with the spinel structure prepared in the present embodiment is 10 wt.%, and other ingredients are sepiolite clay. A preparation method includes the following steps of: taking and adding 10.00g of sepiolite raw materials into 5 mol/L nitric acid; performing magnetic stirring for 4 h under the condition of 80 °C constant temperature water bath; then, performing suction filtration, washing, drying and mechanical crushing to obtain solid powder I; putting the solid powder I into a tubular furnace; heating to 750 °C at a temperature rise speed of 4 °C/min; then, performing calcination for 3 hin an air atmosphere to obtain purified sepiolite; weighing and putting 2.8285 g of Co(NO:3)26H:Oand 1.7512 g of urea (a mol ratio of the urea to metal ions Urea/M 1s 3) into a 250 mL round bottom beaker; adding the mixture into 70 mL of deionized water for complete dissolution to obtain a solution I; weighing and adding 5 g of the purified sepiolite into the solution I; putting the material into a water bath pot; performing 40 °C constant temperature stirring for 4 h to form turbid liquid I; adding the turbid liquid I into a high-pressure reaction kettle to perform a hydrothermal reaction; regulating the temperature of the high-pressure reaction kettle to 190 °C, the pressure to
1.5 Mpa, the rotating speed to 170 r/min and the reaction time to 4 h; after the reaction is completed, performing natural cooling on the high-pressure reaction kettle to a room temperature; performing aging and still standing for 24 h to form a solid-liquid mixture I, performing suction filtration, washing, drying and sieving on the solid-liquid mixture I to obtain solid powder II; putting the solid powder II into the tubular furnace; raising the temperature from the room temperature to 750 °C at a temperature rise speed of 4 °C/min in the air atmosphere; performing constant temperature calcination for 3 h; then, cooling the materials to the room temperature; next, introducing a mixed gas of a hydrogen gas and anitrogen gas with a hydrogen gas volume fraction being 10%; raising the temperature from the room temperature to 750 °C at a temperature rise speed of 4 °C/min; cooling the materials to the room temperature after the constant temperature calcination is performed for 3 h; and obtaining the sepiolite derived catalyst with the spinel structure and with a serial number being 4. According to the present embodiment, through characterization detection calculation, Co existing in a CoAl;Osspinel structure form accounts for 77.5% of the total quantity of the Co, and Co existing in a Co;04 oxide structure form accounts for
20.9% of the total quantity of the Co. Embodiment 5 Preparation of a sepiolite derived catalyst with a spinel structure A content of an active ingredient Co in the sepiolite derived catalyst with the spinel structure prepared in the present embodiment is 15 wt.%, and other ingredients are sepiolite clay. A preparation method includes the following steps of: taking and adding 10.00g of sepiolite raw materials into 10 mol/L nitric acid; performing magnetic stirring for 4 h under the condition of 60 °C constant temperature water bath; then, performing suction filtration, washing, drying and mechanical crushing to obtain solid powder I, putting the solid powder I into a tubular furnace; heating to 800 °C at a temperature rise speed of 5 °C/min; then, performing calcination for 2 h in an air atmosphere to obtain purified sepiolite; weighing and putting 3.7411 g of CoCl,-6H:0and 3.7774 g of urea (a mol ratio of the urea to metal ions Urea/M is 4) into a 250 mL round bottom beaker; adding the mixture into 70 mL of deionized water for complete dissolution to obtain a solution I; weighing and adding 5 g of the purified sepiolite into the solution I; putting the material into a water bath pot; performing 40 °C constant temperature stirring for 4 h to form turbid liquid I; adding the turbid liquid I into a high-pressure reaction kettle to perform a hydrothermal reaction; regulating the temperature of the high-pressure reaction kettle to 200 °C, the pressure to 2.5 Mpa, the rotating speed to 200 r/min and the reaction time to 6 h; after the reaction is completed, performing natural cooling on the high-pressure reaction kettle to a room temperature; performing aging and still standing for 18 h to form a solid-liquid mixture I; performing suction filtration, washing, drying and sieving on the solid-liquid mixture I to obtain solid powder II; putting the solid powder II into the tubular furnace; raising the temperature from the room temperature to 800 °C at a temperature rise speed of 5 °C/min in the air atmosphere; performing constant temperature calcination for 2 h; then, cooling the materials to the room temperature; next, introducing a mixed gas of a hydrogen gas and a nitrogen gas with a hydrogen gas volume fraction being 10%; raising the temperature from the room temperature to 800 °C at a temperature rise speed of 5 °C/min; cooling the materials to the room temperature after the constant temperature calcination 1s performed for 2 h; and obtaining the sepiolite derived catalyst with the spinel structure and with a serial number being 5.
According to the present embodiment, through characterization detection calculation, Co existing in a CoAl;Ouspinel structure form accounts for 71.4% of the total quantity of the Co, and Co existing in a Coz0s4 oxide structure form accounts for
25.9% of the total quantity of the Co.
Embodiment 6 Structure test of a sepiolite derived catalyst with a spinel structure Fig. 1 is an X-ray diffraction pattern of the catalyst prepared in Embodiments 1 to 5 of the present invention. According to a JCPDF card, it is recognized that obvious CoAlOsspinel diffraction peaks occur when 29 is 36.7°, 44.7° and 65.0°, and meanwhile, diffraction peaks of a small amount of CosO:are shielded, so that asymmetry of the spinel diffraction peaks is caused.
Fig. 2 is an X-ray diffraction pattern of a catalyst prepared in Embodiments 1 and 3 of a Chinese patent application with a publication number of 201711377622.6 in the prior art. According to a JCPDF card, it is recognized that symmetrical Co3Oadiffraction peaks occur when 26 is 36.99, 44.8%nd 65.2° the peak intensity increases when a load quantity increases, and the result shows that an increase of a crystallinity degree is caused by sintering process agglomeration.
The result proves that the present invention realizes the preparation of the sepiolite derived catalyst with the spinel structure. An active ingredient Co in the catalyst mostly exists in a CoAl;Osspinel structure form and a Co30: oxide structure form. The catalyst prepared in Embodiments 1 and 3 of the Chinese patent application with the publication number of 201711377622.6 in the prior art does not form the CoAl:O:spinel structure, and the Co mostly exists in the Co30: oxide structure form. In addition, the structure tests on other embodiments of the Chinese patent application with the publication number of 201711377622.6 also prove that a CoAl2Ouspinel structure is not formed. Further description by drawing is omitted herein for the sake of brevity.
Embodiment 7 Bio-oil and bio-oil derivative catalysis reforming hydrogen preparation test of a sepiolite derived catalyst with a spinel structure
0.5 to 1.5 g of the catalyst in Embodiments 1 to 5 is taken and put into a fixed bed reaction vessel, a feeding quantity of reactant raw materials is 5 to 15 g/h, the water-to-carbon mol ratio (S/C) of the raw materials is 1.5 to 6, and the reaction temperature is 500 to 700 °C. Concrete reaction conditions and results are shown in Table 1. Table 1 | | Reactioncondion | Experimentresult | Catalyst ] Reaction |Feeding| Catalyst Raw | Hydrogen . . Raw ‚ . material gas Service serial dal S/C | temperature’ | speed |consumption/ ducti life/h number materia C Ag /h) & conversion | pro uction| life rate/%o rate/% 2 Ethyl | 500 15 0.5 95.3 80.1 400 alcohol acid Pine 4 sawdust | ¢ 700 5 15 91.6 75.1 200 pyrolysis oil 700 Pine Comparativ | sawdust | 700 5 15 50.8 473 20 e example |pvrolysis oil Note: the comparative example is the catalyst prepared in Embodiment 3 in the Chinese patent application with the publication number of 201711377622.6.
From the above results, the sepiolite derived catalyst with the spinel structure of the present invention can realize a raw material conversion rate being 91% or higher, a hydrogen gas production rate being 75% or higher, and a service life being 200 h or longer.
Fig. 3 is a stability test figure of pine sawdust pyrolysis oil reforming hydrogen preparation catalyzed by the sepiolite derived catalyst with the spinel structure prepared in Embodiment 4 of the present invention. Fig. 4 is a stability test figure of pine sawdust pyrolysis oil catalyzed by the catalyst prepared in Embodiment 3 of the Chinese patent application with the publication number of 201711377622.6. It shows that the performance of the catalyst of the present invention is much higher than that of the Chinese patent application with the publication number of 201711377622.6 in the prior art.
It should also be understood that examples and implementation modes according to the present invention are only used for illustration, and are not intended to limit the present invention.
Those in the art can make various modifications or changes according to the present invention.
All modifications, equivalent replacement, improvement, etc. made within the spirit and the principle of the present invention shall be included in the protection scope of the present invention.
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