Classifications

• • 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
  • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
• • 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

Definitions

• the present invention relates to a method for producing an olefin production catalyst, an olefin production catalyst, and an olefin production method.
• Non-Patent Document 1 describes that zirconium oxide doped with an alkali metal is used as a catalyst in order to acetonate acetic acid to synthesize acetone.
• Non-Patent Document 2 describes that 2-butanol is dehydrated to produce butenes. Furthermore, it is known that the high selectivity of 1-butene produced using a zirconium oxide catalyst affects the basic properties of the zirconium oxide surface (see, for example, Non-Patent Document 3).
• Patent Document 1 uses an acid catalyst, particularly zeolite, as a method for producing olefin from ethanol.
• an acid catalyst particularly zeolite
• the dehydration reaction of ethanol is accompanied and there is a problem that propylene selectivity is low because a large amount of ethylene is produced.
• Non-Patent Document 4 and Non-Patent Document 5 report that propylene can be obtained from ethanol using indium oxide as a catalyst.
• Various methods for producing indium oxide powder have been known for a long time, and all are for obtaining a high-density sintered body as ITO (Indium-Tin-Oxide) for electronic materials (for example, (See Patent Documents 2 to 5).
• JP 2007-290991 A Japanese Patent Laid-Open No. 5-193939 JP 2003-277052 A JP 2006-264989 A JP 2006-306669 A
• indium oxide is effective as a catalyst for producing an olefin having at least one carbon atom larger than the number of carbon atoms of the alcohol from alcohol.
• the indium oxide catalyst still has room for improvement in terms of catalyst activity and catalyst life.
• the present invention has been made in view of the above-mentioned problems, and the object thereof is an olefin having at least one carbon atom larger than the alcohol using alcohol as a raw material (hereinafter sometimes referred to as “carbonized olefin”). It is an object of the present invention to provide a method for producing an olefin production catalyst, an olefin production catalyst, and an olefin production method that can be produced stably for a long time with a high yield.
• the present inventors have intensively studied to solve the above problems.
• the pH of the precipitation generation reaction is set within a predetermined range, and then aged under specific conditions, thereby producing a carbon-enriched olefin stably at a high yield for a long time. It has been found that a catalyst for producing olefin can be obtained, and the present invention has been completed. That is, the present invention is as follows.
• a precipitation generating step for introducing a precipitant into an aqueous solution to generate a precipitate containing indium, an aging step for aging at 30 ° C. or lower for 25 hours or more after the completion of the charging, and a baking for baking at 500 ° C. to 1000 ° C. after the aging step A process for producing a catalyst for olefin production comprising a step.
• an olefin production catalyst production method and an olefin production catalyst capable of producing an olefin having at least one carbon atom larger than the alcohol from an alcohol as a raw material in a high yield for a long time and A method for producing an olefin can be provided.
• the method for producing an olefin production catalyst according to the present invention includes a precipitation generating step of adding a precipitant to an aqueous solution containing an indium salt to produce a precipitate containing indium until the pH becomes 8.0 or more, and after completion of the addition, It includes an aging step of aging at 30 ° C. or lower for 25 hours or more and a baking step of baking at 500 ° C. to 1000 ° C. after the aging step.
• the catalyst for olefin manufacture which can manufacture a carbon-enriched olefin stably with a high yield for a long time can be manufactured.
• details of each process will be described.
• the indium salt examples include indium nitrate, indium sulfate, indium chloride, and indium acetate. Of these, indium nitrate is preferably used.
• the indium concentration in the aqueous solution containing the indium salt is preferably 0.1 mol / L or more.
• the precipitant mixed with the aqueous solution containing an indium salt it is preferable to use a basic agent that is added to water.
• a basic agent that is added to water.
• ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, urea, etc. are preferably used as these aqueous solutions. Among these, it is more preferable to use ammonia water.
• the precipitant is added to the aqueous solution containing the indium salt until the pH of the mixed solution becomes 8.0 or more.
• the target high performance catalyst can be obtained by adjusting the pH to 8.0 or more.
• a catalyst (indium oxide) having a desired catalytic activity cannot be obtained.
• the pH is preferably 8.0 to 9.8.
• stirring is performed when the precipitant is added, it is preferable to stir the mixed solution so that the precipitated particles in the aqueous solution do not settle, aggregate, or solidify.
• the precipitation rate of the precipitating agent depends on the concentration of the indium salt and the precipitating agent, it is 10 mL / min. The above is preferable.
• the aging step is provided after the completion of charging the precipitant in the precipitation generation step.
• the target high-performance catalyst is obtained by aging under specific conditions after adding the precipitant.
• “aging” refers to an operation of holding a mixed solution containing a precipitate at a predetermined temperature for a predetermined time with stirring.
• the aging temperature in the present invention is 30 ° C. or less, preferably 10 ° C. to 30 ° C., more preferably 20 ° C. to 30 ° C.
• the aging time is 25 hours or more, preferably 30 hours or more. If the aging time is less than 25 hours, indium oxide having desired catalyst performance cannot be obtained.
• the stirring speed is preferably such that the mixed solution is stirred so that the precipitated particles do not settle, aggregate or solidify.
• the mixed solution containing the precipitate obtained through the aging step is filtered to collect the precipitate, washed, dried and calcined, whereby the target catalyst for olefin production of the present invention can be obtained.
• the catalyst when it is in the form of powder, it is appropriately pulverized and sized so as to have a desired particle size range.
• it when it is a pellet form, it grind
• the firing temperature is 500 ° C. to 1000 ° C., preferably 550 ° C. to 950 ° C., and more preferably 600 ° C. to 900 ° C.
• the olefin production catalyst of the present invention is produced by the above-described production method of the olefin production catalyst of the present invention, and contains indium oxide.
• Examples of the form of the catalyst include forms of indium oxide powder and pellets made of indium oxide.
• indium oxide examples include indium oxide (In 2 O 3).
• examples of the type of indium oxide include cubic or amorphous.
• the catalyst for olefin production of the present invention has a specific surface area of 20 m 2 / g or more measured by a nitrogen adsorption method.
• the nitrogen adsorption method is a method in which nitrogen is adsorbed on a solid catalyst at a liquid nitrogen temperature (77 K), and the surface area per unit catalyst weight is calculated from the amount of nitrogen adsorption. According to the method (Yoshio Ono, Isao Suzuki, “Science and Application of Adsorption”, Kodansha Scientific, page 60 (2003)), it can be measured with a commercially available apparatus (BELSORP-max, etc., manufactured by Nippon Bell Co., Ltd.). If the specific surface area of the catalyst is less than 20 m 2 / g, the increased olefin cannot be stably produced with a high yield for a long time.
• the method for producing an olefin of the present invention is to produce an olefin having at least one carbon atom larger than the number of carbon atoms of the raw material alcohol by bringing the alcohol into contact with the above-described catalyst for producing an olefin of the present invention. .
• the alcohol to be reacted with the olefin production catalyst of the present invention is not particularly limited, but is preferably a primary alcohol having 2 to 12 carbon atoms.
• the primary alcohol having 2 to 12 carbon atoms include ethanol, 1-propanol, 1-butanol, isobutanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1- Examples include decanol, 1-undecanol, and 1-dodecanol.
• the alcohol is preferably a primary alcohol having 2 to 8 carbon atoms, and more preferably a primary alcohol having 2 to 4 carbon atoms. If it is alcohol of this range, the selectivity of the carbon-enriched olefin in a product can be improved.
• alcohol bioalcohol
• biological resources biological resources
• the olefin to be produced is not particularly limited.
• the alcohol as a raw material has n carbon atoms, the number of carbon atoms such as 2n-1 (where n is 2 or more), 2n, 3n-1, etc. Olefin is obtained.
• the starting alcohol is ethanol, in addition to ethylene, propylene, 1-butene, cis 2-butene, trans 2-butene, isobutene, pentene, etc.
• the starting alcohol is 1-propanol.
• pentenes, hexenes, octenes and the like can be exemplified in addition to propylene.
• the reaction temperature when the alcohol is brought into contact with the above-described catalyst for producing olefin of the present invention is preferably 300 ° C. to 700 ° C., more preferably 350 ° C. to 600 ° C.
• the contact method is not particularly limited, but alcohol may be simply introduced into the container filled with the catalyst.
• the reactor include a fixed bed reactor, a fluidized bed reactor, a batch reactor, a semi-batch reactor, and the like, but from the viewpoint of productivity of the increased olefin, a fixed bed reactor or A fluidized bed reactor is preferred, and a fixed bed reactor is more preferred.
• the state of the alcohol as the raw material is not particularly limited, it is preferably a gas at the time of reaction from the viewpoint of increasing the efficiency of generating the carbon-enriched olefin and facilitating the reaction.
• Other components include, for example, nitrogen, water vapor, hydrogen, carbon monoxide, carbon dioxide, all or a part of the product recovered from the reactor outlet, the reactivity of the raw material alcohol and the olefin produced.
• An inert carrier gas or the like that is not included in the above can be exemplified. From the viewpoint of stabilizing the catalyst activity, it is preferable that water vapor, hydrogen, and nitrogen coexist among the other components.
• the amount of the olefin production catalyst of the present invention is not particularly limited, but is preferably 0.000002 to 0.02 tons per ton of alcohol.
• the supply rate of alcohol may be, for example, 0.002 ton / h to 200 ton / h per ton of catalyst, and more preferably 0.02 ton / h to 20 ton / h.
• the contact time between the alcohol and the olefin production catalyst is not particularly limited.
• the volume of the raw material subjected to the reaction is calculated in terms of gas at 25 ° C. and 1 atm, it is preferably 0.001 second to 1 hour. More preferably, it is 0.1 second to 1 minute.
• the selection yield of the increased olefin is not particularly limited, but is preferably 1% or more, more preferably 5% or more, and further preferably 10% or more.
• the selective yield of the increased carbon olefin is determined by the following formula.
• alcohol is ethanol and a carbon increase olefin is propylene.
• Example 1 Indium nitrate n-hydrate (In (NO 3 ) 3 .nH 2 O, manufactured by Kanto Chemical Co., Ltd., product number 20298-08, purity 99.9% or more) 21.16 g as an indium source, and deionized water 500.39 g A liquid A was prepared by mixing. Further, 12.22 g of ammonia water (manufactured by Kanto Chemical Co., Ltd., 28-30%) as a precipitant was mixed with 311.15 g of deionized water to prepare solution B.
• In (NO 3 ) 3 .nH 2 O manufactured by Kanto Chemical Co., Ltd., product number 20298-08, purity 99.9% or more
• the obtained white precipitate was filtered, and the operation of stirring in 500 mL of ion exchange water for 3 minutes and then filtering was repeated 3 times.
• the obtained solid was dried at 80 ° C. overnight to obtain an unfired sample.
• This sample is thinly spread on a magnetic dish and 1 ° C./min.
• the mixture was heated to 700 ° C., calcined in the air for 5 hours, and sieved to 0.3 to 0.6 mm to obtain an indium oxide (In 2 O 3 ) catalyst (olefin production catalyst).
• the specific surface area of this catalyst was 31.7 m 2 / g.
• Example 2 A solution A was prepared in the same manner as in Example 1 except that 21.21 g of indium nitrate n hydrate and 500.14 g of deionized water were used. Further, a liquid B was prepared in the same manner as in Example 1 except that 12.16 g of aqueous ammonia and 311.18 g of deionized water were used.
• the obtained white precipitate was filtered, and the operation of stirring in 500 mL of ion exchange water for 3 minutes and then filtering was repeated 3 times.
• the obtained solid was dried at 80 ° C. overnight to obtain an unfired sample.
• This sample is thinly spread on a magnetic dish and 1 ° C./min.
• the mixture was heated to 700 ° C., calcined in the air for 5 hours, and sized by sieving to 0.3 to 0.6 mm to obtain an indium oxide (In 2 O 3 ) catalyst.
• the specific surface area of this catalyst was 22.4 m 2 / g.
• Example 3 A solution A was prepared in the same manner as in Example 1 except that 21.14 g of indium nitrate n hydrate and 50.13 g of deionized water were used. Further, a liquid B was prepared in the same manner as in Example 1 except that 36.79 g of ammonia water and 286.82 g of deionized water were used.
• This sample is thinly spread on a magnetic dish and 1 ° C./min.
• the mixture was heated to 700 ° C., calcined in the air for 5 hours, and sized by sieving to 0.3 to 0.6 mm to obtain an indium oxide (In 2 O 3 ) catalyst.
• the specific surface area of this catalyst was 21.9 m 2 / g.
• Example 1 A solution A was prepared in the same manner as in Example 1 except that 21.19 g of indium nitrate n hydrate and 50.28 g of deionized water were used. Further, a liquid B was prepared in the same manner as in Example 1 except that 12.11 g of ammonia water and 311.14 g of deionized water were used.
• the resulting white precipitate was filtered and dried at 80 ° C. overnight to obtain an unfired sample.
• This sample is thinly spread on a magnetic dish and 1 ° C./min.
• the mixture was heated to 700 ° C., calcined in the air for 5 hours, and sized by sieving to 0.3 to 0.6 mm to obtain an indium oxide (In 2 O 3 ) catalyst.
• the specific surface area of this catalyst was 13.4 m 2 / g.
• a liquid A was prepared in the same manner as in Example 1 except that 42.40 g of indium nitrate n hydrate and 500.14 g of deionized water were used. Further, a liquid B was prepared in the same manner as in Example 1 except that 24.33 g of aqueous ammonia and 311.19 g of deionized water were used.
• This sample is thinly spread on a magnetic dish and 1 ° C./min.
• the mixture was heated to 700 ° C., calcined in the air for 5 hours, and sized by sieving to 0.3 to 0.6 mm to obtain an indium oxide (In 2 O 3 ) catalyst.
• the surface area of this catalyst was 8.4 m 2 / g.
• the gas at the outlet of the reaction tube was analyzed with an online gas chromatograph device every predetermined time, and the propylene yield was calculated.
• the propylene yield was calculated in terms of carbon yield by the following formula. Table 1 shows the propylene yield when each catalyst was used.
• Propylene yield (%) [(Propylene content in product gas (mol / min.) ⁇ 3) / (Ethanol supply amount (mol / min.) ⁇ 2)] ⁇ 100

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=49483310

Family Applications (1)

Country Status (2)

Cited By (1)

Citations (4)

• 2012
  • 2012-04-27 JP JP2012104020A patent/JP5898558B2/ja active Active
• 2013
  • 2013-04-26 WO PCT/JP2013/062443 patent/WO2013162014A1/fr not_active Ceased

Patent Citations (4)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events