JP5595005B2 - Method for producing catalyst for oxychlorination - Google Patents
Method for producing catalyst for oxychlorination Download PDFInfo
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- JP5595005B2 JP5595005B2 JP2009240687A JP2009240687A JP5595005B2 JP 5595005 B2 JP5595005 B2 JP 5595005B2 JP 2009240687 A JP2009240687 A JP 2009240687A JP 2009240687 A JP2009240687 A JP 2009240687A JP 5595005 B2 JP5595005 B2 JP 5595005B2
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- 239000003054 catalyst Substances 0.000 title claims description 117
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000002002 slurry Substances 0.000 claims description 104
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 82
- 238000001694 spray drying Methods 0.000 claims description 60
- 239000007864 aqueous solution Substances 0.000 claims description 56
- 238000010304 firing Methods 0.000 claims description 36
- 229910052783 alkali metal Inorganic materials 0.000 claims description 33
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 26
- 150000001340 alkali metals Chemical class 0.000 claims description 24
- -1 alkaline earth metal salt Chemical class 0.000 claims description 21
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 150000004645 aluminates Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 63
- 239000000017 hydrogel Substances 0.000 description 56
- 239000002245 particle Substances 0.000 description 51
- 230000000694 effects Effects 0.000 description 38
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 23
- 239000005977 Ethylene Substances 0.000 description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 22
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 22
- 230000007423 decrease Effects 0.000 description 21
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 20
- 239000012266 salt solution Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 13
- 239000011164 primary particle Substances 0.000 description 13
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 229940063656 aluminum chloride Drugs 0.000 description 11
- 229960003280 cupric chloride Drugs 0.000 description 11
- 150000002910 rare earth metals Chemical class 0.000 description 11
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 10
- 239000011163 secondary particle Substances 0.000 description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000000265 homogenisation Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000012798 spherical particle Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 8
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000011033 desalting Methods 0.000 description 8
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000001629 suppression Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 239000011268 mixed slurry Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229940091250 magnesium supplement Drugs 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 238000006388 chemical passivation reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000286819 Malo Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPKITLFRFSTZCI-UHFFFAOYSA-L O.[OH-].[OH-].[Cu++] Chemical compound O.[OH-].[OH-].[Cu++] NPKITLFRFSTZCI-UHFFFAOYSA-L 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、流動性、流動性の低下抑制、耐摩耗性等に優れると共に活性、１，２−ジクロルエタン（1,2-ethylene dichloride。以下、ＥＤＣと略記することがある。）の選択性、エチレン燃焼抑制等に優れ、しかも、エロージョンを低減できるオキシクロリネーション用触媒の製造方法に関する。 The present invention is excellent in fluidity, fluidity reduction suppression, abrasion resistance and the like, and active, selectivity of 1,2-dichloroethane (hereinafter sometimes abbreviated as EDC), The present invention relates to a method for producing an oxychlorination catalyst that is excellent in suppressing ethylene combustion and that can reduce erosion.
従来、オキシクロリネーション法（オキシ塩素化法）による脂肪族炭化水素の塩素化には一般に、多孔質なアルミナ、シリカアルミナ、粘土などの担体に金属塩を担持させた触媒が用いられていた。特に、エチレンのオキシクロリネーションによるＥＤＣの製造には、工業的には古くから塩化第二銅を含浸法によりアルミナ担体に担持させた流動床用触媒が用いられる。しかし、この触媒は活性成分である銅が移動あるいは昇華し、活性の低下や流動性の低下を引き起こし、この結果、触媒層の温度分布が不均一となり高温部においてエチレンの燃焼反応が進行し、ＥＤＣの選択性や収率が低下する等の問題があった。銅の移動、昇華を抑制する為に、更には選択性を向上させるためにアルカリ金属、アルカリ土類金属、希土類金属等を添加することが行われている。 Conventionally, for chlorination of aliphatic hydrocarbons by the oxychlorination method (oxychlorination method), a catalyst in which a metal salt is supported on a carrier such as porous alumina, silica alumina, and clay has been used. In particular, for production of EDC by oxychlorination of ethylene, a fluidized bed catalyst in which cupric chloride is supported on an alumina support by an impregnation method has been used industrially. However, in this catalyst, copper, which is an active component, moves or sublimes, causing a decrease in activity and a decrease in fluidity. There was a problem that the selectivity and yield of EDC were lowered. In order to suppress copper migration and sublimation, addition of an alkali metal, an alkaline earth metal, a rare earth metal, or the like is further performed in order to improve selectivity.
一方、担体成分と活性成分を同時に沈殿（以下、共沈法ということがある。）させ、噴霧乾燥して得た触媒が知られている（特許文献１参照）。更に、共沈法で調合して得た触媒にアルカリ金属、アルカリ土類金属、希土類金属等を担持した触媒も知られている（特許文献２〜４参照）。
本願発明者等は、アルミナ源としてあらかじめ調製した擬ベーマイトアルミナスラリーを用い、これに銅等の活性成分、アルカリ金属、アルカリ土類金属、希土類金属等の助触媒成分を加え、噴霧乾燥して得られる触媒は前記流動性の低下が少なく、かつ、高い活性と選択性を示すことを開示している（特許文献５、６参照）。
On the other hand, a catalyst obtained by simultaneous precipitation (hereinafter sometimes referred to as coprecipitation method) of a carrier component and an active component and spray drying is known (see Patent Document 1). Furthermore, a catalyst in which an alkali metal, an alkaline earth metal, a rare earth metal or the like is supported on a catalyst obtained by coprecipitation is also known (see Patent Documents 2 to 4).
The inventors of the present invention use a pseudo boehmite alumina slurry prepared in advance as an alumina source, add an active component such as copper, a promoter component such as an alkali metal, an alkaline earth metal, and a rare earth metal, and spray dry it. It is disclosed that the obtained catalyst has little decrease in fluidity and exhibits high activity and selectivity (see Patent Documents 5 and 6).
しかしながら、従来の流動床オキシクロリネーションでは、時間の経過とともに活性、選択性が低下したり、触媒が磨耗して飛散しがちであるので、触媒の一部を抜き出しながら、新たな触媒の補給が行われている。また、従来のアルミナを担体とする触媒では初期の活性及び選択性は比較的よいものの、長期に性能を維持することができず、シリカアルミナを担体とする触媒では初期の活性及び選択性が不充分であることに加えてエチレンの燃焼反応が進行しＥＤＣの選択性や収率が低下する問題があった。更にエチレンの燃焼反応の抑制、ＥＤＣの選択性や収率が低下の抑制が求められている。
また、耐摩耗性が高い触媒では、装置の内壁を削るというエロージョンが発生し、プラントの寿命が短くなると共に、その補修コストが高くなるという問題があった。
However, in the conventional fluidized bed oxychlorination, the activity and selectivity decrease with the passage of time, and the catalyst tends to be worn out and scattered, so that a new catalyst can be replenished while extracting a part of the catalyst. Has been done. In addition, although the initial activity and selectivity are relatively good with conventional alumina-supported catalysts, the performance cannot be maintained over a long period of time, and the catalyst with silica-alumina supports does not have the initial activity and selectivity. In addition to being sufficient, the combustion reaction of ethylene progressed, and there was a problem that the selectivity and yield of EDC were lowered. Furthermore, suppression of the combustion reaction of ethylene and suppression of reduction in EDC selectivity and yield are required.
In addition, a catalyst with high wear resistance has a problem that erosion of cutting the inner wall of the apparatus occurs, shortening the life of the plant and increasing its repair cost.
本発明は、流動性、流動性の低下抑制、耐摩耗性等に優れると共に活性、ＥＤＣの選択性、エチレン燃焼抑制等に優れ、しかも、エロージョンを低減できるオキシクロリネーション用触媒の製造方法を提供することを発明が解決しようとする課題とする。 The present invention provides a method for producing a catalyst for oxychlorination that is excellent in fluidity, fluidity reduction suppression, wear resistance and the like, is excellent in activity, EDC selectivity, ethylene combustion suppression, etc., and can reduce erosion. This is a problem to be solved by the invention.
本願発明者等は鋭意検討した結果、オキシクロリネーション用触媒を製造する際に、焼成物にアルカリ土類金属塩水溶液及び／又はアルカリ金属塩水溶液から選ばれる少なくとも１種の金属塩水溶液を含浸した後、焼成することにより、優れた性能（流動性、流動性の低下抑制、耐摩耗性、エチレンの燃焼反応の抑制、ＥＤＣの選択性や収率の低下を抑制等）を維持したまま、エロージョンを低減できることを見出して本発明を完成するに至った。 As a result of diligent study, the inventors of the present application impregnated the calcined product with at least one metal salt aqueous solution selected from an alkaline earth metal salt aqueous solution and / or an alkali metal salt aqueous solution when producing an oxychlorination catalyst. After firing, erosion while maintaining excellent performance (fluidity, fluidity reduction suppression, wear resistance, ethylene combustion reaction suppression, EDC selectivity and yield reduction suppression, etc.) As a result, the present invention was completed.
本発明に係るオキシクロリネーション用触媒の製造方法は、下記の工程（ａ）、（ｃ）〜（ｈ）からなることを特徴とする。
（ａ）アルミニウム塩水溶液にアルミン酸アルカリ水溶液と第二銅塩水溶液とを混合して噴霧乾燥用スラリーを調製する工程
（ｃ）前記噴霧乾燥用スラリーを噴霧乾燥して噴霧乾燥物を得る工程
（ｄ）前記噴霧乾燥物を洗浄して洗浄物を得る工程
（ｅ）前記洗浄物を乾燥して乾燥物を得る工程
（ｆ）前記乾燥物を焼成して焼成物を得る工程
（ｇ）前記焼成物に、アルカリ土類金属塩水溶液及び／又はアルカリ金属塩水溶液から選ばれる少なくとも１種の金属塩水溶液を含浸して含浸物を得る工程
（ｈ）前記含浸物を焼成する工程
The method for producing an oxychlorination catalyst according to the present invention comprises the following steps (a) and (c) to (h).
(A) Step of preparing an aqueous solution of aluminum salt and an aqueous solution of alkali aluminate and an aqueous solution of cupric salt to prepare a slurry for spray drying (c) Step of spray drying the slurry for spray drying to obtain a spray dried product ( d) washing the spray-dried product to obtain a washed product (e) drying the washed product to obtain a dried product (f) firing the dried product to obtain a baked product (g) firing A step of impregnating a product with at least one metal salt aqueous solution selected from an alkaline earth metal salt aqueous solution and / or an alkali metal salt aqueous solution to obtain an impregnated product (h) a step of firing the impregnated product
前記工程（ｈ）で得られたオキシクロリネーション用触媒は、アルカリ土類金属が酸化物として、０．１〜６質量％含まれている、及び／又は、アルカリ金属が、酸化物として、０．１〜３質量％含まれていることが好ましい。
前記アルカリ土類金属塩及び／又はアルカリ金属塩は、硝酸塩又は塩化物であることが好ましい。
前記工程（ｈ）で得られたオキシクロリネーション用触媒は、酸化物（ＣｕＯ）として５〜２０質量％の範囲の銅、およびＡl2Ｏ3として４０〜９０質量％の範囲の担体アルミナを含むことが好ましい。
The catalyst for oxychlorination obtained in the step (h) contains 0.1 to 6% by mass of an alkaline earth metal as an oxide, and / or 0% of an alkali metal as an oxide. It is preferable that 1-3 mass% is contained.
The alkaline earth metal salt and / or alkali metal salt is preferably nitrate or chloride.
The catalyst for oxychlorination obtained in the step (h) contains 5 to 20% by mass of copper as an oxide (CuO) and a carrier alumina in the range of 40 to 90% by mass as Al 2 O 3. It is preferable.
本発明のオキシクロリネーション用触媒の製造方法は、焼成物にアルカリ土類金属塩水溶液及び／又はアルカリ金属塩水溶液から選ばれる少なくとも１種の金属塩水溶液を含浸した後、焼成するので、アルカリ土類金属及び／又はアルカリ金属が焼成物中の酸点（特に、強酸点）に担持され、過剰な酸化反応を抑制し、高Ｃｌ転化率が維持できると共に、アルカリ土類金属及び／又はアルカリ金属が従来の触媒よりも外表面に多く担持されることにより、従来の触媒よりも柔らかくなり、エロージョンを低減すると解される。
In the method for producing an oxychlorination catalyst of the present invention, the fired product is impregnated with at least one metal salt aqueous solution selected from an alkaline earth metal salt aqueous solution and / or an alkali metal salt aqueous solution and then calcined. Alkali metals and / or alkali metals are supported on acid points (especially strong acid points) in the fired product to suppress excessive oxidation reaction and maintain a high Cl conversion rate, and also to alkaline earth metals and / or alkali metals Is supported on the outer surface more than the conventional catalyst, so that it becomes softer than the conventional catalyst and erosion is reduced.
［オキシクロリネーション用触媒］
本発明に係るオキシクロリネーション用触媒は、銅及び担体アルミナを含んでいる。
銅の含有量は、酸化物（ＣｕＯ）として５〜２０質量％、更には８〜１５質量％の範囲にあることが好ましい。銅の含有量が５質量％未満の場合は、活性が不充分となり、ＥＤＣの収率が低下する。銅の含有量が２０質量％を超えると、原料エチレンの燃焼が顕著になり、ＥＤＣの収率が低下するとともに、銅が多すぎて触媒粒子外部表面に移動したり、昇華し、流動性低下の原因となることがある。
[Catalyst for oxychlorination]
The catalyst for oxychlorination according to the present invention contains copper and carrier alumina.
The copper content is preferably 5 to 20% by mass, more preferably 8 to 15% by mass, as an oxide (CuO). When the copper content is less than 5% by mass, the activity is insufficient and the yield of EDC is lowered. When the copper content exceeds 20% by mass, combustion of the raw material ethylene becomes remarkable, and the yield of EDC decreases, too much copper moves to the external surface of the catalyst particles, sublimates, and fluidity decreases. It may cause.
本発明の触媒は、担体としてのアルミナをＡｌ2Ｏ3として４０〜９０質量％、更には６０〜８２質量％の範囲で含有することが好ましい。アルミナの含有量が４０質量％未満の場合は、触媒の比表面積及び細孔容積が小さくなり、比表面積及び細孔容積が小さい一方で活性成分等が多くなるため活性が有効に発現しないことがある。また、耐摩耗性が不充分となることがある。アルミナの含有量が９０質量％を超えると、活性成分及び／又はアルカリ土類金属、アルカリ金属、希土類金属等の助触媒成分が少なくなり活性又は選択性が不充分となることがある。
また、担体アルミナがγ-Ａｌ2Ｏ3であると、触媒の比表面積、細孔容積が大きく、触媒の活性、選択性とともに耐久性に優れる。
The catalyst of the present invention preferably contains alumina as a carrier in the range of 40 to 90% by mass, more preferably 60 to 82% by mass as Al 2 O 3 . When the content of alumina is less than 40% by mass, the specific surface area and pore volume of the catalyst become small, and the specific surface area and pore volume are small, but the active component and the like increase, so that the activity may not be effectively expressed. is there. In addition, the wear resistance may be insufficient. If the content of alumina exceeds 90% by mass, the active component and / or promoter components such as alkaline earth metal, alkali metal, rare earth metal, etc. may be reduced, resulting in insufficient activity or selectivity.
Further, when the carrier alumina is γ-Al 2 O 3 , the specific surface area and pore volume of the catalyst are large, and the durability and the activity and selectivity of the catalyst are excellent.
本発明に係るオキシクロリネーション用触媒は、アルカリ土類金属及び／又はアルカリ金属から選ばれる少なくとも１種の金属を含んでいる。
ここで、アルカリ土類金属の含有量は、酸化物（ＭＯ：Ｍはアルカリ土類金属元素を示す）として、０．１〜６質量％、更には０．２〜４質量％の範囲にあることが好ましい。アルカリ土類金属の含有量が０．１質量％未満の場合は、得られる触媒の嵩密度、耐摩耗性が低下する傾向がある。アルカリ土類金属の含有量が６質量％を超えると、得られる触媒の細孔容積が低下し、活性が不充分となることがある。
前記アルカリ土類金属としてはマグネシウムが好ましく、マグネシウムを用いると活性を低下させることなく耐摩耗性に優れた触媒を得ることができる。
The catalyst for oxychlorination according to the present invention contains at least one metal selected from alkaline earth metals and / or alkali metals.
Here, the content of the alkaline earth metal is in the range of 0.1 to 6% by mass, further 0.2 to 4% by mass as an oxide (MO: M represents an alkaline earth metal element). It is preferable. When the content of alkaline earth metal is less than 0.1% by mass, the bulk density and wear resistance of the resulting catalyst tend to decrease. When the content of the alkaline earth metal exceeds 6% by mass, the pore volume of the resulting catalyst is lowered, and the activity may be insufficient.
Magnesium is preferable as the alkaline earth metal. When magnesium is used, a catalyst having excellent wear resistance can be obtained without reducing the activity.
また、アルカリ金属の含有量は、酸化物（Ｎ2Ｏ：Ｎはアルカリ金属元素を示す）として、０．１〜３質量％、更には０．２〜２質量％の範囲にあることが好ましい。アルカリ金属の含有量が０．１質量％未満の場合は、エチレンの燃焼を抑制する効果が不充分となるためにＥＤＣの収率が低下する。アルカリ金属の含有量が３質量％を超えると、Ｃｌの反応率が低下しＥＤＣの収率が低下する。
前記アルカリ金属としてはカリウムが好ましい。カリウムを用いるとエチレンの酸化抑制効果が他のアルカリ金属に比してマイルドであり、主反応である酸素を介し塩酸から生成されるＣｌのエチレンへの付与反応の活性を大きく低下することなく、エチレンの酸化を抑制することが容易である。
The content of alkali metal oxide: as (N 2 O N represents an alkali metal element), 0.1 to 3 wt%, more preferably in the range of 0.2 to 2 wt% . When the content of the alkali metal is less than 0.1% by mass, the effect of suppressing the combustion of ethylene becomes insufficient, so that the yield of EDC is lowered. When the content of the alkali metal exceeds 3% by mass, the reaction rate of Cl decreases and the yield of EDC decreases.
The alkali metal is preferably potassium. When potassium is used, the oxidation inhibition effect of ethylene is milder than that of other alkali metals, and without significantly reducing the activity of the reaction of imparting Cl to ethylene from hydrochloric acid via oxygen, which is the main reaction, It is easy to suppress ethylene oxidation.
更に、本発明の触媒には希土類金属を含んでいてもよく、希土類金属の含有量は酸化物（ＲＥ2Ｏ3：ＲＥは希土類金属元素を示す）として０．１〜６質量％、更には０．２〜４質量％の範囲にあることが好ましい。希土類金属の含有量が０．１質量％未満の場合は、ＥＤＣの選択性が低下するとともに、エチレンの燃焼を抑制する効果が不充分となるためにＥＤＣの収率も低下する。希土類金属の含有量が６質量％を超えると、Ｃｌの反応率が低下しＥＤＣの収率が低下する。 Furthermore, the catalyst of the present invention may contain a rare earth metal, and the content of the rare earth metal is 0.1 to 6% by mass as an oxide (RE 2 O 3 : RE represents a rare earth metal element), It is preferable that it exists in the range of 0.2-4 mass%. When the rare earth metal content is less than 0.1% by mass, the selectivity of EDC is lowered and the effect of suppressing the combustion of ethylene is insufficient, so that the yield of EDC is also lowered. If the rare earth metal content exceeds 6% by mass, the reaction rate of Cl decreases and the yield of EDC decreases.
また、本発明の触媒は、シリカ−アルミナ粒子を含んでもよく、該シリカ−アルミナ粒子は、シリカとアルミナが複合した一般的なシリカ−アルミナ複合酸化物粒子でも良いが、シリカ粒子をアルミナで被覆した粒子であることが好ましい。シリカ−アルミナ粒子がシリカ粒子をアルミナで被覆した粒子であると、触媒の耐熱性と耐水熱性が改善されることに加えて、エチレンの燃焼反応を抑制することができ、このためＥＤＣの選択性や収率に優れた触媒を得ることができる。 The catalyst of the present invention may contain silica-alumina particles, and the silica-alumina particles may be general silica-alumina composite oxide particles in which silica and alumina are composited, but the silica particles are coated with alumina. It is preferable that the particles are the same. When the silica-alumina particles are particles in which silica particles are coated with alumina, in addition to improving the heat resistance and hydrothermal resistance of the catalyst, it is possible to suppress the combustion reaction of ethylene, and thus the selectivity of EDC. In addition, a catalyst excellent in yield can be obtained.
本発明に係るオキシクロリネーション用触媒は、平均粒子径が４０〜７５μｍ、更には４５〜７０μｍの範囲にあることが好ましい。平均粒子径が４０μｍ未満の場合は充分な流動性が得られなかったり、触媒の損失が増加することがある。平均粒子径が７５μｍを超えても平均粒子径が小さい場合と同様に充分な流動性が得られないことがある。 The oxychlorination catalyst according to the present invention preferably has an average particle size in the range of 40 to 75 μm, more preferably 45 to 70 μm. When the average particle size is less than 40 μm, sufficient fluidity may not be obtained or the loss of the catalyst may increase. May mean particle diameter is not obtained sufficient fluidity as if a small average particle size also exceed the 75 [mu] m.
また、粒子径分布は、概ね正規分布しており、粒子径が３０μｍ未満の微粒子が１０質量％以下であることが好ましく、粒子径が９０μｍを超える粒子が２０質量％以下であることが好ましい。なお、必要に応じて更に分級することもできる。このような粒子径分布は、マイクロメッシュシーブ法によって求めることができる。 In addition, the particle size distribution is generally normal, and the fine particles having a particle size of less than 30 μm are preferably 10% by mass or less, and the particles having a particle size exceeding 90 μm are preferably 20% by mass or less. In addition, it can also classify as needed. Such a particle size distribution can be obtained by a micromesh sieve method.
触媒の比表面積は１５０〜３５０ｍ2／ｇ、更には１８０〜３００ｍ2／ｇの範囲にあることが好ましい。比表面積が１５０ｍ2／ｇ未満の場合は、Ｃｌのエチレンへの付加反応の効率が下がり、目的生成物であるＥＤＣの収率が低下する。触媒の比表面積が３５０ｍ2／ｇを超えると、エチレンの酸化反応が顕著になることがある。 The specific surface area of the catalyst is 150~350m 2 / g, more preferably in the range of 180~300m 2 / g. When the specific surface area is less than 150 m 2 / g, the efficiency of the addition reaction of Cl to ethylene is lowered, and the yield of EDC as the target product is lowered. When the specific surface area of the catalyst exceeds 350 m 2 / g, the oxidation reaction of ethylene may become remarkable.
触媒の細孔容積は０．２５〜０．４０ｍｌ／ｇ、更には０．３０〜０．３５ｍｌ／ｇの範囲にあることが好ましい。０．２５ｍｌ／ｇ未満の場合は、触媒の比表面積も低く、ＥＤＣの収率が不充分となることがある。また、触媒の嵩比重が高くなり、反応時の流動状態が不良となることがある。細孔容積が０．４０ｍｌ／ｇを超えると、耐摩耗性が不充分となり、反応時の触媒飛散が増加する傾向がある。 The pore volume of the catalyst is preferably in the range of 0.25 to 0.40 ml / g, more preferably 0.30 to 0.35 ml / g. When it is less than 0.25 ml / g, the specific surface area of the catalyst is also low, and the yield of EDC may be insufficient. In addition, the bulk specific gravity of the catalyst is increased, and the flow state during the reaction may be poor. When the pore volume exceeds 0.40 ml / g, the abrasion resistance becomes insufficient and the catalyst scattering during the reaction tends to increase.
触媒の嵩比重（ＣＢＤ）は０．８５〜１．２０ｇ／ｍｌ、更には０．９５〜１．１０ｇ／ｍｌの範囲にあることが好ましい。嵩比重が０．９０ｇ／ｍｌ未満の場合は、触媒が軽すぎて反応槽外へ飛散することがある。嵩比重が１．２０ｇ／ｍｌを超えると、流動不良を生じることがあり、反応槽内の偏流・偏熱によるエチレンの燃焼が問題となることがある。このような嵩比重は、所定の条件で加熱処理をした触媒を定量容器（例えば、メスシリンダー）へ一定量を充填し、充分に振動を加え最も細密に充填された状態での体積（嵩）を測定し、触媒の充填量を体積（嵩）で除して求めることができる。 The bulk specific gravity (CBD) of the catalyst is preferably in the range of 0.85 to 1.20 g / ml, more preferably 0.95 to 1.10 g / ml. When the bulk specific gravity is less than 0.90 g / ml, the catalyst may be too light and may be scattered outside the reaction vessel. If the bulk specific gravity exceeds 1.20 g / ml, flow failure may occur, and ethylene combustion due to drift / heat drift in the reaction tank may be a problem. Such bulk specific gravity is the volume (bulk) in a state where a fixed amount of a catalyst that has been heat-treated under predetermined conditions is filled into a metering container (for example, a graduated cylinder), and the vibration is sufficiently applied. Can be obtained by dividing the packing amount of the catalyst by the volume (bulk).
［オキシクロリネーション用触媒の製造方法］
本発明に係るオキシクロリネーション用触媒の製造方法は、下記の工程（ａ）〜（ｈ）からなり、工程（ｂ）と工程（ｄ）の洗浄工程はいずれかを実施すれば良い。以下、順に説明する。
（ａ）アルミニウム塩水溶液にアルミン酸アルカリ水溶液と第二銅塩水溶液とを混合して混合スラリーを調製する工程
（ｂ）前記混合スラリーを洗浄して噴霧乾燥用スラリーを調製する工程
（ｃ）前記噴霧乾燥用スラリーを噴霧乾燥して噴霧乾燥物を得る工程
（ｄ）前記噴霧乾燥物を洗浄して洗浄物を得る工程
（ｅ）前記洗浄物を乾燥して乾燥物を得る工程
（ｆ）前記乾燥物を焼成（１次焼成）して焼成物を得る工程
（ｇ）前記焼成物に、アルカリ土類金属塩水溶液及び／又はアルカリ金属塩水溶液から選ばれる少なくとも１種の金属塩水溶液を含浸して含浸物を得る工程
（ｈ）前記含浸物を焼成（２次焼成）する工程
[Method for producing catalyst for oxychlorination]
The manufacturing method of the catalyst for oxychlorination according to the present invention includes the following steps (a) to (h), and either the cleaning step (b) or the step (d) may be performed. Hereinafter, it demonstrates in order.
(A) A step of preparing a mixed slurry by mixing an aluminum aluminate aqueous solution and a cupric salt aqueous solution with an aluminum salt aqueous solution (b) A step of washing the mixed slurry to prepare a slurry for spray drying (c) A step of spray-drying a slurry for spray-drying to obtain a spray-dried product (d) a step of washing the spray-dried product to obtain a washed product (e) a step of drying the washed product to obtain a dried product (f) (G) impregnating the calcined product with at least one metal salt aqueous solution selected from an alkaline earth metal salt aqueous solution and / or an alkali metal salt aqueous solution. (H) a step of firing (secondary firing) the impregnated product
《工程（ａ）》
本発明に用いるアルミニウム塩としては、塩化アルミニウム、硝酸アルミニウム、硫酸アルミニウム、酢酸アルミニウム等が挙げられる。特に、塩化アルミニウムは、繊維状の擬ベーマイトアルミナゲルを調製することが容易であり、活性、選択性に優れたオキシクロリネーション用触媒を得ることができるので好ましい。
<< Step (a) >>
Examples of the aluminum salt used in the present invention include aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum acetate. In particular, aluminum chloride is preferred because it is easy to prepare a fibrous pseudoboehmite alumina gel, and an oxychlorination catalyst having excellent activity and selectivity can be obtained.
このようなアルミニウム塩の水溶液の濃度はＡｌ2Ｏ3として０．１〜５質量％、更には０．５〜２質量％の範囲にあることが好ましい。アルミニウム塩水溶液の濃度が０．１質量％未満の場合は、前記擬ベーマイトアルミナの一次粒子が大きくなる傾向があり、比表面積が高くならず活性が低下したり、耐摩耗性が不充分となることがある。アルミニウム塩水溶液の濃度が５質量％を超えると、擬ベーマイトアルミナの一次粒子が小さく凝集した粒子となり、このため耐摩耗性が不充分となったり、結晶性が高くならず活性が不充分となることがある。 The concentration of such an aluminum salt aqueous solution is preferably 0.1 to 5% by mass, more preferably 0.5 to 2% by mass as Al 2 O 3 . When the concentration of the aluminum salt aqueous solution is less than 0.1% by mass, the primary particles of the pseudo boehmite alumina tend to increase, the specific surface area does not increase, the activity decreases, and the wear resistance becomes insufficient. Sometimes. When the concentration of the aluminum salt aqueous solution exceeds 5% by mass, the primary particles of pseudoboehmite alumina become small and agglomerated particles, so that the wear resistance is insufficient, the crystallinity is not high, and the activity is insufficient. Sometimes.
アルミン酸アルカリ（ＭＡｌＯ2：Ｍはアルカリ金属）としては、アルミン酸ナトリウム、アルミン酸カリウム等が挙げられる。特に、アルミン酸ナトリウムを前記塩化アルミニウムと組み合わせて用いると、前記繊維状の擬ベーマイトアルミナゲルを調製することが容易で、活性、選択性に優れたオキシクロリネーション用触媒を得ることができる。 Examples of the alkali aluminate (MAlO 2 : M is an alkali metal) include sodium aluminate and potassium aluminate. In particular, when sodium aluminate is used in combination with the aluminum chloride, the fibrous pseudo-boehmite alumina gel can be easily prepared, and an oxychlorination catalyst excellent in activity and selectivity can be obtained.
このようなアルミン酸アルカリ水溶液の濃度はＡｌ2Ｏ3として０．１〜３０質量％、更には１〜２５質量％の範囲にあることが好ましい。この濃度が０．１質量％未満の場合は、アルミン酸アルカリの溶解安定性が低く、容易に加水分解し、前記繊維状の擬ベーマイトアルミナゲルの調製が困難となることがある。一方、濃度が３０質量％を超えると、擬ベーマイトアルミナの一次粒子が小さく凝集した粒子となり、このため耐摩耗性が不充分となったり、結晶性が高くならず活性が不充分となることがある。 The concentration of such an alkali aluminate aqueous solution is preferably in the range of 0.1 to 30% by mass, more preferably 1 to 25% by mass as Al 2 O 3 . When this concentration is less than 0.1% by mass, the dissolution stability of the alkali aluminate is low, it is easily hydrolyzed, and it may be difficult to prepare the fibrous pseudo-boehmite alumina gel. On the other hand, if the concentration exceeds 30% by mass, the primary particles of pseudoboehmite alumina become small and agglomerated particles, which may result in insufficient wear resistance, insufficient crystallinity, and insufficient activity. is there.
第二銅塩としては塩化第二銅、硝酸第二銅、硫酸銅、酢酸第二銅等の第二銅塩が挙げられる。なかでも、塩化第二銅は触媒に適度な量の塩素を随伴するためか、活性、選択性に優れたオキシクロリネーション用触媒を得ることができる。第二銅塩水溶液の濃度は触媒中の銅の含有量等によって適宜調整することができるが、ＣｕＯとして概ね０．１〜２０質量％、更には１〜５質量％の範囲にあることが好ましい。 Examples of cupric salts include cupric salts such as cupric chloride, cupric nitrate, copper sulfate, and cupric acetate. Among them, cupric chloride can be obtained with an appropriate amount of chlorine accompanying the catalyst, or an oxychlorination catalyst having excellent activity and selectivity can be obtained. The concentration of the aqueous cupric salt solution can be appropriately adjusted depending on the copper content in the catalyst, etc., but is preferably in the range of 0.1 to 20% by mass, more preferably 1 to 5% by mass as CuO. .
本工程では、まず、アルミニウム塩水溶液にアルミン酸アルカリ水溶液と第二銅塩水溶液とを混合する。
アルミニウム塩水溶液にアルミン酸アルカリ水溶液と第二銅塩水溶液とを混合することによって、高い比表面積を有し、高い活性及び選択性を有するとともに、長期にわたって使用した場合にも活性及び選択性の低下の少ないオキシクロリネーション用触媒を得ることができる。
In this step, first, an alkali aluminate aqueous solution and a cupric salt aqueous solution are mixed with an aluminum salt aqueous solution.
By mixing an aqueous aluminum salt solution and an aqueous cupric salt solution into an aqueous aluminum salt solution, it has a high specific surface area, high activity and selectivity, and a decrease in activity and selectivity even when used over a long period of time. A catalyst for oxychlorination with a low content can be obtained.
アルミニウム塩のモル数（Ｍａ）とアルミン酸アルカリのモル数（Ｍｂ）との比（Ｍａ）／（Ｍｂ）は概ね０．１〜０．４５、更には０．１５〜０．３５の範囲にあることが好ましい。モル比（Ｍａ）／（Ｍｂ）が前記範囲にあると前記繊維状の一次粒子、二次粒子の擬ベーマイトアルミナゲルを調製することが容易で、活性、選択性に優れ、活性、選択性の低下の少ない触媒寿命に優れたオキシクロリネーション用触媒を得ることができる。 The ratio (Ma) / (Mb) of the number of moles of aluminum salt (Ma) to the number of moles of alkali aluminate (Mb) is generally in the range of 0.1 to 0.45, more preferably 0.15 to 0.35. Preferably there is. When the molar ratio (Ma) / (Mb) is within the above range, it is easy to prepare the fibrous primary particle and secondary particle pseudo-boehmite alumina gel, and the activity and selectivity are excellent. A catalyst for oxychlorination excellent in catalyst life with little decrease can be obtained.
アルミニウム塩水溶液にアルミン酸アルカリ水溶液を混合した際のｐＨは７〜１２．５、更には８〜１２の範囲にあることが好ましい。このときのｐＨが７未満の場合は、前記繊維状の一次粒子、二次粒子の擬ベーマイトアルミナゲルが得られないことがあり、ｐＨが１２を超えると、次いで混合する第二銅塩水溶液の加水分解による水酸化銅（水和物）が擬ベーマイトアルミナ粒子上に高分散状態で析出せず、分離した状態で析出することがあり、活性、選択性及び触媒寿命が不充分となることがある。 The pH of the aqueous aluminum salt solution mixed with the aqueous alkali aluminate solution is preferably in the range of 7 to 12.5, more preferably 8 to 12. When the pH at this time is less than 7, the fibrous primary particles and secondary particles of pseudoboehmite alumina gel may not be obtained. When the pH exceeds 12, the cupric salt aqueous solution to be mixed next is mixed. Copper hydroxide (hydrate) by hydrolysis may not precipitate on pseudoboehmite alumina particles in a highly dispersed state but may separate in a separated state, resulting in insufficient activity, selectivity and catalyst life. is there.
次いで、第二銅塩水溶液を添加する。
第二銅塩水溶液は、最終的に得られる触媒中のＣｕＯの含有量が前記した範囲となるように混合することが好ましい。
混合する際の温度は特に制限はないが０〜６０℃、更には２０〜３０℃の範囲にあることが好ましい。混合温度が０℃未満の場合は、第二銅塩の加水分解による銅成分の析出に長時間を要したり、最終的に得られる触媒中の含有量が不足することがある。混合温度が６０℃を超えると、必ずしも理由は明らかではないが活性、選択性及び触媒寿命が不充分となることがある。
Then, an aqueous cupric salt solution is added.
The aqueous cupric salt solution is preferably mixed so that the content of CuO in the catalyst finally obtained is in the above-described range.
Although the temperature at the time of mixing does not have a restriction | limiting in particular, It is preferable that it exists in the range of 0-60 degreeC, Furthermore, 20-30 degreeC. When the mixing temperature is less than 0 ° C., it may take a long time to precipitate the copper component by hydrolysis of the cupric salt, or the content in the catalyst finally obtained may be insufficient. When the mixing temperature exceeds 60 ° C., the reason is not always clear, but the activity, selectivity and catalyst life may be insufficient.
また、第二銅塩水溶液を混合する際の混合スラリーのｐＨは概ね４．０〜９．５、更には４．５〜６．５の範囲にあることが好ましい。ｐＨが上記範囲にない場合は、繊維状の擬ベーマイト粒子が得られないために耐摩耗性が悪化したり、触媒の比表面積や細孔容積が低下して活性及び選択性及び触媒寿命が不充分となることがある。 Moreover, it is preferable that pH of the mixing slurry at the time of mixing cupric salt aqueous solution exists in the range of about 4.0-9.5, and also 4.5-6.5. If the pH is not within the above range, fibrous pseudoboehmite particles cannot be obtained, resulting in poor wear resistance, and a decrease in the specific surface area and pore volume of the catalyst, resulting in poor activity, selectivity, and catalyst life. May be sufficient.
工程（ａ）では、前記混合スラリーを必要に応じて熟成することができる。熟成温度は３０〜６０℃の範囲にあることが好ましい。このような熟成を行うことによって、耐摩耗性、活性、選択性等に優れたオキシクロリネーション用触媒を再現性よく製造することができる。 In the step (a), the mixed slurry can be aged as necessary. The aging temperature is preferably in the range of 30 to 60 ° C. By performing such aging, an oxychlorination catalyst excellent in wear resistance, activity, selectivity and the like can be produced with good reproducibility.
本工程では、希土類金属塩水溶液を混合してもよい。このような金属塩水溶液は、あらかじめアルミニウム塩水溶液に混合するか、第二銅塩水溶液と同時にあるいは第二銅塩水溶液に次いで混合することが好ましい。
更に、本工程（ａ）では、混合スラリーのｐＨを前記範囲に調整し、維持するため酸又はアルカリ金属を混合することができる。酸としては塩酸、硝酸、硫酸等を用いることができ、アルカリ金属としてはアルカリ金属水酸化物、アンモニア、有機アミン等を用いることができる。
In this step, a rare earth metal salt aqueous solution may be mixed. Such an aqueous metal salt solution is preferably mixed in advance with an aqueous aluminum salt solution, or simultaneously with the aqueous cupric salt solution or subsequently mixed with the aqueous cupric salt solution.
Furthermore, in this step (a), an acid or an alkali metal can be mixed in order to adjust and maintain the pH of the mixed slurry within the above range. As the acid, hydrochloric acid, nitric acid, sulfuric acid or the like can be used, and as the alkali metal, alkali metal hydroxide, ammonia, organic amine or the like can be used.
《工程（ｂ）》
混合スラリーを洗浄して噴霧乾燥用スラリーを調製する。
先ず、工程（ａ）で調製した混合スラリーを濾過する。濾過する際には必要に応じて温水等を掛けることができ、この濾過によって混合スラリー中の塩化ナトリウム、硝酸ナトリウム等の過剰の塩を低減することができる。過剰の塩を低減しておくと耐摩耗性等に優れた触媒を得ることができる。
次いで、必要に応じて、更に濾過し脱水するか、水を加えることによって濃度調整して噴霧乾燥用スラリーを調製する。
<< Step (b) >>
The mixed slurry is washed to prepare a slurry for spray drying.
First, the mixed slurry prepared in step (a) is filtered. When filtering, hot water or the like can be applied as necessary, and excess salt such as sodium chloride and sodium nitrate in the mixed slurry can be reduced by this filtration. If excessive salt is reduced, a catalyst excellent in wear resistance and the like can be obtained.
Next, if necessary, the slurry is further filtered and dehydrated, or the concentration is adjusted by adding water to prepare a slurry for spray drying.
噴霧乾燥用スラリーの濃度は固形分として５〜２０質量％、更には８〜１８質量％の範囲にあることが好ましい。濃度が５質量％未満の場合は、噴霧乾燥して得られる球状微粒子の平均粒子径が小さくなるとともに２０μｍ以下の微小粒子が増大することがあり、また水分が多いために噴霧乾燥の熱エネルギーを多く必要とし経済的でない。一方、濃度が２０質量％を超えると、スラリーの粘度が高すぎて噴霧乾燥が困難となることがある。
なお、噴霧乾燥用スラリーは、必要に応じてホモジナイザー、コロイドミル等により乳化処理、均一化処理等を行ってもよい。
It is preferable that the density | concentration of the slurry for spray drying exists in the range of 5-20 mass% as solid content, and also 8-18 mass%. When the concentration is less than 5% by mass, the average particle size of the spherical fine particles obtained by spray drying may decrease and the fine particles of 20 μm or less may increase. Needs a lot and is not economical. On the other hand, if the concentration exceeds 20% by mass, the viscosity of the slurry may be too high and spray drying may be difficult.
Note that the slurry for spray drying may be subjected to an emulsification treatment, a homogenization treatment, or the like using a homogenizer, a colloid mill, or the like, if necessary.
このような噴霧乾燥用スラリーのｐＨは４〜９．５、更には４．５〜６．５の範囲にあることが好ましい。ｐＨが４未満の場合は、得られる触媒の比表面積や細孔容積が低下し、活性及び触媒寿命が不充分となる傾向にある。一方、ｐＨが９．５を超えると、アルミナ担体上に銅成分が高分散した状態で沈着しないためか、活性や触媒寿命及び長期流動性が低下する傾向がある。 The pH of such a spray drying slurry is preferably in the range of 4 to 9.5, more preferably 4.5 to 6.5. When the pH is less than 4, the specific surface area and pore volume of the resulting catalyst are lowered, and the activity and catalyst life tend to be insufficient. On the other hand, if the pH exceeds 9.5, activity, catalyst life, and long-term fluidity tend to decrease because the copper component does not deposit in a highly dispersed state on the alumina support.
《工程（ｃ）》
工程（ｂ）で得た噴霧乾燥用スラリーを噴霧乾燥して噴霧乾燥物（微小球状粒子）を得る。噴霧乾燥する方法としては、従来公知のオキシクロリネーション用流動触媒と同様に微小球状の流動触媒が得られれば特に制限はないが、例えば熱風気流中でディスク回転式、ノズル式等の種々の噴霧乾燥機を用いることができる。
このとき、熱風気流温度は１５０〜５００℃、さらには２００〜３５０℃の範囲にあることが好ましい。熱風気流温度が１５０℃未満の場合は、乾燥が不充分となることがある。一方、５００℃を超えると、乾燥が急激に起こるために、活性成分や助触媒成分が粒子表面に偏在することがある。
<< Step (c) >>
The slurry for spray drying obtained in the step (b) is spray-dried to obtain a spray-dried product (microspherical particles). The spray drying method is not particularly limited as long as a microsphere fluid catalyst can be obtained in the same manner as a conventionally known fluid catalyst for oxychlorination. For example, various sprays such as a disk rotation type and a nozzle type in a hot air stream are used. A dryer can be used.
At this time, the hot air stream temperature is preferably in the range of 150 to 500 ° C, more preferably 200 to 350 ° C. When the hot air flow temperature is less than 150 ° C., drying may be insufficient. On the other hand, Exceeding 500 ° C., for drying occurs rapidly, is that the active ingredient or cocatalyst component is unevenly distributed on the particle surface.
噴霧乾燥して得られる微小球状粒子である噴霧乾燥物は、平均粒子径が５０〜８０μｍ、さらには５５〜７５μｍの範囲にあることが好ましい。平均粒子径が５０μｍ未満の場合は、後述する焼成工程で焼成して得られる触媒の平均粒子径が４０μｍ未満となることがあり、充分な流動性が得られなかったり、触媒の損失が増加することがある。平均粒子径が８０μｍを超える場合は、焼成工程で焼成して得られる触媒の平均粒子径が７５μｍを超えることがあり、平均粒子径が小さい場合と同様に充分な流動性が得られないことがある。 The spray-dried product which is fine spherical particles obtained by spray-drying preferably has an average particle size in the range of 50 to 80 μm, more preferably 55 to 75 μm. When the average particle size is less than 50 μm, the average particle size of the catalyst obtained by calcination in the calcination step described later may be less than 40 μm, and sufficient fluidity may not be obtained or the loss of the catalyst will increase. Sometimes. When the average particle diameter is a 80μm is exceeded, it is the average particle diameter of the catalyst obtained by calcining at firing step obtain ultra the 75 [mu] m, can not be obtained sufficient fluidity as in the case the average particle diameter is smaller Sometimes.
また、噴霧乾燥物の粒子径分布は、概ね正規分布しており、粒子径が３０μｍ未満の微粒子が１０質量％以下であることが好ましく、粒子径が９０μｍを超える粒子が２０質量％以下であることが好ましい。なお、必要に応じてさらに分級することもできる。
上記した平均粒子径、粒子径分布は、例えばマイクロメッシュシーブ法によって求めることができる。
Further, the particle size distribution of the spray-dried product is generally normal distribution, and the fine particles having a particle size of less than 30 μm are preferably 10% by mass or less, and the particles having a particle size exceeding 90 μm are 20% by mass or less. It is preferable. Further classification can be performed as necessary.
The above-mentioned average particle size and particle size distribution can be determined by, for example, a micromesh sieve method.
《工程（ｄ）》
次いで、工程（ｃ）で得た噴霧乾燥物を洗浄して洗浄物を得る。洗浄する方法としては触媒中の有効成分（担体成分としてのアルミナ、活性成分としての銅、希土類金属）以外の不純分塩を低減あるいは除去できれば特に制限はなく、従来公知の方法を採用することができる。例えば、噴霧乾燥物を水に分散させ、濾過し、水（温水）等を掛けて洗浄することができる。洗浄後の残留塩は固形分として５質量％以下、更には２質量％以下、特に１質量％以下であることが望ましい。
<< Step (d) >>
Next, the spray-dried product obtained in step (c) is washed to obtain a washed product. The washing method is not particularly limited as long as it can reduce or remove impurities other than the active ingredients in the catalyst (alumina as a carrier component, copper as an active ingredient, rare earth metal), and a conventionally known method can be adopted. it can. For example, the spray-dried product can be dispersed in water, filtered, and washed with water (hot water) or the like. The residual salt after washing is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less as a solid content.
《工程（ｅ）》
次いで、工程（ｄ）で得た洗浄物を乾燥して乾燥物を得る。乾燥する方法としては従来公知の方法を採用することができ、乾燥温度としては特に制限はないが、通常６０〜２００℃、更には８０〜１５０℃の範囲にあることが好ましい。乾燥時間は温度によっても異なるが通常１〜２４時間の範囲である。
<< Process (e) >>
Next, the washed product obtained in step (d) is dried to obtain a dried product. A conventionally known method can be employed as the drying method, and the drying temperature is not particularly limited, but it is usually preferably in the range of 60 to 200 ° C, more preferably 80 to 150 ° C. Although drying time changes with temperature, it is the range of 1 to 24 hours normally.
《工程（ｆ）》
次いで、工程（ｅ）で得た乾燥物を焼成（１次焼成）して焼成物を得る。このとき、焼成温度は３５０〜８５０℃、特に４００〜７００℃の範囲にあることが好ましい。焼成温度が３５０℃未満の場合は、擬ベーマイトアルミナの脱水及び結晶化（γ−Ａｌ2Ｏ3化）が不充分となり、また活性成分や助触媒成分との結合が不充分となるためか活性及び選択性が不充分となる。焼成温度が８５０℃を超えるとγ−Ａｌ2Ｏ3がε−Ａｌ2Ｏ3、α−Ａｌ2Ｏ3等に結晶型が変化したり、活性成分である銅が完全に酸化物化し活性が不充分となる。焼成時間は焼成温度によって変えることができ、特に限定されないが、概ね０．１〜２４時間の範囲である。一次焼成により、銅−アルミナを触媒としての機能を発現させることができる。
<< Step (f) >>
Next, the dried product obtained in step (e) is fired (primary firing) to obtain a fired product. At this time, the firing temperature is preferably in the range of 350 to 850 ° C, particularly 400 to 700 ° C. If the calcination temperature is less than 350 ° C., the dehydration and crystallization (γ-Al 2 O 3 conversion) of pseudoboehmite alumina will be insufficient, and the binding with active components and promoter components may be insufficient. And the selectivity is insufficient. When the firing temperature exceeds 850 ° C., the crystal form of γ-Al 2 O 3 changes to ε-Al 2 O 3 , α-Al 2 O 3 or the like, or the active component copper is completely oxidized and activated. It becomes insufficient. The firing time can be changed depending on the firing temperature and is not particularly limited, but is generally in the range of 0.1 to 24 hours. By primary firing, copper-alumina can function as a catalyst.
《工程（ｇ）》
次いで、工程（ｆ）で得た焼成物に、アルカリ土類金属塩水溶液及び／又はアルカリ金属塩水溶液から選ばれる少なくとも１種の金属塩水溶液を含浸して含浸物を得る。
ここで、アルカリ土類金属の含有量は、酸化物（ＭＯ：Ｍはアルカリ土類金属元素を示す）として、０．１〜６質量％、更には０．２〜４質量％の範囲にあることが好ましい。アルカリ土類金属の含有量が０．１質量％未満の場合は、得られる触媒の嵩密度、耐摩耗性が低下する傾向がある。アルカリ土類金属の含有量が６質量％を超えると、得られる触媒の細孔容積が低下し、活性が不充分となることがある。
<< Step (g) >>
Next, the fired product obtained in the step (f) is impregnated with at least one metal salt aqueous solution selected from an alkaline earth metal salt aqueous solution and / or an alkali metal salt aqueous solution.
Here, the content of the alkaline earth metal is in the range of 0.1 to 6% by mass, further 0.2 to 4% by mass as an oxide (MO: M represents an alkaline earth metal element). It is preferable. When the content of alkaline earth metal is less than 0.1% by mass, the bulk density and wear resistance of the resulting catalyst tend to decrease. When the content of the alkaline earth metal exceeds 6% by mass, the pore volume of the resulting catalyst is lowered, and the activity may be insufficient.
アルカリ土類金属としては、マグネシウムが好ましく、マグネシウムを用いると活性を低下させることなく耐摩耗性に優れた触媒を得ることができる。
また、アルカリ金属の含有量は、酸化物（Ｎ2Ｏ：Ｎはアルカリ金属元素を示す）として、０．１〜３質量％、更には０．２〜２質量％の範囲にあることが好ましい。アルカリ金属の含有量が０．１質量％未満の場合は、エチレンの燃焼を抑制する効果が不充分となるためにＥＤＣの収率が低下する。アルカリ金属の含有量が３質量％を超えると、Ｃｌの反応率が低下しＥＤＣの収率が低下する。
As the alkaline earth metal, magnesium is preferable. When magnesium is used, a catalyst having excellent wear resistance can be obtained without reducing the activity.
The content of alkali metal oxide: as (N 2 O N represents an alkali metal element), 0.1 to 3 wt%, more preferably in the range of 0.2 to 2 wt% . When the content of the alkali metal is less than 0.1% by mass, the effect of suppressing the combustion of ethylene becomes insufficient, so that the yield of EDC is lowered. When the content of the alkali metal exceeds 3% by mass, the reaction rate of Cl decreases and the yield of EDC decreases.
アルカリ金属としてはカリウムが好ましい。カリウムを用いるとエチレンの酸化抑制効果が他のアルカリ金属に比してマイルドであり、主反応である酸素を介し塩酸から生成されるＣｌのエチレンへの付与反応の活性を大きく低下することなく、エチレンの酸化を抑制することが容易である。
更に、アルカリ土類金属塩及び／又はアルカリ金属塩は、硝酸塩又は塩化物であることが好ましい。
また、本工程において、希土類金属塩水溶液を混合してもよい。
As the alkali metal, potassium is preferred. When potassium is used, the oxidation inhibition effect of ethylene is milder than that of other alkali metals, and without significantly reducing the activity of the reaction of imparting Cl to ethylene from hydrochloric acid via oxygen, which is the main reaction, It is easy to suppress ethylene oxidation.
Further, the alkaline earth metal salt and / or alkali metal salt is preferably a nitrate or chloride.
In this step, a rare earth metal salt aqueous solution may be mixed.
《工程（ｈ）》
乾燥した後、ついで焼成（２次焼成）することによってオキシクロリネーション用触媒物を得ることができる。このとき焼成温度は、３５０〜８５０℃、特に４００〜７００℃の範囲にあることが好ましい。焼成時間は焼成温度によって変えることができ、特に限定されないが、概ね０．１〜２４時間の範囲である。
<< Step (h) >>
After drying, the catalyst for oxychlorination can be obtained by calcination (secondary calcination). At this time, the firing temperature is preferably in the range of 350 to 850 ° C, particularly 400 to 700 ° C. The firing time can be changed depending on the firing temperature and is not particularly limited, but is generally in the range of 0.1 to 24 hours.
得られたオキシクロリネーション用触媒は、銅の含有量が、酸化物（ＣｕＯ）として、５〜２０質量％の範囲にあり、アルカリ土類金属の含有量が酸化物として０．１〜６質量％の範囲にあり、アルカリ金属の含有量が酸化物として０．１〜３質量％の範囲にあり、希土類金属の含有量が酸化物として０．１〜６質量％の範囲にあり、担体用アルミナの含有量は概ね４０〜９０質量％、さらには６０〜８２質量％の範囲にあることが好ましい。
The obtained catalyst for oxychlorination has a copper content in the range of 5 to 20 mass% as an oxide (CuO), and an alkaline earth metal content in the range of 0.1 to 6 mass as an oxide. %, The alkali metal content is in the range of 0.1 to 3 mass% as an oxide, the rare earth metal content is in the range of 0.1 to 6 mass% as an oxide, The content of alumina is preferably in the range of about 40 to 90% by mass, more preferably 60 to 82% by mass.
以下、本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
［実施例１：オキシクロリネーション用触媒（１）］
《噴霧乾燥用スラリーの調製》
純水２４．１３ｋｇに純度９９質量％の塩化アルミニウム六水和物０．９９ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．８８ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Example 1: Oxychlorination catalyst (1)]
<< Preparation of slurry for spray drying >>
In 24.13 kg of pure water, 0.99 kg of aluminum chloride hexahydrate having a purity of 99% by mass was dissolved to prepare an aluminum chloride aqueous solution. To this was added 2.88 kg of an aqueous sodium aluminate solution having a concentration of 22% by mass as Al 2 O 3 to prepare an alumina hydrogel slurry having an oxide concentration of 3% by mass. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．６７ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇを溶解し、ＣｕＯとしての濃度が３質量％の混合塩水溶液５．００ｋｇを調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．２であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass was dissolved in 4.67 kg of pure water to prepare 5.00 kg of a mixed salt aqueous solution having a concentration of 3% by mass as CuO. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.2. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し洗浄物を得た。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
《１次焼成》
次いで、１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成して焼成物（焼成物）を得た。
《含浸》
焼成物の吸水率は０．３３ｍｌ／ｇであった。吸水率相当の純水に純度９７質量％硝酸マグネシウム６水和物０．０７ｋｇを溶解し、焼成物に添加して含浸物を得た。
<< Primary firing >>
Next, after drying at 120 ° C. for 2 hours, baking was performed at 400 ° C. for 0.5 hours in a rotary baking furnace to obtain a fired product (baked product).
《Impregnation》
The water absorption of the fired product was 0.33 ml / g. 0.07 kg of 97 mass% magnesium nitrate hexahydrate was dissolved in pure water equivalent to the water absorption rate, and added to the calcined product to obtain an impregnated product.
《２次焼成》
次いで、含浸物を、１２０℃で２時間乾燥した後、回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション触媒（１）を得た。表１にオキシクロリネーション用触媒（１）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成を示す。
<< Secondary firing >>
Next, the impregnated product was dried at 120 ° C. for 2 hours and then calcined in a rotary calciner at 550 ° C. for 0.5 hour to obtain an oxychlorination catalyst (1). Table 1 shows the average particle diameter, CBD, specific surface area, crystal form of alumina, and composition of the oxychlorination catalyst (1).
［実施例２：オキシクロリネーション用触媒（２）］
《噴霧乾燥用スラリーの調製》
純水２４．２８ｋｇに純度９９質量％の塩化アルミニウム六水和物１．００ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．８９ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Example 2: Oxychlorination catalyst (2)]
<< Preparation of slurry for spray drying >>
In 24.28 kg of pure water, 1.00 kg of 99% by mass aluminum chloride hexahydrate was dissolved to prepare an aluminum chloride aqueous solution. To this was added 2.89 kg of an aqueous solution of sodium aluminate having a concentration of 22% by mass as Al 2 O 3 to prepare an alumina hydrogel slurry having an oxide concentration of 3% by mass. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．６７ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇを溶解し、ＣｕＯとしての濃度が３質量％の混合塩水溶液５．００ｋｇを調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．１であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass was dissolved in 4.67 kg of pure water to prepare 5.00 kg of a mixed salt aqueous solution having a concentration of 3% by mass as CuO. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.1. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し洗浄物を得た。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
《１次焼成》
次いで、洗浄物を１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成して焼成物を得た。
《含浸》
焼成物の吸水率は０．３３ｍｌ／ｇであった。吸水率相当の純水に純度９７質量％硝酸マグネシウム６水和物０．０３ｋｇを溶解し、焼成物に添加し、含浸物を得た。
<< Primary firing >>
Next, the washed product was dried at 120 ° C. for 2 hours and then fired at 400 ° C. for 0.5 hour in a rotary firing furnace to obtain a fired product.
《Impregnation》
The water absorption of the fired product was 0.33 ml / g. 0.03 kg of 97 mass% magnesium nitrate hexahydrate was dissolved in pure water equivalent to the water absorption rate and added to the fired product to obtain an impregnated product.
《２次焼成》
次いで、含浸物を、１２０℃で２時間乾燥した後、回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション触媒（２）を得た。表１に、オキシクロリネーション用触媒（２）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成を示す。
<< Secondary firing >>
Next, the impregnated product was dried at 120 ° C. for 2 hours and then calcined at 550 ° C. for 0.5 hour in a rotary calciner to obtain an oxychlorination catalyst (2). Table 1 shows the average particle size, CBD, specific surface area, alumina crystal form, and composition of the oxychlorination catalyst (2).
［実施例３：オキシクロリネーション用触媒（３）］
《噴霧乾燥用スラリーの調製》
純水２３．５６ｋｇに純度９９質量％の塩化アルミニウム六水和物０．９７ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．８１ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Example 3: Oxychlorination catalyst (3)]
<< Preparation of slurry for spray drying >>
0.97 kg of aluminum chloride hexahydrate having a purity of 99% by mass was dissolved in 23.56 kg of pure water to prepare an aluminum chloride aqueous solution. To this, 2.81 kg of an aqueous sodium aluminate solution having a concentration of 22% by mass as Al 2 O 3 was added to prepare an alumina hydrogel slurry having an oxide concentration of 3% by mass. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．６７ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇを溶解し、ＣｕＯとしての濃度が３質量％の混合塩水溶液５．００ｋｇを調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．１であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass was dissolved in 4.67 kg of pure water to prepare 5.00 kg of a mixed salt aqueous solution having a concentration of 3% by mass as CuO. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.1. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し、洗浄物を得た。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
《１次焼成》
次いで、洗浄物を１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成して焼成物を得た。
《含浸》
焼成物の吸水率は０．３３ｍｌ／ｇであった。吸水率相当の純水に純度９７質量％硝酸マグネシウム６水和物０．２０ｋｇを溶解し、焼成物に添加し、含浸物を得た。
<< Primary firing >>
Next, the washed product was dried at 120 ° C. for 2 hours and then fired at 400 ° C. for 0.5 hour in a rotary firing furnace to obtain a fired product.
《Impregnation》
The water absorption of the fired product was 0.33 ml / g. 0.20 kg of 97 mass% magnesium nitrate hexahydrate was dissolved in pure water corresponding to the water absorption rate and added to the fired product to obtain an impregnated product.
《２次焼成》
次いで、含浸物を１２０℃で２時間乾燥した後、回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション触媒（３）を得た。表１にオキシクロリネーション用触媒（３）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成を示す。
<< Secondary firing >>
Next, the impregnated product was dried at 120 ° C. for 2 hours and then calcined at 550 ° C. for 0.5 hour in a rotary calciner to obtain an oxychlorination catalyst (3). Table 1 shows the average particle size, CBD, specific surface area, alumina crystal form, and composition of the oxychlorination catalyst (3).
［実施例４：オキシクロリネーション用触媒（４）］
《噴霧乾燥用スラリーの調製》
純水２２．９８ｋｇに純度９９質量％の塩化アルミニウム六水和物０．９４ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．７４ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Example 4: Oxychlorination catalyst (4)]
<< Preparation of slurry for spray drying >>
An aluminum chloride aqueous solution was prepared by dissolving 0.94 kg of aluminum chloride hexahydrate having a purity of 99% by mass in 22.98 kg of pure water. To this was added 2.74 kg of a 22 mass% sodium aluminate aqueous solution as Al 2 O 3 to prepare an alumina hydrogel slurry having an oxide concentration of 3 mass%. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．６７ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇを溶解し、ＣｕＯとしての濃度が３質量％の混合塩水溶液５．００ｋｇを調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．１であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass was dissolved in 4.67 kg of pure water to prepare 5.00 kg of a mixed salt aqueous solution having a concentration of 3% by mass as CuO. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.1. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し、洗浄物を得た。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
《１次焼成》
次いで、洗浄物を１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成して焼成物を得た。
《含浸》
焼成物の吸水率は０．３３ｍｌ／ｇであった。吸水率相当の純水に純度９７質量％硝酸マグネシウム６水和物０．３３ｋｇを溶解し、焼成物に添加し、含浸物を得た。
<< Primary firing >>
Next, the washed product was dried at 120 ° C. for 2 hours and then fired at 400 ° C. for 0.5 hour in a rotary firing furnace to obtain a fired product.
《Impregnation》
The water absorption of the fired product was 0.33 ml / g. 0.33 kg of 97 mass% magnesium nitrate hexahydrate was dissolved in pure water equivalent to the water absorption rate, and added to the fired product to obtain an impregnated product.
《２次焼成》
次いで、含浸物を１２０℃で２時間乾燥した後、回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション触媒（４）を得た。表１にオキシクロリネーション用触媒（４）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成を示す。
<< Secondary firing >>
Next, the impregnated product was dried at 120 ° C. for 2 hours and then calcined at 550 ° C. for 0.5 hour in a rotary calciner to obtain an oxychlorination catalyst (4). Table 1 shows the average particle size, CBD, specific surface area, alumina crystal form and composition of the oxychlorination catalyst (4).
［実施例５：オキシクロリネーション用触媒（５）］
《噴霧乾燥用スラリーの調製》
純水２４．１３ｋｇに純度９９質量％の塩化アルミニウム六水和物０．９９ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．８８ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Example 5: Oxychlorination catalyst (5)]
<< Preparation of slurry for spray drying >>
In 24.13 kg of pure water, 0.99 kg of aluminum chloride hexahydrate having a purity of 99% by mass was dissolved to prepare an aluminum chloride aqueous solution. To this was added 2.88 kg of an aqueous sodium aluminate solution having a concentration of 22% by mass as Al 2 O 3 to prepare an alumina hydrogel slurry having an oxide concentration of 3% by mass. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．６７ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇを溶解し、ＣｕＯとしての濃度が３質量％の混合塩水溶液５．００ｋｇを調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．２であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass was dissolved in 4.67 kg of pure water to prepare 5.00 kg of a mixed salt aqueous solution having a concentration of 3% by mass as CuO. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.2. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し、洗浄物を得た。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
《１次焼成》
次いで、洗浄物を１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成して焼成物を得た。
《含浸》
焼成物の吸水率は０．３３ｍｌ／ｇであった。吸水率相当の純水に純度９７質量％硝酸カリウム０．０２ｋｇを溶解し、焼成物に添加し、含浸物を得た。
<< Primary firing >>
Next, the washed product was dried at 120 ° C. for 2 hours and then fired at 400 ° C. for 0.5 hour in a rotary firing furnace to obtain a fired product.
《Impregnation》
The water absorption of the fired product was 0.33 ml / g. 0.02 kg of 97 mass% potassium nitrate was dissolved in pure water equivalent to the water absorption rate and added to the fired product to obtain an impregnated product.
《２次焼成》
次いで、含浸物を１２０℃で２時間乾燥した後、回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション触媒（５）を得た。表１にオキシクロリネーション用触媒（５）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成を示す。
<< Secondary firing >>
Next, the impregnated product was dried at 120 ° C. for 2 hours and then calcined at 550 ° C. for 0.5 hour in a rotary calciner to obtain an oxychlorination catalyst (5). Table 1 shows the average particle size, CBD, specific surface area, crystal form and composition of alumina of the oxychlorination catalyst (5).
［実施例６：オキシクロリネーション用触媒（６）］
《噴霧乾燥用スラリーの調製》
純水２４．１３ｋｇに純度９９質量％の塩化アルミニウム六水和物０．９９ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．８８ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Example 6: Oxychlorination catalyst (6)]
<< Preparation of slurry for spray drying >>
In 24.13 kg of pure water, 0.99 kg of aluminum chloride hexahydrate having a purity of 99% by mass was dissolved to prepare an aluminum chloride aqueous solution. To this was added 2.88 kg of an aqueous sodium aluminate solution having a concentration of 22% by mass as Al 2 O 3 to prepare an alumina hydrogel slurry having an oxide concentration of 3% by mass. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．６７ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇを溶解し、ＣｕＯとしての濃度が３質量％の混合塩水溶液５．００ｋｇを調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．２であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass was dissolved in 4.67 kg of pure water to prepare 5.00 kg of a mixed salt aqueous solution having a concentration of 3% by mass as CuO. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.2. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し、洗浄物を得た。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
《１次焼成》
次いで、洗浄物を１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成して焼成物を得た。
《含浸》
焼成物の吸水率は０．３３ｍｌ／ｇであった。吸水率相当の純水に純度９７質量％塩化マグネシウム６水和物０．０５ｋｇを溶解し、焼成物に添加し、含浸物を得た。
<< Primary firing >>
Next, the washed product was dried at 120 ° C. for 2 hours and then fired at 400 ° C. for 0.5 hour in a rotary firing furnace to obtain a fired product.
《Impregnation》
The water absorption of the fired product was 0.33 ml / g. In pure water equivalent to water absorption, 0.05 kg of 97 mass% magnesium chloride hexahydrate was dissolved and added to the fired product to obtain an impregnated product.
《２次焼成》
次いで、含浸物を１２０℃で２時間乾燥した後、回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション触媒（６）を得た。表１にオキシクロリネーション用触媒（６）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成を示す。
<< Secondary firing >>
Next, the impregnated product was dried at 120 ° C. for 2 hours and then calcined at 550 ° C. for 0.5 hour in a rotary calciner to obtain an oxychlorination catalyst (6). Table 1 shows the average particle diameter, CBD, specific surface area, crystal form and composition of alumina of the oxychlorination catalyst (6).
［比較例１：オキシクロリネーション用触媒（８）］
《噴霧乾燥用スラリーの調製》
純水２４．４２ｋｇに、純度９９質量％の塩化アルミニウム六水和物１．００ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．９１ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Comparative Example 1: Oxychlorination catalyst (8)]
<< Preparation of slurry for spray drying >>
In 24.42 kg of pure water, 1.00 kg of 99% by mass aluminum chloride hexahydrate was dissolved to prepare an aluminum chloride aqueous solution. To this was added 2.91 kg of an aqueous solution of sodium aluminate having a concentration of 22% by mass as Al 2 O 3 to prepare an alumina hydrogel slurry having an oxide concentration of 3% by mass. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．９３ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇを溶解し、ＣｕＯとしての濃度が３質量％の混合塩水溶液を調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．２であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass was dissolved in 4.93 kg of pure water to prepare a mixed salt aqueous solution having a concentration of 3% by mass as CuO. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.2. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し、洗浄物を得た。
《焼成》
次いで、洗浄物を１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成してオキシクロリネーション用触媒（８）を調製した。表１にオキシクロリネーション用触媒（８）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成、耐摩耗性を示す。
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
<Baking>
Next, the washed product was dried at 120 ° C. for 2 hours and then calcined at 400 ° C. for 0.5 hour in a rotary calciner to prepare an oxychlorination catalyst (8). Table 1 shows the average particle diameter, CBD, specific surface area, crystal form of alumina, composition, and wear resistance of the oxychlorination catalyst (8).
［比較例２：オキシクロリネーション用触媒（９）］
《噴霧乾燥用スラリーの調製》
純水２４．１３ｋｇに純度９９質量％の塩化アルミニウム六水和物０．９９ｋｇを溶解し、塩化アルミニウム水溶液を調製した。これにＡｌ2Ｏ3としての濃度２２質量％のアルミン酸ナトリウム水溶液２．８８ｋｇを加え、酸化物濃度が３質量％のアルミナヒドロゲルスラリーを調製した。このとき、混合温度は３０℃、得られたアルミナヒドロゲルスラリーのｐＨは１１．５であった。アルミナヒドロゲルスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ１０ｎｍ、平均幅０．５ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。また、Ｘ線回折によれば擬ベーマイトアルミナであった。
[Comparative Example 2: Oxychlorination catalyst (9)]
<< Preparation of slurry for spray drying >>
In 24.13 kg of pure water, 0.99 kg of aluminum chloride hexahydrate having a purity of 99% by mass was dissolved to prepare an aluminum chloride aqueous solution. To this was added 2.88 kg of an aqueous sodium aluminate solution having a concentration of 22% by mass as Al 2 O 3 to prepare an alumina hydrogel slurry having an oxide concentration of 3% by mass. At this time, the mixing temperature was 30 ° C., and the pH of the resulting alumina hydrogel slurry was 11.5. A part of the alumina hydrogel slurry was dried and observed with a scanning electron micrograph, and as a result, it was fibrous secondary particles in which fibrous primary particles having an average length of 10 nm and an average width of 0.5 nm were bundled. Moreover, according to X-ray diffraction, it was pseudo boehmite alumina.
別途、純水４．６２ｋｇに純度９７質量％の塩化第二銅二水和物０．３３ｋｇ、純度９７質量％塩化マグネシウム０．０５ｋｇを溶解し、[ＣｕＯ＋ＭｇＯ]としての濃度が３質量％の混合塩水溶液５．００ｋｇを調製した。上記アルミナヒドロゲルスラリーへ混合塩水溶液を混合し、混合ヒドロゲルスラリーを調製した。混合ヒドロゲルスラリーのｐＨは６．１であった。次いで、混合ヒドロゲルスラリーを脱水脱塩した後、純水を加えて固形分濃度を１０質量％に調整し、ホモジナイザーを用いて均一化処理をして噴霧乾燥用スラリー１０．００ｋｇを調製した。噴霧乾燥用スラリーのｐＨは６．８であった。 Separately, 0.33 kg of cupric chloride dihydrate having a purity of 97% by mass and 0.05 kg of purity 97% by mass of magnesium chloride are dissolved in 4.62 kg of pure water, and the concentration of [CuO + MgO] is 3% by mass. A salt solution of 5.00 kg was prepared. A mixed salt solution was mixed with the alumina hydrogel slurry to prepare a mixed hydrogel slurry. The pH of the mixed hydrogel slurry was 6.1. Subsequently, after dehydrating and desalting the mixed hydrogel slurry, pure water was added to adjust the solid content concentration to 10% by mass, and homogenization was performed using a homogenizer to prepare 10.00 kg of a slurry for spray drying. The pH of the slurry for spray drying was 6.8.
《噴霧乾燥》
噴霧乾燥用スラリーを温度２５０℃の熱風気流中に噴霧して微小球状粒子である噴霧乾燥物を得た。噴霧乾燥物の平均粒子径は６５μｍであり、２０μｍ以下が１０質量％、１４９μｍ以上が５質量％であった。
《洗浄》
噴霧乾燥物を重量比で１０倍量の６０℃温水に懸濁し、充分撹拌した後、濾過し、１０倍量の６０℃温水を掛けて洗浄し、洗浄物を得た。
《Spray drying》
The slurry for spray drying was sprayed into a hot air stream at a temperature of 250 ° C. to obtain a spray-dried product having fine spherical particles. The average particle size of the spray-dried product was 65 μm, 20 μm or less was 10% by mass, and 149 μm or more was 5% by mass.
"Washing"
The spray-dried product was suspended in 10 times the amount of 60 ° C. warm water by weight, sufficiently stirred, filtered, and washed with 10 times the amount of 60 ° C. warm water to obtain a washed product.
《焼成》
次いで、洗浄物を１２０℃で２時間乾燥した後、回転式焼成炉にて、４００℃で０．５時間焼成してオキシクロリネーション用触媒（９）を得た。表１にオキシクロリネーション用触媒（９）の平均粒子径、ＣＢＤ、比表面積、アルミナの結晶形、組成、耐摩耗性を示す。
<Baking>
Next, the washed product was dried at 120 ° C. for 2 hours and then calcined at 400 ° C. for 0.5 hour in a rotary calciner to obtain an oxychlorination catalyst (9). Table 1 shows the average particle diameter, CBD, specific surface area, crystal form of alumina, composition, and wear resistance of the oxychlorination catalyst (9).
［触媒性能評価］
以下のように、オキシクロリネーション用触媒（１）〜（９）について、活性及び流動性を評価し、表１にそれらの結果を示す。
《活性評価》
固定流動床式反応器を用い、これに各オキシクロリネーション用触媒を５ｇ充填し、温度２３０℃で、窒素ガスを２８．８ｍｌ／ｍｉｎで供給しながら流動化させ、次いで窒素ガスに代えて反応用混合ガス（エチレン３９．２ｖｏｌ％、塩酸４６．１ｖｏｌ％、酸素１４．７ｖｏｌ％）を６２．５ｍｌ／ｍｉｎで供給して反応を行った。このとき、ＷＨＳＶ＝７５０ｈ-1である。
生成ガスをガスクロマトグラフにて分析し、活性、選択性、収率及びエチレン燃焼率を表に示した。
・活性：塩酸転化率＝（供給塩酸−未反応塩酸）／供給塩酸Ｘ１００（モル％）
・選択性：ＥＤＣ選択率＝ＥＤＣの実生成量／理論的ＥＤＣ生成量×１００（モル％）
・収率（塩酸基準）：ＥＤＣ収率＝塩酸転化率 ×ＥＤＣ選択率（モル％）
・燃焼性：エチレン燃焼率＝（ＣＯ＋ＣＯ2）モル数／Ｃ2Ｈ4モル数Ｘ１００（モル％）
《流動性評価》
前記反応中に、流動層下部温度と流動層上部温度との温度差（ΔＴ：℃）を測定し、以下の基準で評価し、結果を表１に示す。
ΔＴが３℃未満で、良好な流動性を示した ：◎
ΔＴが３℃以上、５℃未満で、比較的良好な流動性を示した：○
ΔＴが５℃以上、７℃未満で、問題のない流動性を示した ：△
ΔＴが７℃以上で、流動性に問題があった ：×
《耐金属磨耗評価》
ＡＳＴＭ Ｃ ７０４に準拠した試験装置を用いて評価した。試験片ＳＵＳ３０４板に角度２２．５°、圧力０．１４７ＭＰａ、２００ｇの触媒を５分間吹き付け、試験片の質量減少より評価した。結果は表１に示す。
磨耗質量が０．００１ｇ未満 ：◎
磨耗質量が０．００１ｇ〜０．００５ｇ未満：○
磨耗質量が０．００５ｇ〜０．０１未満 ：△
磨耗質量が０．０１ｇ以上 ：×
[Catalyst performance evaluation]
The activity and fluidity of the oxychlorination catalysts (1) to (9) were evaluated as follows, and Table 1 shows the results.
<Activity evaluation>
Using a fixed fluidized bed reactor, 5 g of each oxychlorination catalyst is charged into the reactor, fluidized at a temperature of 230 ° C. while supplying nitrogen gas at 28.8 ml / min, and then reacted in place of nitrogen gas. The reaction was carried out by supplying a mixed gas (ethylene 39.2 vol%, hydrochloric acid 46.1 vol%, oxygen 14.7 vol%) at 62.5 ml / min. At this time, WHSV = 750h −1 .
The product gas was analyzed with a gas chromatograph, and the activity, selectivity, yield and ethylene combustion rate were shown in the table.
Activity: Hydrochloric acid conversion rate = (feed hydrochloric acid−unreacted hydrochloric acid) / feed hydrochloric acid X100 (mol%)
Selectivity: EDC selectivity = actual production amount of EDC / theoretical EDC production amount × 100 (mol%)
Yield (hydrochloric acid basis): EDC yield = hydrochloric acid conversion rate × EDC selectivity (mol%)
Combustibility: ethylene combustion rate = (CO + CO 2 ) moles / C 2 H 4 moles X100 (mol%)
<Fluidity assessment>
During the reaction, the temperature difference (ΔT: ° C.) between the fluidized bed lower temperature and the fluidized bed upper temperature was measured and evaluated according to the following criteria, and the results are shown in Table 1.
ΔT was less than 3 ° C. and showed good fluidity: ◎
ΔT was 3 ° C. or higher and lower than 5 ° C., and showed relatively good fluidity:
ΔT was 5 ° C. or higher and lower than 7 ° C., showing no problem fluidity: Δ
ΔT was 7 ° C. or higher, and there was a problem with fluidity: ×
《Metallic wear resistance evaluation》
Evaluation was performed using a test apparatus conforming to ASTM C704. A test piece SUS304 plate was sprayed with a catalyst having an angle of 22.5 °, a pressure of 0.147 MPa, and 200 g for 5 minutes, and evaluation was performed based on a decrease in mass of the test piece. The results are shown in Table 1.
Wear mass is less than 0.001 g: ◎
Wear mass is 0.001 to less than 0.005 g: ○
Wear mass is 0.005 g to less than 0.01: Δ
Wear mass is 0.01g or more: ×
Claims (4)
（ａ）アルミニウム塩水溶液にアルミン酸アルカリ水溶液と第二銅塩水溶液とを混合して噴霧乾燥用スラリーを調製する工程
（ｃ）前記噴霧乾燥用スラリーを噴霧乾燥して噴霧乾燥物を得る工程
（ｄ）前記噴霧乾燥物を洗浄して洗浄物を得る工程
（ｅ）前記洗浄物を乾燥して乾燥物を得る工程
（ｆ）前記乾燥物を焼成して焼成物を得る工程
（ｇ）前記焼成物に、アルカリ土類金属塩水溶液及び／又はアルカリ金属塩水溶液から選ばれる少なくとも１種の金属塩水溶液を含浸して含浸物を得る工程
（ｈ）前記含浸物を焼成する工程 The manufacturing method of the catalyst for oxychlorination characterized by consisting of the following process (a), (c)-(h).
(A) Step of preparing an aqueous solution of aluminum salt and an aqueous solution of alkali aluminate and an aqueous solution of cupric salt to prepare a slurry for spray drying (c) Step of spray drying the slurry for spray drying to obtain a spray dried product ( d) washing the spray-dried product to obtain a washed product (e) drying the washed product to obtain a dried product (f) firing the dried product to obtain a baked product (g) firing A step of impregnating a product with at least one metal salt aqueous solution selected from an alkaline earth metal salt aqueous solution and / or an alkali metal salt aqueous solution to obtain an impregnated product (h) a step of firing the impregnated product
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