JP4753724B2 - Novel platinum-based catalyst and method for producing the same - Google Patents
Novel platinum-based catalyst and method for producing the same Download PDFInfo
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- JP4753724B2 JP4753724B2 JP2006010854A JP2006010854A JP4753724B2 JP 4753724 B2 JP4753724 B2 JP 4753724B2 JP 2006010854 A JP2006010854 A JP 2006010854A JP 2006010854 A JP2006010854 A JP 2006010854A JP 4753724 B2 JP4753724 B2 JP 4753724B2
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- platinum
- alumina
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- based catalyst
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 210
- 239000003054 catalyst Substances 0.000 title claims description 156
- 229910052697 platinum Inorganic materials 0.000 title claims description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 102
- 238000000034 method Methods 0.000 claims description 66
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 49
- 239000002131 composite material Substances 0.000 claims description 45
- 229910052718 tin Inorganic materials 0.000 claims description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 40
- 239000012188 paraffin wax Substances 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 235000010981 methylcellulose Nutrition 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229920001983 poloxamer Polymers 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002563 ionic surfactant Substances 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 230000002146 bilateral effect Effects 0.000 claims description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 46
- 229930195733 hydrocarbon Natural products 0.000 description 33
- 150000002430 hydrocarbons Chemical class 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 230000000694 effects Effects 0.000 description 23
- 239000004215 Carbon black (E152) Substances 0.000 description 22
- 239000002243 precursor Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 13
- -1 aliphatic olefins Chemical class 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 150000005673 monoalkenes Chemical class 0.000 description 12
- 238000007086 side reaction Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000571 coke Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000001491 aromatic compounds Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000009849 deactivation Effects 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910002846 Pt–Sn Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000003057 platinum Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は新規の白金系触媒及びその製造方法に関するものであって、より詳しくは非多孔性の高密度セラミック酸化物の表面に、メソ細孔の大きさの多孔性アルミナがコーティングされてなる複合担体に白金と錫の二元金属（バイメタル）錯化合物を担持させた後、マイクロ波を照射して製造された白金系触媒を用いて炭化水素の転換工程を行うと、従来の酸点による活性低下なく転換率の向上とモノーオレフィンの選択性を向上させ、副反応物である芳香族化合物の生成を抑制させて石油化学工業に有用に活用できる新規の白金系触媒及びその製造方法に関するものである。 The present invention relates to a novel platinum-based catalyst and a method for producing the same, and more specifically, a composite in which a porous alumina having a mesopore size is coated on the surface of a non-porous high-density ceramic oxide. after the bimetallic (bimetallic) complex compound of platinum and tin supported on carrier, when the conversion process of hydrocarbons using a platinum-based catalyst prepared using microwave radiation, activity by conventional acid sites The present invention relates to a novel platinum-based catalyst that can be effectively used in the petrochemical industry by improving the conversion rate and improving the selectivity of mono-olefin without lowering, suppressing the generation of aromatic compounds as side reactions, and a method for producing the same. is there.
炭化水素の転換工程は水素化反応、接触分解反応、接触改質反応及び脱水素反応などの最も重要な石油化学反応工程である。 The hydrocarbon conversion process is the most important petrochemical reaction process such as hydrogenation reaction, catalytic cracking reaction, catalytic reforming reaction and dehydrogenation reaction.
石油化学産業に用いられている脱水素化反応工程の代表的な応用分野ではプロピレン、イソ−ブテン、Ｃ １０ 〜Ｃ １５ 範囲の直鎖形モノ−オレフィンなどのような脂肪族オレフィンを製造する工程と、スチレン単量体のような不飽和芳香族化合物の製造工程とで分ける。脂肪族パラフィンから生成された脂肪族モノ−オレフィンは分子量によって可塑剤、生分解性洗剤（LAS）、洗剤型アルコール（Detergent alcohol）、エトキシレート（Ethoxylate）などの原料として活用されている。 Propylene In a typical field of application of the dehydrogenation reaction step used in the petrochemical industry, iso - butene, C 10 -C 15 range of linear type mono - process for producing the aliphatic olefins such as olefins And a process for producing an unsaturated aromatic compound such as a styrene monomer. Aliphatic mono-olefins produced from aliphatic paraffins are used as raw materials for plasticizers, biodegradable detergents (LAS), detergent-type alcohols, ethoxylates, etc., depending on the molecular weight.
脱水素化工程は見掛けには単純にみえるが詳しく調べてみれば非常に複雑な工程中の１つである。一般に、脱水素化反応は熱力学的に限界を持つ反応であって、特に転換率の制限と最も高い吸熱反応であるため熱をたくさん必要とし、転換率を上げるために温度を高める場合、分解、異性質化、芳香族化、少重合（oligomer）反応などの複雑な副反応が増大されるからである。また、最も大きな問題になるものはコーク生成による触媒の非活性化であって、コークの前駆体になる分子量の大きな芳香族化合物が生成される場合、非可逆的に触媒表面に吸着して触媒を非活性化させるようになり、燃焼または塩基性化合物による洗滌などのみによって触媒表面のコーク除去が可能である。熱力学的な観点からみて、Ｃ−Ｃ結合エネルギーが２４５kJ／molでＣ−Ｈ結合エネルギーの３６５kJ／molより小さいため、直鎖形パラフィンの脱水素の過程が効果的に進めるためにはＣ−Ｃ結合の分解を抑制してＣ−Ｈ結合の解離、つまり脱水素が効果的に起きられる触媒と反応条件の選定が非常に重要である。従って、熱分解反応を抑制するために脱水素触媒反応が比較的低い温度で行わなければならなく、副産物生成を抑制して工程経済性を合せられる適切なモノ−オレフィンの選択性と転換率が必要である。 Although the dehydrogenation process looks simple, it is one of the most complicated processes if it is examined in detail. In general, the dehydrogenation reaction is a thermodynamically limited reaction, especially if it requires a lot of heat because it is the highest endothermic reaction with limited conversion, and if the temperature is increased to increase the conversion, This is because complicated side reactions such as isomerization, aromatization, and oligomer reaction are increased. The biggest problem is the deactivation of the catalyst due to coke formation. When an aromatic compound with a large molecular weight that is a precursor of coke is produced, the catalyst is adsorbed on the catalyst surface irreversibly. The catalyst surface can be decoked only by combustion or washing with a basic compound. From the thermodynamic point of view, the C—C bond energy is 245 kJ / mol, which is smaller than the C—H bond energy of 365 kJ / mol. It is very important to select a catalyst and reaction conditions that suppress the decomposition of the C bond and effectively dissociate the C—H bond, that is, dehydrogenation. Therefore, the dehydrogenation catalytic reaction must be performed at a relatively low temperature in order to suppress the thermal decomposition reaction, and the appropriate mono-olefin selectivity and conversion rate that can suppress the by-product formation and match the process economy can be obtained. is necessary.
モノ−オレフィン化合物を製造するために工業的にいろいろ多様な脱水素工程が適用されているが、一般に白金を活性成分として使用し、助触媒の成分として錫（Ｓn）、コバルト（Ｃo）、鉛（Ｐb）、インジウム（Ｉn）、ゲルマニウム（Ｇe）、セシウム（Ｃe）の中の１つの成分を使用し、触媒の酸性による副反応を抑制するためにアルカリ金属及びアルカリ土類金属の中の１つ成分以上を添加剤として使用している。 A variety of industrial dehydrogenation processes have been applied to produce mono-olefin compounds. In general, platinum is used as an active component, and tin (Sn), cobalt (Co), and lead are used as promoter components. (Pb), indium (In), germanium (Ge), cesium (Ce), and one of the alkali metals and alkaline earth metals to suppress side reactions due to the acidity of the catalyst. More than one component is used as an additive.
直鎖形パラフィン（n-paraffin）の脱水素化反応によって、直鎖形モノ−オレフィン（n-monoolefin）を生成する過程から生成できる主反応物を調べてみれば次の通りである。 The main reactants that can be produced from the process of producing the linear mono-olefin by the dehydrogenation reaction of the linear paraffin (n-paraffin) are as follows.
直鎖形パラフィン（n-paraffin）の脱水素化反応によって、直鎖形モノ−オレフィン（n-monoolefin）を生成する過程から生成できる主反応物を、図６に示す。 FIG. 6 shows main reactants that can be produced from the process of producing linear mono-olefin by the dehydrogenation reaction of linear paraffin (n-paraffin).
前述のように、直鎖形モノ−オレフィンのみを選択的に得るためにはさらに選択的な脱水素化触媒が要求され、転換率は温度、圧力、反応物である水素／直鎖形パラフィンのモル比によって決められるが、温度が上がると転換率が増加し、圧力と水素／直鎖形パラフィンの割合が高ければ減少する。また、最適収率は空間速度の関数で得ることができ、空間速度が高ければ平衡に至らなく転換率が低くなり、空間速度が低ければ副反応によって直鎖形モノ−オレフィンの選択度が劣るので適正な空間速度が存在する。一般に用いられる直鎖形パラフィンの脱水素反応条件はほぼ反応温度が４５０〜５００℃、圧力が１〜２気圧、空間速度（LHSV）１０〜２０ｈ−１、水素対炭化水素のモル比は３〜９であり、この際得られる炭化水素の転換率は１０〜１８％、モノ−オレフィンの選択度は８０〜９５％程度で得られる。 As described above, in order to selectively obtain only the linear mono-olefin, a more selective dehydrogenation catalyst is required, and the conversion rate is the temperature, pressure, and the reaction conditions of the hydrogen / linear paraffin. As determined by the molar ratio, the conversion increases with increasing temperature and decreases with higher pressure and hydrogen / linear paraffin ratio. The optimum yield can be obtained as a function of space velocity. If the space velocity is high, the equilibrium is not reached and the conversion rate is low. If the space velocity is low, the selectivity of the linear mono-olefin is poor due to side reactions. So there is a proper space velocity. Generally used dehydrogenation reaction conditions for linear paraffin are approximately 450 to 500 ° C., pressure is 1 to 2 atm, space velocity (LHSV) is 10 to 20 h −1 , and hydrogen to hydrocarbon molar ratio is 3 to 3. The conversion rate of the hydrocarbon obtained in this case is 10 to 18%, and the selectivity for mono-olefin is about 80 to 95%.
直鎖形パラフィン脱水素化反応に用いられる代表的な白金系担持触媒はガンマ−アルミナに担持された白金（Ｐt）−錫（Ｓn）−リチウム（Ｌi）触媒であって、活性成分は高分散された白金であり錫の役割が活性と選択性、そして触媒安定性に最も重要であると知られている（例えば、特許文献１参照）。 A typical platinum-based supported catalyst used in the linear paraffin dehydrogenation reaction is a platinum (Pt) -tin (Sn) -lithium (Li) catalyst supported on gamma-alumina, and the active component is highly dispersed. It is known that the role of tin is the most important for activity, selectivity, and catalyst stability (see, for example, Patent Document 1).
ガンマ−アルミナ担体は脱水素触媒において白金の分散を安定化するのに最適の担体として知られている。触媒の安定性が減少する要因では炭素沈積物の発生、つまりコーキングによる活性点の微細表面と反応物との接触効率の減少と反応或いは後の活性成分間の焼結による活性表面と反応物との接触面積の減少などによって生じる。白金（Pt）−錫（Sn）触媒において錫の役割は、錫の水食された白金系触媒は錫の添加によって小さい白金粒子で担体表面に高分散でき、白金の活性を大きく変化させてコーク前駆体が白金表面に吸着されることを封鎖し、コーク前駆体を担体相に移動させて結局は活性点の非活性化を防ぐようになることで知られている。なお、脱水素化触媒において、触媒の酸点は直鎖形パラフィンのＣ−Ｃ結合の水素化分解反応を促進させて触媒の選択性を劣らせ触媒の非活性化を誘発するため、リチウムのようなアルカリ金属が担体の酸点を中和させるためによく添加される。 A gamma-alumina support is known as an optimal support for stabilizing the dispersion of platinum in a dehydrogenation catalyst. The cause of the decrease in the stability of the catalyst is the generation of carbon deposits, that is, the contact efficiency between the fine surface of the active site and the reactant due to coking and the reaction or the subsequent sintering between the active components and the active surface and the reactant. This is caused by a decrease in the contact area. The role of tin in platinum (Pt) -tin (Sn) catalysts is that platinum-plated catalysts that have been water-eroded with tin can be dispersed highly on the support surface with small platinum particles by adding tin, and the activity of platinum is greatly changed to produce coke. It is known that the precursor is blocked from being adsorbed on the platinum surface, and the coke precursor is moved to the support phase to eventually prevent deactivation of the active sites. In the dehydrogenation catalyst, the acid point of the catalyst promotes the hydrocracking reaction of the C—C bond of the straight-chain paraffin to deteriorate the selectivity of the catalyst and induce the deactivation of the lithium. Such alkali metals are often added to neutralize the acid sites of the support.
一方、直鎖形パラフィンの脱水素化反応の触媒に関する従来技術を調べると、今まで主に３つの側面に焦点が合せられている。第一は白金及び助触媒の高分散に活用できる担体粒子の効率的な製造方法、第二は脱水素触媒の活性及び選択性を高めるための白金及び助触媒の高分散方法、第３は脱水素触媒の非活性化を抑制できる触媒の製造方法などに関する３つがある。 On the other hand, when examining the prior art relating to the catalyst for the dehydrogenation reaction of linear paraffins, up to now, three main aspects have been focused. The first is an efficient method for producing carrier particles that can be used for high dispersion of platinum and cocatalyst, the second is a high dispersion method of platinum and cocatalyst for enhancing the activity and selectivity of the dehydrogenation catalyst, and the third is dehydration. There are three methods relating to a method for producing a catalyst capable of suppressing the deactivation of an elementary catalyst.
まず、白金系脱水素の触媒担体としては球形のアルミナ担体が広く用いられているが、直鎖形パラフィンの脱水素化反応には触媒活性成分の高分散担持と脱水素工程への適用性を高めるために、一般に０.５g/mL以下の低密度、１００m２／ｇ以上の高表面積、大きな細孔サイズと高い細孔体積を有するアルミナ担体の特性が要求される（例えば、特許文献２及び特許文献３参照）。 First, a spherical alumina carrier is widely used as the catalyst carrier for platinum-based dehydrogenation. However, for the dehydrogenation reaction of linear paraffins, high dispersion support of catalytic active components and applicability to the dehydrogenation process are important . In order to enhance, characteristics of an alumina support having a low density of 0.5 g / mL or less, a high surface area of 100 m 2 / g or more, a large pore size and a high pore volume are generally required (for example, Patent Document 2 and (See Patent Document 3).
飽和炭化水素の脱水素化触媒の反応の転換率と選択度を増加させるために、触媒成分を大きい表面積と大きい細孔体積の多孔性ガンマアルミナに連続的な含浸法に従って担持する方法が使用された（例えば、特許文献４参照）。また、Ｐｔ−Ｓｎ／Ａｌ２Ｏ３触媒においてコーク生成緩和のためガンマ−アルミナの酸点を弱化させるために助触媒であるアルカリ金属且つアルカリ土類金属を担持して製造する方法が例示されている（例えば、特許文献５参照）。そして、Ｃ２〜Ｃ３０範囲のパラフィン炭化水素の脱水素触媒成分として白金（Pt）、錫（Sn）、リチウム、そして担体としてガンマ−アルミナ（γ−Al2O3）の使用を報告している（例えば、特許文献６、７、８参照）。 In order to increase the conversion and selectivity of the reaction of the saturated hydrocarbon dehydrogenation catalyst, a method in which the catalyst components are supported on a porous gamma alumina with a large surface area and a large pore volume according to a continuous impregnation method is used. (For example, see Patent Document 4). In addition, a method of supporting an alkali metal and an alkaline earth metal, which are cocatalysts, in order to weaken the acid sites of gamma-alumina for coke formation relaxation in a Pt—Sn / Al 2 O 3 catalyst is exemplified. (For example, see Patent Document 5). Then, the use of platinum (Pt), tin (Sn), lithium as a dehydrogenation catalyst component of paraffin hydrocarbons in the C2 to C30 range, and gamma-alumina (γ-Al 2 O 3 ) as a carrier has been reported ( For example, see Patent Documents 6, 7, and 8).
なお、脱水素触媒として活性成分である白金、助触媒として錫(Sn)またはインジウム(In)、そしてリチウム(Li)またはカリウム(K)を担体の酸性度を低める添加剤として使用することを特徴としている（例えば、特許文献９、１０、１１、１２参照）。多くの場合、白金系触媒の一般の製造方法として球形ガンマ−アルミナ表面と内部に白金と錫または助触媒成分の濃度が相対的に均一に分布するように導く均一含浸法（Uniform impregnation）が提示された。
It is characterized by using platinum as an active component as a dehydrogenation catalyst, tin (Sn) or indium (In) as a co-catalyst, and lithium (Li) or potassium (K) as additives for reducing the acidity of the carrier. (For example, see
しかし、触媒活性点において、反応物または生成物の過度な露出によって特定な副反応が促進されてオレフィン選択性が劣ることを防ぐために、既存の白金系触媒の製造方法である均一含浸法の代わりに表面含浸法（Surface impregnation）を使用して製造された白金系触媒が提案された。例えば、白金族金属がガンマ−アルミナ担体表面の４００μm以内に担持される触媒を記述しており（例えば、特許文献１３参照）、同様に、白金は担体の表面にそして助触媒成分は担体の全体に均一に分布する触媒を提示しているが（例えば、特許文献１４参照）、この場合にも錫成分は担体表面と内部全体的に分布されるため、白金との助触媒作用のために使用される錫成分以外に余分の錫がさらに添加されなければならない。 However, in order to prevent specific side reactions from being promoted due to excessive exposure of the reactants or products at the catalyst active point, the olefin selectivity is deteriorated. A platinum-based catalyst manufactured using the surface impregnation method was proposed. For example, a catalyst is described in which a platinum group metal is supported within 400 μm of the surface of the gamma-alumina support (see, for example, Patent Document 13), similarly, platinum is on the surface of the support and the promoter component is on the support. Although a catalyst that uniformly distributes throughout the whole is presented (see, for example, Patent Document 14), in this case as well, the tin component is distributed throughout the surface of the support and inside thereof, and therefore, for the cocatalyst action with platinum. Extra tin must be added in addition to the tin component used.
また、担体内部（inner core）と表面（outer layerまたはshell）の組成や特性が合い異なる２層形担体上に触媒活性成分が担持されている触媒や触媒の製造方法も前々から提示されてきたが、最近はこのような類型の担体を使用した白金系触媒が炭化水素脱水素工程に良好な触媒活性及び安定性を示すという特許が報告された。α−アルミナのような素材を担体内部の物質で使用し、噴霧法でγ−アルミナのような耐熱性（Refractory）無機酸化物を表面にコーティングした２層形担体の表面に白金と錫、そしてリチウムを均一に分散させた触媒が炭化水素脱水素反応の選択性と触媒の耐久性を向上させるという特徴を報告し、有機結合剤であるポリビニルアルコール（polyvinyl alcohol）を使用してα−アルミナとγ−アルミナとを結合させるとき、触媒の磨耗度を向上させる方法を記載している（例えば、特許文献１５参照）。 In addition, a catalyst in which a catalytically active component is supported on a two-layered carrier in which the composition and characteristics of the inner core and the surface (outer layer or shell) are different and a method for producing the catalyst have been presented. Recently, however, a patent has been reported that a platinum-based catalyst using such a type of support exhibits good catalytic activity and stability in the hydrocarbon dehydrogenation process. Platinum and tin are formed on the surface of a two-layered carrier using a material such as α-alumina as a material inside the carrier and coated with a refractory inorganic oxide such as γ-alumina on the surface by a spray method. We have reported that the catalyst in which lithium is uniformly dispersed improves the selectivity of the hydrocarbon dehydrogenation reaction and the durability of the catalyst, and uses α-alumina using polyvinyl alcohol, which is an organic binder. A method for improving the degree of wear of the catalyst when bonding with γ-alumina is described (for example, see Patent Document 15).
特許文献１５から得られる触媒を用いた炭化水素の水素化、脱水素、酸化反応のような炭化水素転換工程（例えば、特許文献１６参照）、低い水含量を有する脱水素の条件で炭化水素の脱水素工程を提示したことがある（例えば、特許文献１７参照）。
これによって、本発明者は前記のような従来の多孔性酸化物担体の酸点形成による触媒が非活性化と、活性成分の不均一な分布などの問題が改善された新しい炭化水素の転換工程触媒及び製造方法を開発しようと研究した。その結果、担体で非多孔性の高密度セラミック酸化物表面に、特定のメソ細孔の範囲を有する多孔性アルミナがコーティングされて酸点が最小化された複合担体に活性成分である白金と助触媒である錫の二元金属錯化合物を担持してなる白金系触媒を製造し、活性成分と助触媒が均一に分布されて低い含量にも活性が大きく低下されないということがわかって、本発明を完成するようになった。 As a result, the present inventor has developed a new hydrocarbon conversion process in which problems such as deactivation of the catalyst due to acid spot formation of the conventional porous oxide support as described above and non-uniform distribution of active components are improved. We studied to develop catalysts and production methods. As a result, the composite non-porous high-density ceramic oxide coated with porous alumina having a specific mesopore range to minimize the acid sites and the active ingredient platinum and auxiliary to produce a platinum catalyst obtained by carrying a bimetallic complex compound of tin as a catalyst, and found that activity in low content active ingredient and cocatalyst are uniformly distributed can not be greatly reduced, the present invention Has come to be completed.
従って、本発明は活性の低下なく高い転換率で、副反応物を生成を減少しながら脱水素化反応において高い選択性を示す新規の炭化水素の転換工程用白金系触媒を提供することにその目的がある。 Accordingly, the present invention provides a novel platinum-based catalyst for a hydrocarbon conversion process that exhibits high selectivity in a dehydrogenation reaction at a high conversion rate without a decrease in activity, while reducing the production of by-products. There is a purpose.
また、本発明は乾燥時、マイクロ波を用いて活性成分と助触媒の効率的な分散を導く前記新規の炭化水素の転換工程用白金系触媒の製造方法を提供することにもう１つの目的がある。 Another object of the present invention is to provide a novel method for producing a platinum-based catalyst for a hydrocarbon conversion process that leads to efficient dispersion of an active component and a promoter using microwaves during drying. is there.
本発明は、非多孔性の高密度セラミック酸化物表面に２〜５０nmのメソサイズの細孔を有する多孔性アルミナがコーティングされてなる複合担体に、活性成分である白金と助触媒である錫の二元金属が担持される直鎖パラフィンの脱水素化工程用白金系触媒にその特徴がある。また、前記多孔性アルミナは４０m２／ｇ以上の比表面積を有することを特徴とする。 The present invention relates to a composite carrier obtained by coating porous alumina having mesosize pores of 2 to 50 nm on a non-porous high-density ceramic oxide surface, and two active metals, platinum and cocatalyst. The platinum-based catalyst for the dehydrogenation process of straight-chain paraffin on which the original metal is supported is characterized. The porous alumina has a specific surface area of 40 m 2 / g or more.
なお、本発明はアルミナゾル９０〜１００重量％、ジルコニアゾルまたはチタニアゾル０〜１０重量％が含有された混合溶液に前記混合溶液１００重量部に対して有機酸０.５〜１０重量部及び水溶性高分子０.１〜５重量部が含有されたアルミナ混合溶液を高密度セラミック酸化物の表面にコーティングして複合担体を製造する第１段階；前記第１段階の複合担体１００重量部に対して、アルコールに溶解された白金塩化物０.１〜１０重量部、錫塩化物０.１〜２０重量部及び無機酸１〜１０重量部を添加した後、２５〜８０℃の温度で反応させ白金−錫の錯化合物溶液を形成する第２段階；及び前記第２段階の白金−錫の錯化合物溶液に第１段階の複合担体を担持させ１００〜１５００Ｗの電力範囲で３０秒〜１０分間マイクロ波を照射して熱処理する第３段階；とを含めてなる直鎖パラフィンの脱水素化工程用白金系触媒の製造方法にさらに他の特徴がある。 In the present invention, 0.5 to 10 parts by weight of an organic acid and high water-solubility are added to a mixed solution containing 90 to 100% by weight of alumina sol and 0 to 10% by weight of zirconia sol or titania sol with respect to 100 parts by weight of the mixed solution. A first step of preparing a composite carrier by coating an alumina mixed solution containing 0.1 to 5 parts by weight of the molecule on the surface of the high-density ceramic oxide; After adding 0.1 to 10 parts by weight of platinum chloride dissolved in alcohol, 0.1 to 20 parts by weight of tin chloride and 1 to 10 parts by weight of inorganic acid, the reaction was effected at a temperature of 25 to 80 ° C. A second stage of forming a complex solution of tin; and a first stage of the composite carrier supported on the platinum-tin complex solution of the second stage, and applying microwaves in a power range of 100 to 1500 W for 30 seconds to 10 minutes. Irradiate There is still another feature in the method for producing a platinum-based catalyst for linear paraffin dehydrogenation process , including the third stage of heat treatment.
前記から説明したように、本発明によって非多孔性の高密度セラミック酸化物表面に２〜５０nmのメソ細孔及び４０m２／ｇ以上の比表面積を有するメソ細孔の大きさの多孔性アルミナがコーティングされてなる複合担体が担持された白金系触媒をマイクロ波の照射を介して製造して、触媒活性及びモノオレフィン選択性が向上され、副反応で生成される芳香族化合物の量が半ば水準で低下され石油化学産業の代表的な脱水素工程の効率を大きく改善させる効果がある。 As described above, according to the present invention, porous alumina having a mesopore size of 2-50 nm mesopores and a specific surface area of 40 m 2 / g or more on a non-porous high-density ceramic oxide surface is provided. A platinum-based catalyst carrying a coated composite carrier is manufactured through microwave irradiation, improving the catalytic activity and monoolefin selectivity, and the amount of aromatic compounds produced by side reactions is half the level. This has the effect of greatly improving the efficiency of the typical dehydrogenation process in the petrochemical industry.
以下、本発明を詳細に説明すると次の通りである。
本発明は炭化水素の脱水素化反応時に転換率を向上させて副反応は阻害しながら直鎖形パラフィン炭化水素の選択性の高い新規の炭化水素の転換工程用白金系触媒とその製造方法、そしてこれを用いた炭化水素の転換工程に関するものである。
Hereinafter, the present invention will be described in detail as follows.
The present invention is a novel platinum-based catalyst for a hydrocarbon conversion process having a high selectivity for linear paraffin hydrocarbons while improving the conversion rate during the dehydrogenation reaction of hydrocarbons and inhibiting side reactions, and a method for producing the same. And it is related with the conversion process of the hydrocarbon using this.
先ず、本発明による新規の白金系触媒についてより具体的に調べてみれば次の通りである。 First, the new platinum-based catalyst according to the present invention will be more specifically examined as follows.
本発明の触媒は非多孔性の高密度セラミック酸化物表面を、２〜５０nmのメソ細孔のサイズを有するように調節された多孔性アルミナがコーティングされた複合担体に活性成分である白金と助触媒である錫をマイクロ波の照射条件で担持させたことに技術構成上の最も大きな特徴がある。 The catalyst of the present invention has a non-porous high-density ceramic oxide surface and an active component platinum and a support on a composite support coated with porous alumina adjusted to have a mesopore size of 2 to 50 nm. The most significant feature of the technical configuration is that the catalyst tin is supported under microwave irradiation conditions.
また、本発明において前記メソ細孔のサイズを有する多孔性アルミナの場合、４０m２／ｇ以上の比表面積をさらに有することに特徴がある。 In the present invention, the porous alumina having the mesopore size is characterized by further having a specific surface area of 40 m 2 / g or more.
従来には前記活性成分と助触媒の分散度を極大化するための目的で高表面積を有する多孔性酸化物のアルミナを担体として多く使用したが、前記担体の表面酸点がコーク形成をはじめ触媒の非活性化の原因として作用した。このような問題を防止するためにアルカリ金属またはアルカリ土類金属を少量添加して酸点を中和したり、錫及びアルミナを同時にゲル化させて錫が均一に分布されたアルミナ担体を製造して使用した。しかし、前記の方法は酸点を根本的に除去できないため、前記触媒を用いて炭化水素の脱水素化工程を行う場合、芳香族化合物のような副反応を抑制させることに限界があった。 Conventionally, a porous oxide alumina having a high surface area has been used as a carrier for the purpose of maximizing the degree of dispersion of the active ingredient and the cocatalyst. Acted as a cause of deactivation. In order to prevent such problems, a small amount of alkali metal or alkaline earth metal is added to neutralize the acid sites, or tin and alumina are simultaneously gelled to produce an alumina carrier in which tin is uniformly distributed. Used. However, since the above method cannot fundamentally remove the acid sites, there is a limit in suppressing side reactions such as aromatic compounds when the hydrocarbon is dehydrogenated using the catalyst.
また、低表面積の高密度酸化物の担体は酸性度に基づいた触媒の非活性化は避けることができるが、活性成分と助触媒成分の分散度を大きく低下させるというもう１つの問題があって、これは殆ど活用性がなかった。 In addition, the low surface area high density oxide support can avoid deactivation of the catalyst based on the acidity, but there is another problem that the dispersibility of the active component and the promoter component is greatly reduced. This has little utility.
本発明は前記担体の選択使用の重要性に対して認知し、これに対して深く研究を続けた結果、非多孔性の高密度セラミック酸化物をコアとし、これの表面を２〜５０nmのメソ細孔及び４０m２／ｇ以上の比表面積を有するように調節された多孔性アルミナがコーティングするシェル構造を形成すれば、前記高密度セラミック酸化物によって酸点による問題発生は形成されず、多孔性のアルミナがコーティングされて一定成分比で含有され、活性成分と助触媒の分散度を向上させることができる。即ち、従来の担体である非多孔性の高密度セラミック酸化物と多孔性アルミナを組合せる単純な混合形態でなく、特定範囲で調節された均一なメソ細孔を有する多孔性アルミナを形成して反応物である炭化水素の移動を円滑にすることによってモノオレフィンに対する高い選択性とコーク形成による副反応を抑制させる効果が得られる。単純に混合して使用する場合には酸点によるコーク発生及びガンマアルミナのメソ細孔の不均一性による反応物の接近性の容易でない問題が生じるので、本発明が目的とする効果が得られなく、前記のように非多孔性のコアの表面を２〜５０nmの均一なメソ細孔及び４０m２／ｇ以上の比表面積を有するように調節された多孔性のシェルがコーティングした構造を形成する場合のみ可能である。 The present invention recognizes the importance of the selective use of the carrier, and as a result of intensive research on it, the non-porous high-density ceramic oxide is used as a core, and the surface thereof is 2 to 50 nm. If a shell structure coated with porous alumina adjusted to have pores and a specific surface area of 40 m 2 / g or more is formed, the high density ceramic oxide does not cause a problem due to acid sites, and is porous. The alumina is coated and contained at a constant component ratio, so that the dispersibility of the active component and the cocatalyst can be improved. That is, it is not a simple mixed form combining conventional non-porous high-density ceramic oxide and porous alumina, but forms porous alumina having uniform mesopores adjusted within a specific range. By smooth movement of the reactant hydrocarbon, high selectivity to monoolefin and the effect of suppressing side reactions due to coke formation can be obtained. In the case of simple mixing, coke generation due to acid sites and non-easy access of reactants due to non-uniformity of the mesopores of gamma alumina occur, so the intended effect of the present invention can be obtained. As described above, the surface of the non-porous core is coated with a porous shell adjusted to have uniform mesopores of 2 to 50 nm and a specific surface area of 40 m 2 / g or more. Only possible if.
前記非多孔性の高密度セラミック酸化物は当分野において一般に使用されるものであって特に限られてはいないが、具体的に例えばマグネシウムを含有したアルミナ、アルミナを含有したマグネシウム及びカルシウムアルミネートスピネル酸化物、ムライト（Mullite）、イットリウムが安定化されたジルコニア（YSZ）、カルシウムが安定化されたジルコニア（CSZ）、アルミナ及びコーディエライト（Cordierite）の中から選ばれることが良い。より望ましくは、マグネシウムを含有したアルミナを使用する方がよく、前記マグネシウムは５重量％以下を含有するのが望ましい。前記マグネシウムの含量が５重量％を超過する場合には球形高密度担体の機械的強度が弱くなる問題が生じるため、前記範囲内のマグネシウムを含有するアルミナを使用するのが良い。 The non-porous high-density ceramic oxide is generally used in the art and is not particularly limited. Specifically, for example, alumina containing magnesium, magnesium containing alumina, and calcium aluminate spinel. It may be selected from among oxide, mullite, yttrium-stabilized zirconia (YSZ), calcium-stabilized zirconia (CSZ), alumina, and cordierite. More preferably, it is better to use alumina containing magnesium, and the magnesium preferably contains 5% by weight or less. When the magnesium content exceeds 5% by weight, there is a problem that the mechanical strength of the spherical high-density carrier is weakened. Therefore, it is preferable to use alumina containing magnesium within the above range.
前記多孔性アルミナは前記複合担体のうち、０.５〜１０重量％で含有され、含有量が０.５重量％未満であれば触媒充填期間の熱的安定性の問題が生じ、１０重量％を超過する場合には活性触媒層が厚くなって反応性の低下をもたらす問題が生じる。また、前記アルミナ以外にジルコニア、チタニアなどの遷移金属が１つ以上置換された複合担体は前記遷移金属対比アルミナは０.０５〜５：９９.９５〜９５モル比で混合され、前記含量はアルミナの酸点の問題を解決する範囲で、さらに好ましくは０.０５〜１：９９.９５〜９９モル比で混合される。 The porous alumina is contained in the composite carrier in an amount of 0.5 to 10% by weight, and if the content is less than 0.5% by weight, a thermal stability problem occurs during the catalyst filling period. When the ratio exceeds 1, the active catalyst layer becomes thick, resulting in a problem that the reactivity is lowered. In addition to the alumina, the composite carrier in which one or more transition metals such as zirconia and titania are substituted is mixed with the transition metal contrast alumina in a molar ratio of 0.05 to 5: 99.95 to 95, and the content is alumina. In a range that solves the problem of acid sites, 0.05 to 1: 99.95 to 99 molar ratio is more preferable.
このような多孔性アルミナはメソ大きさ、望ましくは２〜５０nmの細孔を有するものがよく、前記細孔の大きさが２nm未満であれば反応物の移動に問題が生じ、５０nmを超える場合にはメソ細孔による細孔調節の効果を期待し難い問題があるため、前記範囲を保持することが好ましい。なお、多孔性アルミナの比表面積は最小限４０m２／ｇ以上の値を有するのがよく、前記比表面積が４０m２／ｇ以下であればメソ細孔による担持金属の高分散効果が得られないという問題が生じる。 Such porous alumina should have meso size, preferably 2 to 50 nm pores. If the pore size is less than 2 nm, there will be a problem in the movement of the reactant, and if it exceeds 50 nm. Has a problem that it is difficult to expect the effect of pore adjustment by mesopores, so it is preferable to keep the above range. The specific surface area of the porous alumina should have a value of at least 40 m 2 / g or more, and if the specific surface area is 40 m 2 / g or less, the high dispersion effect of the supported metal by the mesopores cannot be obtained. The problem arises.
前記アルミナのコーティング溶液はアルミナゾル９０〜１００重量％、ジルコニアゾルまたはチタニアゾル０〜１０重量％に、高密度セラミック担体に接着を容易にするため有機酸と水溶性高分子を混合使用する。前記有機酸は例えばクエン酸、酒石酸及びオレイン酸などを選択使用することができ、前記アルミナ溶液１００重量部に対して０.５〜１０重量部を使った方が良い。また、前記水溶性高分子はメチルセルローズまたはポリエチレングリコールを使用することができ、前記アルミナ溶液１００重量部に対して０.１〜５重量部を使用する方が良い。 The alumina coating solution is 90-100% by weight of alumina sol, 0-10% by weight of zirconia sol or titania sol, and an organic acid and a water-soluble polymer are mixed for easy adhesion to a high-density ceramic carrier. For example, citric acid, tartaric acid and oleic acid can be selectively used as the organic acid, and it is better to use 0.5 to 10 parts by weight with respect to 100 parts by weight of the alumina solution. In addition, methyl cellulose or polyethylene glycol can be used as the water-soluble polymer, and it is better to use 0.1 to 5 parts by weight with respect to 100 parts by weight of the alumina solution.
前記有機酸と水溶性高分子は必須成分でなく前述した効果を発現するために追加的に付加される成分であって、前記範囲を外れる場合には相対的に必須成分であるアルミナ成分の含量が低下されるから前記範囲を保持するのが好ましい。 The organic acid and the water-soluble polymer are not essential components but are additionally added in order to exhibit the above-mentioned effects, and if they are out of the range, the content of the relatively essential component of the alumina component The above-mentioned range is preferably maintained because of a decrease in
なお、前記アルミナ複合担体の均一なメソ細孔を調節するためにコーティング溶液に界面活性剤を追加して使用する。前記界面活性剤はイオン性界面活性剤、両側性高分子界面活性剤及びプルーロニック（Pluronic）の中から選んで使用することができる。前記イオン性界面活性剤はＣｎＨ２ｎ＋１Ｎ(ＣＨ３)３Ｘと ＣｎＨ２ｎ＋１Ｎ(Ｃ２Ｈ５)３Ｘ系列（この時、ｎ＝８〜２２の整数、Ｘ＝Ｃｌ、Ｂr、ＩまたはＦなどのハロゲン原子）、両側性高分子界面活性剤はＣｎＨ２ｎ＋１(ＯＣＨ２ＣＨ２)ｘＯＨ 系列（この時、ｎ＝１２〜２３の整数、ｘ＝０〜１００の整数）、プルーロニック（Pluronic）は(ＥＯ)ｘ(ＰＯ)ｙ(ＥＯ)ｘ系列（この時、２０＜ｘ＜１２０、２０＜ｙ＜１２０）が使用でき、これら界面活性剤は前記コーティング溶液１００重量部に対して１〜１０重量部を使用する。前記界面活性剤使用量が１重量部未満であればその量があまりにも微々であって目的とする効果発現が低調であり、１０重量部を超過する場合にも粘度の急激な増加によってコーティング時に均一性の問題が生じるため前記範囲を保持するのが良い。 In order to adjust the uniform mesopores of the alumina composite carrier, a surfactant is added to the coating solution. The surfactant may be selected from ionic surfactants, bilateral polymer surfactants, and Pluronic. The ionic surfactant includes C n H 2n + 1 N (CH 3 ) 3 X and C n H 2n + 1 N (C 2 H 5 ) 3 X series (at this time, an integer of n = 8 to 22, X = Cl, Br , Halogen atoms such as I or F), the bifunctional polymer surfactant is a C n H 2n + 1 (OCH 2 CH 2 ) x OH series (where n is an integer of 12 to 23, and x is an integer of 0 to 100) ), Pluronic (EO) x (PO) y (EO) x series (20 <x <120, 20 <y <120) can be used at this time, and these surfactants are 100 weights of the coating solution. 1-10 parts by weight are used per part. If the amount of the surfactant used is less than 1 part by weight, the amount is too small and the desired effect is low. Even if the amount exceeds 10 parts by weight , the viscosity increases rapidly during coating. Since the problem of uniformity occurs, it is preferable to maintain the above range.
このように製造されたコーティング溶液は焼成後に高密度セラミック酸化物の表面に２０〜５００μmの厚さでコーティングされ、前記厚さが２０μm未満であれば反応時に熱的安定性の問題があり、５００μmを超過する場合は反応物の拡散問題が生じる。 The coating solution thus prepared is coated with a thickness of 20 to 500 μm on the surface of the high-density ceramic oxide after firing. If the thickness is less than 20 μm , there is a problem of thermal stability during the reaction. If it exceeds 500 μm , there will be a problem of diffusion of reactants.
以上から製造された複合担体を活性成分である白金と助触媒成分である錫が一定の成分比で含有された錯化合物溶液に担持させて白金系触媒を製造した。 The composite carrier produced as described above was supported on a complex compound solution containing platinum as an active component and tin as a promoter component in a certain component ratio to produce a platinum-based catalyst.
前記担体を担持させる方法は当分野で使用される触媒の製造に用いられるもので特に限られてはいなく、本発明では含浸法を使用する。 The method for supporting the carrier is not particularly limited and is used in the production of a catalyst used in this field, and the impregnation method is used in the present invention.
前記白金と錫は塩化物、窒化物、硫化物及び炭化物などの前駆体化合物から導かれるもので特に限られてはいないが、望ましくは塩化物を使用するのが良く、これら白金と錫は１：０.５〜３.０のモル比で含有されるのが望ましい。前記錫のモル比が０.５モル比未満であれば白金と錫の合金を形成し難くてコーク形成の可能性が高く、３.０モル比を超過する場合にはコーク発生は抑制できるものの多量の錫によって活性が劣るという問題が生じるので、前記範囲を保持するのが良い。この際、活性金属である白金は複合担体中に０.０３〜５重量％含有され、前記含有量が０.０３重量％未満であれば活性が著しく劣って、５重量％を超過する場合には経済性のない問題が生じる。 The platinum and tin are derived from precursor compounds such as chlorides, nitrides, sulfides and carbides, and are not particularly limited. However, it is desirable to use chlorides. : It is desirable to contain in the molar ratio of 0.5-3.0. If the molar ratio of tin is less than 0.5 molar ratio, it is difficult to form an alloy of platinum and tin, and the possibility of coke formation is high. If the molar ratio exceeds 3.0 molar, generation of coke can be suppressed. Since the problem that the activity is inferior due to a large amount of tin occurs, it is preferable to keep the above range. In this case, platinum as an active metal is contained in the composite carrier in an amount of 0.03 to 5% by weight, and if the content is less than 0.03% by weight, the activity is remarkably inferior and exceeds 5% by weight. Causes problems that are not economical.
前記複合担体１００重量部に対して、アルコールに溶解された白金塩化物０.１〜１０重量部、錫塩化物０.１〜２０重量部及び無機酸１〜２０重量部を添加した後、反応させて白金−錫の錯化合物溶液を形成する。 After adding 0.1 to 10 parts by weight of platinum chloride dissolved in alcohol, 0.1 to 20 parts by weight of tin chloride and 1 to 20 parts by weight of an inorganic acid to 100 parts by weight of the composite carrier, the reaction To form a platinum-tin complex solution.
前記白金と錫の錯化合物を形成するために使用される無機酸は例えば、硫酸、窒酸及び塩酸を使用することができ、本発明では塩酸を使用する。前記塩酸の使用量が１重量部未満または１０重量部超過時には錯化物形成が成されないという問題があるから前記範囲内で適正量を注入するのが望ましい。 As the inorganic acid used to form the complex compound of platinum and tin, for example, sulfuric acid, nitric acid and hydrochloric acid can be used, and hydrochloric acid is used in the present invention. When the amount of the hydrochloric acid used is less than 1 part by weight or more than 10 parts by weight, there is a problem that complexation is not formed. Therefore, it is desirable to inject an appropriate amount within the above range.
前記白金−錫の錯化合物溶液の製造時、反応溶媒で通常的なアルコールを例として上げると、メタノール、エタノール及びイソプロパノールを使用することができ、錯化合物溶液の製造時の反応器は酸による反応性のためにガラス反応器を使った方が望ましい。また、反応温度は２５〜８０℃を保持し、前記反応温度を外れる場合には望ましいＰｔ−Ｓｎの錯化合物が形成されないという問題がある。 In the production of the platinum-tin complex solution, methanol, ethanol, and isopropanol can be used as an example of a normal alcohol as a reaction solvent, and the reactor used in the production of the complex solution is an acid reaction. It is desirable to use a glass reactor because of its properties. Further, the reaction temperature is maintained at 25 to 80 ° C. When the reaction temperature is exceeded, there is a problem that a desirable Pt—Sn complex compound is not formed.
以上から製造された白金−錫錯化合物溶液に前記複合担体を担持させ、この際、担持温度は２５〜６０℃を保持する。その後に前記複合担体が担持された触媒前駆体溶液を真空蒸発機（Rotary Evaporator, Heidolph社モデル4000）を用いて１００mmHg以下の真空度と４０〜８０℃の条件のオイル槽（oil bath）で１〜３時間以上蒸発させてPt-Sn前駆体が複合担体表面に担持された試料を得る。しかし、真空蒸発機で乾燥した複合担体表面上のPt−Sn前駆体には水とアルコールが配位されており追加的な乾燥過程が必要となるが、この際に一般的な対流形乾燥機における触媒乾燥の場合、乾燥時に担体表面と内部で水と溶媒の急激な濃度偏差によって触媒成分の均一な分散が容易でなく、さらに白金と錫の不均等な分布により触媒活性及び選択性低下が大きく起きることを観察した。 The composite carrier is supported on the platinum-tin complex solution prepared as described above, and the supporting temperature is maintained at 25 to 60 ° C. Thereafter, the catalyst precursor solution on which the composite carrier is supported is 1 in an oil bath using a vacuum evaporator (Rotary Evaporator, Heidolph Model 4000) in a vacuum degree of 100 mmHg or less and a temperature of 40 to 80 ° C. By evaporating for ˜3 hours or more, a sample in which the Pt—Sn precursor is supported on the surface of the composite carrier is obtained. However, the Pt-Sn precursor on the surface of the composite carrier dried by a vacuum evaporator is coordinated with water and alcohol, which requires an additional drying process. In this case, a general convection dryer is used. In the case of catalyst drying in the catalyst, uniform dispersion of catalyst components is not easy due to abrupt concentration deviation of water and solvent on the support surface and inside during drying, and catalyst activity and selectivity decrease due to uneven distribution of platinum and tin. Observed what happened greatly.
これによって、本発明では１００〜１５００Wの範囲で電力調節が可能なマイクロ波乾燥機を用いてPt−Sn前駆体が複合担体表面に担持された試料を試料の量に応じて３０秒〜１０分の範囲でマイクロ波を照射して白金−錫成分の均一分散を導く。前記マイクロ波の電力範囲が１００W未満であれば乾燥効果が微々であり、１５００Wを超過する場合は低エネルギー効率の問題があり、また照射時間が３０秒未満であれば十分な乾燥の効果がなく、１０分を超過する場合にはPt−Sn前駆体間の焼結（sintering）問題が生じる。 Accordingly, in the present invention, a sample in which the Pt-Sn precursor is supported on the surface of the composite carrier is used for 30 seconds to 10 minutes depending on the amount of the sample using a microwave dryer capable of adjusting power in the range of 100 to 1500 W. In this range, uniform dispersion of the platinum-tin component is induced by irradiation with microwaves. If the microwave power range is less than 100 W, the drying effect is insignificant; if it exceeds 1500 W, there is a problem of low energy efficiency, and if the irradiation time is less than 30 seconds, there is no sufficient drying effect. If it exceeds 10 minutes, a problem of sintering between Pt-Sn precursors occurs.
また、マイクロ波乾燥機はマイクロ波加熱中に熱風を分当り１００mL〜１０Lの範囲で吹き込まれ、排出機を取り付けて加熱時に発生する塩酸気体をマイクロ波乾燥機の外に排出させて塩酸気体の表面に再吸着を防止させる。マイクロ波乾燥機内における触媒処理後に残留する塩素濃度を測定したとき、その濃度は触媒の重量基準にて０.２％以内であるものと確認され、マイクロ波の加熱中に空気を熱風に通過させるときには触媒乾燥は勿論触媒焼成の効果まで得られるから追加的な焼成処理は不要になる。 In addition, the microwave dryer blows hot air in the range of 100 mL to 10 L per minute during microwave heating, and attaches a discharger to discharge hydrochloric acid gas generated during heating to the outside of the microwave dryer to remove hydrochloric acid gas. Prevent re-adsorption on the surface. When the concentration of chlorine remaining after the catalyst treatment in the microwave dryer was measured, it was confirmed that the concentration was within 0.2% based on the weight of the catalyst, and air was passed through hot air during microwave heating. In some cases, the catalyst is dried and, of course, the effect of catalyst calcination is obtained, so that no additional calcination treatment is required.
前記のような方法で得られる触媒は、５００〜６５０℃で２〜６時間水素に還元した後、最終的に二元金属に担持される白金系触媒が製造される。 The catalyst obtained by the above method is reduced to hydrogen at 500 to 650 ° C. for 2 to 6 hours, and finally a platinum catalyst supported on a binary metal is produced.
前記方法によって製造された新規の脱水素白金系触媒の表面の酸性度は高表面積の多孔性担体を使用した既存の脱水素触媒に比べて大幅に低くなって表面酸点を中和させるために従来のように追加的にアルカリ金属を添加する必要がなくなる。 In order to neutralize the surface acid sites, the surface acidity of the new dehydrogenated platinum catalyst produced by the above method is significantly lower than that of the existing dehydrogenation catalyst using a high surface area porous support. There is no need to add an alkali metal as in the prior art.
一方、前記から製造された白金系触媒を選択的パラフィン脱水素化反応に適用することができる。前記脱水素化反応は当分野において通常的に使用される工程であって特に限られていなく、一例に本発明では次のような脱水素化反応装置、反応条件及び触媒活性の測定方法などの条件で反応を行う。 On the other hand, the platinum-based catalyst produced from the above can be applied to the selective paraffin dehydrogenation reaction. The dehydrogenation reaction is a process usually used in the art and is not particularly limited. For example, in the present invention, the following dehydrogenation reaction apparatus, reaction conditions, a method for measuring catalyst activity, etc. The reaction is performed under conditions.
先ず、本発明で使用された装置は実験室で直接製作した典型的な固定層触媒反応装置が使用される。３／８インチのサイズのステンレススチル反応器に、反応中に触媒粉末が反応器の下部に沈むことを防止するために１μmの気孔を有するステンレススチルフィルタを反応器の中間に溶接して固定させた後、その上に還元された白金系触媒３〜１５mLを満たす。液状の炭化水素反応物はHPLCポンプ（ICI LC 1110）を使用して定量的に反応器に注入し、触媒非活性化を抑制するために水素気体は流量調節装置（Mass flow controller）を使用して流入する。直鎖形パラフィンの脱水素反応条件は反応温度が４００〜５００℃、圧力が０.５〜５気圧、空間速度LHSV＝１〜２０ｈ−１、水素対炭化水素のモル比＝３〜９の範囲で設定された。この際、前記脂肪族炭化水素混合物はＣ１０からＣ１６までの直鎖形炭化水素から構成されている。そして、反応前後の炭化水素の組成は屈折率（Refractive Index）検出器が取り付けられたHPLCを用いて分析し、この際にカラムは２つのシリカHPLCカラムを直列で連結して使用し、HPLCの溶出溶媒はイソ−オクタン炭化水素を使用する。 First, the apparatus used in the present invention is a typical fixed bed catalytic reactor manufactured directly in a laboratory. A stainless steel filter with 1 μm pores is welded to the middle of the reactor to prevent the catalyst powder from sinking to the bottom of the reactor during the reaction. After that, 3-15 mL of the platinum-based catalyst reduced thereon is filled. Liquid hydrocarbon reactants are quantitatively injected into the reactor using an HPLC pump (ICI LC 1110), and hydrogen gas is flowed through a mass flow controller to suppress catalyst deactivation. Inflow. The dehydrogenation reaction conditions for linear paraffins are as follows: reaction temperature 400-500 ° C., pressure 0.5-5 atm, space velocity LHSV = 1-20 h −1 , hydrogen to hydrocarbon molar ratio = 3-9 Was set in In this case, the aliphatic hydrocarbon mixture is composed of C 10 to C 16 linear hydrocarbons. The hydrocarbon composition before and after the reaction was analyzed using HPLC equipped with a refractive index detector. At this time, the column was used by connecting two silica HPLC columns in series. Iso-octane hydrocarbon is used as an elution solvent.
前記反応は従来と殆ど類似した条件で行うもので、本発明の新規の白金系触媒を使用した場合に触媒活性及びモノオレフィンの選択性が向上され、副反応で生成される芳香族化合物の量が半ばの水準に低下される効果を現す。 The reaction is carried out under almost the same conditions as in the past. When the novel platinum-based catalyst of the present invention is used, the catalytic activity and monoolefin selectivity are improved, and the amount of aromatic compound produced in the side reaction. Will be reduced to a mid-level.
以下、本発明を次の実施例に基づいてより詳しく説明するが、本発明がこれに限られるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on the following Example, this invention is not limited to this.
セラミック担体の製造ガンマ−アルミナ粉末７６重量％にベントナイト（日本Junsei社）１.６重量％、メチルセルローズ２.４重量％及び蒸留水２０重量％を混合した後、回転式球形セラミック成形機（Rotary granulator）を用いて直径１.５〜２.０mmの大きさの球形担体を成形し、１２０℃で５時間乾燥させた後、１１００℃で１２時間焼成して製造した。 Manufacture of ceramic carrier After mixing 76% by weight of gamma-alumina powder with 1.6% by weight of bentonite (Japan Junsei), 2.4% by weight of methylcellulose and 20% by weight of distilled water, a rotary spherical ceramic molding machine (Rotary A spherical carrier having a diameter of 1.5 to 2.0 mm was molded using a granulator, dried at 120 ° C. for 5 hours, and then fired at 1100 ° C. for 12 hours.
前記から製造された球形担体を１Nの薄い窒酸溶液中で７０℃で１時間全処理した後、蒸留水で残留する窒酸塩が殆どないように十分洗滌し、１２０℃で１２時間乾燥して活性化された酸化物表面を有する球形のマグネシウムアルミナ酸化物担体を製造した。 The spherical support prepared from the above is fully treated in a 1N thin nitric acid solution at 70 ° C. for 1 hour, then thoroughly washed with distilled water so that there is almost no residual nitrate, and dried at 120 ° C. for 12 hours. A spherical magnesium alumina oxide support having an activated oxide surface was prepared .
セラミック担体の製造イットリウムが安定化されたジルコニア（YSZ）粉末７６重量％にベントナイト（日本Junsei社）１.６重量％、メチルセルローズ２.４重量％及び蒸留水２０重量％を混合した後、回転式球形セラミック成形機（rotary granulator）を用いて直径１.５〜２.０mmの大きさの球形担体を成形し、１２０℃で５時間乾燥させた後、１１００℃で１２時間焼成して酸化物担体を製造した。 Manufacture of ceramic support 76% by weight of zirconia (YSZ) powder with stabilized yttrium was mixed with 1.6% by weight of bentonite (Japan Junsei), 2.4% by weight of methylcellulose and 20% by weight of distilled water, and then rotated. A spherical carrier having a diameter of 1.5 to 2.0 mm is formed using a rotary granulator, dried at 120 ° C. for 5 hours, and then calcined at 1100 ° C. for 12 hours to form an oxide. A carrier was produced.
前記から製造された球形担体を１Nの薄い窒酸溶液中で７０℃で１時間全処理した後、蒸留水で残留する窒酸塩が殆どないように十分洗滌し、１２０℃で１２時間乾燥して活性化された酸化物表面を形成した。 The spherical support prepared from the above is fully treated in a 1N thin nitric acid solution at 70 ° C. for 1 hour, then thoroughly washed with distilled water so that there is almost no residual nitrate, and dried at 120 ° C. for 12 hours. Activated oxide surfaces.
多孔性アルミナ担持の白金系触媒（触媒Ａ）
アルミニウムイソプロポキシド５４.１１ｇをイソプロピルアルコール溶媒２００ｇが入っている５００mL大きさのビーカーに入れ常温で撹拌しながら混ぜた。他のビーカーに４.７４ｇのクエン酸（Citric acid）と３.５ｇのポリエチレングリコールを２４ｇの蒸留水と１３ｇの濃い塩酸溶液が含まれている溶液に完全に溶かした。前記２つの溶液を混合した後、８０℃で３時間撹拌してアルミニウムコーティング溶液を製造した。
Porous alumina supported platinum catalyst (catalyst A)
Aluminum isopropoxide (54.11 g) was placed in a 500 mL beaker containing 200 g of isopropyl alcohol solvent and mixed at room temperature with stirring. In another beaker 4.74 g of citric acid and 3.5 g of polyethylene glycol were completely dissolved in a solution containing 24 g of distilled water and 13 g of concentrated hydrochloric acid solution. The two solutions were mixed and then stirred at 80 ° C. for 3 hours to prepare an aluminum coating solution.
以後に、前記から製造されたアルミニウム溶液を前記実施例１から得られた球形のマグネシウムアルミナ酸化物担体上にアルミナ酸化物が１０重量％を有するように添加した後振動形撹拌機（Shaker）で３時間撹拌の後８０℃で真空蒸発させた。次に、１２０℃で５時間乾燥、６００℃で６時間の焼成過程を経てアルミナ／マグネシウムアルミネート複合担体を製造した。 Thereafter, the aluminum solution prepared as described above was added to the spherical magnesium alumina oxide support obtained in Example 1 so that the alumina oxide had 10% by weight, and then shaken with a shaker. After stirring for 3 hours, it was evaporated in vacuo at 80 ° C. Next, an alumina / magnesium aluminate composite carrier was manufactured through a baking process at 120 ° C. for 5 hours and at 600 ° C. for 6 hours.
次の図１は前記から製造されたコーティング溶液を使用して形成された粉末のBET等温吸脱着グラフを示したものであって、多孔性のナノ細孔を有することを確認することができた。前記製造された触媒のBET分析結果、平均比表面積が１０８m２／ｇであることを確認した。 Next, FIG. 1 shows a BET isothermal adsorption / desorption graph of a powder formed using the coating solution prepared from the above, and it was confirmed that the powder had porous nanopores. . As a result of BET analysis of the produced catalyst, it was confirmed that the average specific surface area was 108 m 2 / g.
前記から製造されたアルミナ／マグネシウムアルミネート複合担体に、活性成分である白金と助触媒である錫が含有された触媒（触媒Ａ）を次のような方法で製造した。この際、白金と錫の活性成分が同時に含有されている化合物としてred trans-PtCl 2 (SnCl 3 ) 2 という白金−錫錯化合物を触媒の製造に使用した。 A catalyst (catalyst A) containing platinum as an active component and tin as a cocatalyst on the alumina / magnesium aluminate composite carrier produced as described above was produced by the following method. In this case, the active ingredient of the platinum and tin red trans-PtCl 2 platinum as (SnCl 3) 2 as a compound contained simultaneously - using Suzu錯compound for the preparation of the catalyst.
前記錯化合物は０.２２３ｇの白金塩（Ｈ２ＰtＣｌ６．ｘＨ２Ｏ）と０.１９４ｇの塩化第二錫水化物（ＳnＣｌ２．２Ｈ２Ｏ）を先ず５０ｍＬエタノール溶媒に混ぜてここに１Ｎ塩酸水溶液３００mLを添加して製造した。 The complex compound was prepared by mixing 0.223 g of platinum salt (H 2 PtCl 6 .xH 2 O) and 0.194 g of stannic chloride hydrate (SnCl 2 .2H 2 O) in 50 mL ethanol solvent and adding 1N It was prepared by adding 300 mL of hydrochloric acid aqueous solution.
前記から製造された白金−錫錯化合物溶液に、１２０℃で乾燥された５０ｇの複合担体を添加して振動形撹拌機（Shaker）で３時間撹拌した後、８０℃で真空蒸発させた。その後、熱風機と排出機を装着したマイクロ波乾燥機に触媒を移しておきマイクロ波の電力を１２００Wに合せた後、マイクロ波を５分間照射して白金系触媒を乾燥及び焼成した。 50 g of the composite carrier dried at 120 ° C. was added to the platinum-tin complex solution prepared above, and the mixture was stirred for 3 hours with a shaker (Shaker), and then evaporated in vacuo at 80 ° C. Thereafter, the catalyst was transferred to a microwave dryer equipped with a hot air blower and a discharger, the microwave power was adjusted to 1200 W, and the platinum-based catalyst was dried and calcined by irradiation with microwaves for 5 minutes.
前記から得られた白金系触媒を誘導結合プラズマ（Inductively Coupled Plasma,ICP）元素分析を介して含量を調査した時に、０.１６重量％の白金と０.２１重量％の錫が含有されていることが確認できた。 When the content of the platinum-based catalyst obtained from the above was investigated through inductively coupled plasma (ICP) elemental analysis, it contained 0.16% by weight of platinum and 0.21% by weight of tin. I was able to confirm.
多孔性ジルコニウム−アルミナ担持白金系触媒（触媒Ｂ）
アルミニウムイソプロポキシド５２.３１ｇとジルコニウムオキシ塩素化合物（ＺrＯＣｌ２．８Ｈ２Ｏ）２.０３７ｇをイソプロピルアルコール溶媒２００ｇが入っている５００mL大きさのビーカーに入れ常温で撹拌しながら混ぜた。他のビーカーに４.７４ｇのクエン酸（Citric acid）と３.５ｇのポリエチレングリコールを２４ｇの蒸留水と１３ｇの濃い塩酸溶液が含まれている溶液に完全に溶かした。前記２つの溶液を混合した後、８０℃で３時間撹拌してジルコニウム−アルミニウム（Al：Zr＝９５：５モル比）コーティング溶液を製造した。
Porous zirconium-alumina supported platinum-based catalyst (catalyst B)
Aluminum isopropoxide 52.31g zirconium oxy chloride compounds (ZrOCl 2 .8H 2 O) 2.037g was mixed with stirring at room temperature into a beaker of 500mL size that contains the isopropyl alcohol solvent 200 g. In another beaker 4.74 g of citric acid and 3.5 g of polyethylene glycol were completely dissolved in a solution containing 24 g of distilled water and 13 g of concentrated hydrochloric acid solution. The two solutions were mixed and then stirred at 80 ° C. for 3 hours to prepare a zirconium-aluminum (Al: Zr = 95: 5 molar ratio) coating solution.
以後に、前記から製造されたジルコニウム−アルミニウム溶液を前記実施例１から得られた球形のマグネシウムアルミネート酸化物担体上にジルコニウム−アルミナ酸化物が１０重量％を有するように添加した後振動形撹拌機（Shaker）で３時間撹拌の後８０℃で真空蒸発させた。次に、１２０℃で５時間乾燥、６００℃で６時間の焼成過程を経てジルコニウム−アルミナ／マグネシウムアルミネート複合担体を製造した。前記製造されたコーティング溶液を使用して形成された粉末の平均比表面積は１０３m２/gであることを確認した。 Thereafter, the zirconium-aluminum solution prepared above was added to the spherical magnesium aluminate oxide support obtained in Example 1 so that the zirconium-alumina oxide had 10% by weight, and then the vibration-type stirring was performed. The mixture was stirred for 3 hours in a shaker and evaporated in vacuo at 80 ° C. Next, a zirconium-alumina / magnesium aluminate composite carrier was manufactured through a drying process at 120 ° C. for 5 hours and a firing process at 600 ° C. for 6 hours. It was confirmed that the average specific surface area of the powder formed using the prepared coating solution was 103 m 2 / g.
次の図２は前記から製造されたコーティング溶液を使用して形成された粉末のBET等温吸脱着グラフを示したものであって、多孔性のナノ細孔を有することを確認することができた。 FIG. 2 shows a BET isothermal adsorption / desorption graph of the powder formed using the coating solution prepared from the above, and it was confirmed that the powder had porous nanopores. .
前記から製造されたジルコニウム−アルミナ／マグネシウムアルミネート複合担体に、活性成分である白金と助触媒である錫が含有された触媒（触媒B）を次のような方法で製造した。この際、白金と錫の活性成分が同時に含有されている化合物としてred trans-ＰtＣｌ２(ＳnＣｌ３)２という白金−錫錯化合物が触媒の製造に使用した。 A catalyst (catalyst B) containing platinum as an active ingredient and tin as a cocatalyst on the zirconium-alumina / magnesium aluminate composite carrier produced as described above was produced by the following method. At this time, a platinum-tin complex compound called red trans-PtCl 2 (SnCl 3 ) 2 was used for the production of the catalyst as a compound containing the active components of platinum and tin at the same time.
前記錯化合物は０.２２３ｇの白金塩（Ｈ２ＰtＣｌ６．ｘＨ２Ｏ）と０.１９４ｇの塩化第二錫水和物（ＳnＣｌ２ ・２Ｈ２Ｏ）を先ず５０mLエタノール溶媒に混ぜてここに１Ｎ塩酸水溶液３００mLを添加して製造した。 The complex compound was prepared by mixing 0.223 g of platinum salt (H 2 PtCl 6 .xH 2 O) and 0.194 g of stannic chloride hydrate (SnCl 2 · 2H 2 O) in a 50 mL ethanol solvent. It was prepared by adding 300 mL of 1N aqueous hydrochloric acid.
前記から製造された白金−錫錯化合物溶液に、１２０℃で乾燥された５０ｇの複合担体を添加して振動形撹拌機（Shaker）で３時間撹拌した後、８０℃で真空蒸発させた。その後、熱風機と排出機を装着したマイクロ波乾燥機に触媒を移っておきマイクロ波の電力を１２００Wに合せた後、マイクロ波を５分間照射して白金系触媒を乾燥及び焼成した。 50 g of the composite carrier dried at 120 ° C. was added to the platinum-tin complex solution prepared above, and the mixture was stirred for 3 hours with a shaker (Shaker), and then evaporated in vacuo at 80 ° C. Thereafter, the catalyst was transferred to a microwave dryer equipped with a hot air blower and a discharger, the microwave power was adjusted to 1200 W, and then the platinum-based catalyst was dried and calcined by irradiation with microwaves for 5 minutes.
前記から得られた白金系触媒を誘導結合プラズマ（Inductively Coupled Plasma,ICP）元素分析を介して含量を調査した時に、０.１６重量％の白金と０.２０重量％の錫が含有されていることが確認できた。 When the content of the platinum-based catalyst obtained from the above was investigated through inductively coupled plasma (ICP) elemental analysis, it contained 0.16% by weight of platinum and 0.20% by weight of tin. I was able to confirm.
また、図３は製造された白金系触媒をHFと１N濃度のＮaＯＨを用いて酸化物成分を全て溶かした後、残っている白金−錫成分の金属粒子を漉してから透過電子顕微鏡で観察した写真で、５〜１０nmの均一なサイズを有する結晶性の優れる金属粒子が得られることが確認できた。このような金属粒子はエネルギー分散X線分析（Energy Disperse Ｘ-ray Ａnalysis, ＥＤＡＸ）を介して白金と錫の二元合金から構成されたＰtｘＳnｙ（この際、ｘとｙは１〜４の整数を示す）化学種であることが確認できた。 Also, FIG. 3 shows the manufactured platinum catalyst dissolved in HF and 1N NaOH, all oxide components were dissolved, and then the remaining platinum-tin component metal particles were observed and observed with a transmission electron microscope. The photograph confirmed that metal particles having a uniform size of 5 to 10 nm and excellent crystallinity were obtained. Such metal particles are PtxSny composed of a binary alloy of platinum and tin through energy disperse X-ray analysis (EDAX) (where x and y are integers of 1 to 4). It was confirmed that it was a chemical species.
界面活性剤を用いた多孔性アルミナ担持白金系触媒(触媒Ｃ)
前記実施例１のセラミック複合担体表面に中性の高分子界面活性剤を追加に使用してメソ細孔形アルミナ担体を製造した。
Porous alumina-supported platinum catalyst using catalyst (catalyst C)
A mesoporous alumina support was prepared by additionally using a neutral polymer surfactant on the surface of the ceramic composite support of Example 1.
アルミニウムイソプロポキシド４０.６５ｇ、５０ｇのイソプロピルアルコール及び３０ｇの濃い塩酸（３７重量％HCl含有）の混合溶液を還流冷却機が取り付けられた２５０mLサイズの丸いフラスコ反応器に入れ、８５℃で５時間混合させた後、常温に冷却した。前記から冷却された混合溶液に１０ｇの高分子界面活性剤（BASF社の商品名、Pluronic F127l；(EO)106(PO)70(EO)106）と、５ｇの添加剤（Aldrich, PPO; Poly(propylene oxide)）を添加した後、常温で２時間撹拌してゾル溶液を製造した。 A mixed solution of 40.65 g of aluminum isopropoxide, 50 g of isopropyl alcohol, and 30 g of concentrated hydrochloric acid (containing 37 wt% HCl) was placed in a 250 mL round flask reactor equipped with a reflux condenser, and at 85 ° C. for 5 hours. After mixing, it was cooled to room temperature. 10 g of polymer surfactant (trade name of BASF, Pluronic F127l; (EO) 106 (PO) 70 (EO) 106) and 5 g of additive (Aldrich, PPO; Poly) were added to the mixed solution cooled from above. (propylene oxide)) was added and stirred at room temperature for 2 hours to produce a sol solution.
前記実施例１の球形マグネシウムアルミネート酸化物担体表面に、前記から製造されたアルミニウム混合溶液７重量％を添加してコーティングしてから、常温２時間乾燥した後、１２０℃で５時間乾燥した。以後に前記コーティングされた担体を６００℃で６時間の焼成過程を経てアルミナ／マグネシウムアルミネート複合担体を製造した。 The spherical magnesium aluminate oxide support surface of Example 1 was coated with 7% by weight of the aluminum mixed solution prepared above, dried at room temperature for 2 hours, and then dried at 120 ° C. for 5 hours. Thereafter, the coated carrier was subjected to a baking process at 600 ° C. for 6 hours to produce an alumina / magnesium aluminate composite carrier.
この際、前記複合担体製造過程において、球形の担体は漉して溶液中に一部残っている粉末を濾過して、１２０℃で５時間乾燥、６００℃で６時間の焼成を行った。図４に示したように、前記から製造された複合担体は１０nmの細孔構造を有し、表面積が２８０m２/gであるメソ細孔の構造のアルミナ酸化物が合成されるということが確認できた。 At this time, in the process of producing the composite carrier, the spherical carrier was removed and the powder partially remaining in the solution was filtered, dried at 120 ° C. for 5 hours, and calcined at 600 ° C. for 6 hours. As shown in FIG. 4, it was confirmed that the composite carrier produced from the above has a mesopore structure having a pore structure of 10 nm and a surface area of 280 m 2 / g. did it.
以後の実施例３と同様な方法で、前記界面活性剤を用いて製造された複合担体に活性成分である白金０.１６重量％、助触媒である錫０.２０重量％が含有された白金系触媒（触媒C）を製造した。 Platinum containing 0.16% by weight of platinum as an active ingredient and 0.20% by weight of tin as a cocatalyst in a composite carrier produced using the above surfactant in the same manner as in Example 3 A system catalyst (Catalyst C) was produced.
多孔性アルミナ担持白金系触媒(触媒Ｄ)
前記実施例３と同様に実施し、アルミナ混合溶液中、アルミニウムの前駆体溶液であるアルミニウムイソプロポキシドの代わりに５重量％のベーマイト（boehmite、AlOOH）系列のアルミナ前駆体と１N濃度の酢酸が含有されたアルミナゾル溶液を使用して、前記実施例２から得られたイットリウムが安定化されたジルコニア（YSZ）酸化物担体の表面にコーティングして複合担体を製造した。
Porous alumina supported platinum catalyst (catalyst D)
The same procedure as in Example 3 was carried out. In the alumina mixed solution, 5% by weight of boehmite (AlOOH) series alumina precursor and 1N concentration of acetic acid were used instead of aluminum isopropoxide, which is an aluminum precursor solution. Using the contained alumina sol solution, a composite carrier was manufactured by coating the surface of the zirconia (YSZ) oxide carrier stabilized with yttrium obtained from Example 2 above.
以後、前記から製造された複合担体に活性成分である白金０.１６重量％と助触媒である錫０.２０重量％が含有された白金系触媒(触媒D)を製造した。 Thereafter, a platinum-based catalyst (catalyst D) containing 0.16% by weight of platinum as an active ingredient and 0.20% by weight of tin as a co-catalyst was prepared in the composite carrier prepared above.
多孔性ジルコニウム−アルミナ担持白金系触媒(触媒Ｅ)
前記実施例４と同様に実施し、ジルコニウム−アルミナ混合溶液中、アルミニウムの前駆体溶液であるアルミニウムイソプロポキシドの代わりに５重量％のベーマイト（boehmite、AlOOH）系列のアルミナ前駆体と１N濃度の酢酸が含有されたアルミナゾル溶液を使用して、前記実施例２から得られたイットリウムが安定化されたジルコニア（YSZ）酸化物担体の表面にコーティングして複合担体を製造した。
Porous zirconium-alumina supported platinum catalyst (catalyst E)
The same procedure as in Example 4 was carried out. In the zirconium-alumina mixed solution, 5% by weight of boehmite (AlOOH) series alumina precursor and 1N concentration were used instead of aluminum isopropoxide, which is an aluminum precursor solution. Using an alumina sol solution containing acetic acid, the surface of the zirconia (YSZ) oxide support stabilized with yttrium obtained from Example 2 was coated to prepare a composite support.
以後に、前記から製造された複合担体に活性成分である白金０.１６重量％と助触媒である錫０.２０重量％が含有された白金系触媒（触媒E）を製造した。 Thereafter, a platinum-based catalyst (catalyst E) containing 0.16% by weight of platinum as an active ingredient and 0.20% by weight of tin as a co-catalyst was produced in the composite carrier produced as described above.
多孔性アルミナ担持白金系触媒(触媒Ｆ)
前記実施例４と同様に実施し、ジルコニウム−アルミナ混合溶液中、アルミニウムの前駆体溶液であるアルミニウムイソプロポキシドの代わりに５重量％のベーマイト(boehmite,AlOOH)系列のアルミナ前駆体と１N濃度の酢酸が含有されたアルミナゾル溶液を使用し、ポリエチレングリコールの代わりに４.０ｇのメチルセルローズを添加して、前記実施例２から得られたイットリウムが安定化されたジルコニア（YSZ）の表面にコーティングして複合担体を製造した。
Porous alumina supported platinum catalyst (catalyst F)
The same procedure as in Example 4 was carried out. In the zirconium-alumina mixed solution, 5% by weight of boehmite, AlOOH series alumina precursor and 1N concentration were used instead of aluminum isopropoxide, which is an aluminum precursor solution. Using an alumina sol solution containing acetic acid and adding 4.0 g of methyl cellulose instead of polyethylene glycol , the surface of yttrium-stabilized zirconia (YSZ) obtained from Example 2 was coated. Thus, a composite carrier was produced.
以後に、前記から製造された複合担体に活性成分である白金０.１６重量％と助触媒である錫０.２０重量％が含有された白金系触媒（触媒F）を製造した。 Thereafter, a platinum-based catalyst (catalyst F) containing 0.16% by weight of platinum as an active ingredient and 0.20% by weight of tin as a co-catalyst was prepared in the composite carrier prepared as described above.
多孔性アルミナ担持白金系触媒(触媒Ｇ)
前記実施例４と同様に実施し、ジルコニウム−アルミナ混合溶液中、アルミニウムの前駆体溶液であるアルミニウムイソプロポキシドの代わりに５重量％のベーマイト（boehmite、AlOOH）系列のアルミナ前駆体と１N濃度の酢酸が含有されたアルミナゾル溶液を使用し、ポリエチレングリコールの代わりに４.０ｇのメチルセルローズを添加して、前記実施例１から得られた球形のマグネシウムアルミネート酸化物担体の表面にコーティングして複合担体を製造した。
Porous alumina supported platinum catalyst (catalyst G)
The same procedure as in Example 4 was carried out. In the zirconium-alumina mixed solution, 5% by weight of boehmite (AlOOH) series alumina precursor and 1N concentration were used instead of aluminum isopropoxide, which is an aluminum precursor solution. Using an alumina sol solution containing acetic acid, adding 4.0 g of methylcellulose instead of polyethylene glycol , coating the surface of the spherical magnesium aluminate oxide carrier obtained from Example 1, and combining A carrier was produced.
以後に、前記から製造された複合担体に活性成分である白金０.１６重量％と助触媒である錫０.２０重量％が含有された白金系触媒（触媒G）を製造した。 Thereafter, a platinum-based catalyst (catalyst G) containing 0.16% by weight of platinum as an active ingredient and 0.20% by weight of tin as a co-catalyst was prepared in the composite carrier prepared as described above.
（比較例１）非多孔性アルミナ担持白金系触媒(触媒Ｈ)
前記実施例５と同様に実施し、アルミナ混合溶液に界面活性剤を使用しないことを除いては同一の方法によって触媒を製造した。製造された複合担体に活性成分である白金０.１６重量％、助触媒である錫０.２０重量％が含有された白金系触媒（触媒Ｈ）を製造した。次の図５は前記から製造されたコーティング溶液を使用して形成された粉末のBET等温吸脱着グラフを示したものであって、細孔のみを有する非多孔性物質であることが確認できた。前記製造された表面触媒層のBET分析結果、平均３０m２/gであった。
Comparative Example 1 Nonporous Alumina-Supported Platinum-Based Catalyst (Catalyst H)
The same procedure as in Example 5 was carried out, and a catalyst was produced by the same method except that no surfactant was used in the alumina mixed solution. A platinum-based catalyst (catalyst H) containing 0.16% by weight of platinum as an active ingredient and 0.20% by weight of tin as a co-catalyst was produced in the produced composite carrier. Next, FIG. 5 shows a BET isothermal adsorption / desorption graph of the powder formed using the coating solution produced from the above, confirming that it is a non-porous substance having only pores. . As a result of BET analysis of the produced surface catalyst layer, the average was 30 m 2 / g.
（比較例２）一般乾燥法で製造したＰt-Ｓn-γ−Ａｌ ２ Ｏ ３ ／α−Ａｌ ２ Ｏ ３
（触媒Ｉ）
担体は表面にガンマアルミナが担持されたバルク密度が０.７０g/mLである球形のαアルミナ担体を使用した。０.１６５重量％の白金、０.２０重量％の錫（モル比：Ｓn／Ｐt＝２）含有Ａｌ２Ｏ３をコーティングするために、担持溶液を０.２２３ｇの白金塩（Ｈ２ＰtＣｌ６．ｘＨ２Ｏ）と０.１９４ｇの塩化第二錫水化物（ＳnＣｌ２．２Ｈ２Ｏ）を５０mLのエタノールに混ぜ、１Ｎ塩酸３００mLを添加した。１２０℃のオーブンで乾燥された５０ｇのアルミナ担体を担持溶液に担持して８０℃で真空蒸発させてから１２０℃で１２時間乾燥した後、５５０℃で３時間焼成して白金−錫含有のアルミナ触媒を製造した。
(Comparative Example 2) Pt-Sn-γ-Al 2 O 3 / α-Al 2 O 3 produced by a general drying method
(Catalyst I)
As the carrier, a spherical α-alumina carrier having a bulk density of 0.70 g / mL with gamma-alumina supported on the surface was used. In order to coat 0.165% by weight of platinum and 0.20% by weight of tin (molar ratio: Sn / Pt = 2) containing Al 2 O 3 , the support solution was charged with 0.223 g of platinum salt (H 2 PtCl 6 .XH 2 O) and 0.194 g of stannic chloride hydrate (SnCl 2 .2H 2 O) were mixed in 50 mL of ethanol and 300 mL of 1N hydrochloric acid was added. 50 g of alumina carrier dried in an oven at 120 ° C. was supported on a supporting solution, evaporated in vacuo at 80 ° C., dried at 120 ° C. for 12 hours, and then calcined at 550 ° C. for 3 hours to contain platinum-tin-containing alumina. A catalyst was prepared.
（比較例３）一般乾燥法で製造したＰt-Ｓn-Ｌi／γ-Ａｌ ２ Ｏ ３ （触媒J）
担体は米国特許第４,６７７，２３７号の実施例３と類似した方法で、０.５３１ｇの白金塩（Ｈ２ＰtＣｌ６．ｘＨ２Ｏ）と３.９７４ｇのＬiＮＯ３、１Ｎ塩酸（ＨＣｌ）３００mLを混ぜた溶液に表面積がバルク密度が０.４６g/mLである球形の５０ｇの錫−アルミナ（ＳnＯ２／γ-Ａｌ２Ｏ３）に混ぜ、４０℃で真空蒸発の後、１２０℃で１２時間乾燥してから５５０℃で３時間焼成して白金−錫含有のアルミナ触媒を製造した。この際、前記から製造された触媒Ｋの組成は０.３８重量％のＰt、０.４９５重量％のＬiを示した。
(Comparative Example 3) Pt—Sn—Li / γ-Al 2 O 3 produced by a general drying method (Catalyst J)
The support was prepared in a manner similar to Example 3 of US Pat. No. 4,677,237, with 0.531 g of platinum salt (H 2 PtCl 6 .xH 2 O) and 3.974 g of LiNO 3 , 1N hydrochloric acid (HCl). The solution mixed with 300 mL was mixed with spherical 50 g of tin-alumina (SnO 2 / γ-Al 2 O 3 ) having a surface area of 0.46 g / mL of bulk density, vacuum evaporated at 40 ° C., and then 120 ° C. It was dried for 12 hours and then calcined at 550 ° C. for 3 hours to produce a platinum-tin-containing alumina catalyst. At this time, the composition of the catalyst K produced from the above showed 0.38 wt% Pt and 0.495 wt% Li.
（比較例４）畳層構造の脱水素触媒（触媒Ｋ）
米国特許第６，１７７，３８１号の実施例２に提示されたものと類似した方法によって白金、錫及びリチウムがガンマアルミナ／ガンマアルミナ畳層構造にコーティングされた脱水素触媒を製造する。この際、前記から製造された触媒Kの組成は０.１０重量％のPt、０.１０重量％のSn、０.２５重量％のLiを示した。
（実験例）脱水素反応実験
(Comparative Example 4) Dehydrogenation catalyst having a tatami layer structure (Catalyst K)
A dehydrogenation catalyst in which platinum, tin and lithium are coated in a gamma alumina / gamma alumina tatami layer structure is prepared by a method similar to that presented in Example 2 of US Pat. No. 6,177,381. At this time, the composition of the catalyst K prepared as described above was 0.10 wt% Pt, 0.10 wt% Sn, and 0.25 wt% Li.
(Experimental example) Dehydrogenation reaction experiment
前記実施例３〜９及び比較例１〜４から製造された触媒を固定層触媒反応器で直鎖形炭化水素の脱水素活性と選択性を測定した。 The catalysts prepared from Examples 3 to 9 and Comparative Examples 1 to 4 were measured for the dehydrogenation activity and selectivity of linear hydrocarbons in a fixed bed catalytic reactor.
前記それぞれの触媒を各々５mLずつ３／８インチのサイズのステンレススチル管型反応器に入れ満たし、３００mL流量の水素を溢しながら常温で５００℃まで分当り５℃の速度で昇温し、５００℃の温度で２時間還元処理した後、反応条件に合せてパラフィン脱水素化反応を行った。反応器を通過した生成物溶液を４℃以下の温度で冷却させて捕集し、反応後の溶液はHPLCを用いて濃度を分析し、触媒の活性と選択性を確認した。 Each 5 mL of each catalyst was filled into a 3/8 inch stainless steel tube reactor, filled with 300 mL of hydrogen, heated to 500 ° C. at room temperature, and heated at a rate of 5 ° C. per minute. After a reduction treatment at a temperature of 0 ° C. for 2 hours, a paraffin dehydrogenation reaction was performed according to the reaction conditions. The product solution that passed through the reactor was collected by cooling at a temperature of 4 ° C. or less, and the concentration of the solution after the reaction was analyzed using HPLC to confirm the activity and selectivity of the catalyst.
この際、直鎖形炭化水素はＣ１０炭化水素１１.８重量％、Ｃ１１炭化水素３４.７重量％、Ｃ１２炭化水素３０.５重量％、Ｃ１３炭化水素１９.９重量％、Ｃ１４炭化水素０.２７重量％を含有しているものを使用した。なお、前記脱水素反応条件は１気圧、４６０℃、ＬＨＳＶ＝２０／ｈ、水素対炭化水素のモル比＝４.５の条件から得られた反応結果を下記の表１に示した。 In this case, a straight-chain form hydrocarbon C 10 hydrocarbons 11.8 wt%, C 11 hydrocarbons 34.7 wt%, C 12 hydrocarbons 30.5 wt%, C 13 hydrocarbons 19.9 wt%, C A hydrocarbon containing 0.27% by weight of 14 hydrocarbons was used. The dehydrogenation reaction conditions are 1 atm, 460 ° C., LHSV = 20 / h, and the reaction results obtained from the hydrogen to hydrocarbon molar ratio = 4.5 are shown in Table 1 below.
前記表１からわかるように、本発明による複合担体を使用してマイクロ波を用いて焼成させた実施例３〜９の白金系触媒を用いて脱水素反応を行った場合、従来に提示された方法で製造された活性成分である白金の含量が高い比較例２〜４の触媒に比べてオレフィンの選択度が向上され、副反応物である芳香族化合物の収率が５０％以下に低下される傾向を示すことが確認された。特に、比較例１の非多孔性触媒Hに比べて比表面積の大きな実施例３〜５の多孔性触媒においては（Ａ、Ｂ及びＣ）広い比表面積に活性成分であるＰt、Ｓnの均一な分散によって非常に向上された転換率及びオレフィン選択度を示した。 As can be seen from Table 1 above, when the dehydrogenation reaction was performed using the platinum-based catalysts of Examples 3 to 9 calcined using microwaves using the composite carrier according to the present invention, it was conventionally presented. Compared with the catalysts of Comparative Examples 2 to 4 having a high content of platinum, which is an active ingredient produced by the method, the selectivity of olefins is improved and the yield of aromatic compounds as side reactions is reduced to 50% or less. It was confirmed that this tendency was shown. In particular, in the porous catalysts of Examples 3 to 5 having a large specific surface area compared to the non-porous catalyst H of Comparative Example 1, (A, B and C) the active components Pt and Sn are uniformly distributed over a wide specific surface area. The conversion and olefin selectivity were greatly improved by dispersion.
前記から説明したように、本発明によって非多孔性の高密度セラミック酸化物表面に２〜５０nmのメソ細孔及び４０m２／ｇ以上の比表面積を有するメソ細孔の大きさの多孔性アルミナがコーティングされてなる複合担体が担持された白金系触媒をマイクロ波の照射を介して製造して、触媒活性及びモノオレフィン選択性が向上され、副反応で生成される芳香族化合物の量が半ば水準で低下され石油化学産業の代表的な脱水素工程の効率を大きく改善させる効果がある。 As described above, according to the present invention, porous alumina having a mesopore size of 2-50 nm mesopores and a specific surface area of 40 m 2 / g or more on a non-porous high-density ceramic oxide surface is provided. A platinum-based catalyst carrying a coated composite carrier is manufactured through microwave irradiation, improving the catalytic activity and monoolefin selectivity, and the amount of aromatic compounds produced by side reactions is half the level. This has the effect of greatly improving the efficiency of the typical dehydrogenation process in the petrochemical industry.
符号の説明はない。 There is no description of the symbols.
Claims (14)
前記第１段階の複合担体１００重量部に対して、アルコールに溶解された白金塩化物０.１〜１０重量部、錫塩化物０.１〜２０重量部及び無機酸１〜１０重量部を添加した後、２５〜８０℃の温度で反応させ白金−錫の錯化合物溶液を形成する第２段階；及び前記第２段階の白金−錫の錯化合物溶液に第１段階の複合担体を担持させ１００〜１５００Ｗの電力範囲で３０秒〜１０分間マイクロ波を照射して熱処理する第３段階；
とを含めてなることを特徴とする直鎖パラフィンの脱水素化工程用白金系触媒の製造方法。 In a mixed solution containing 90 to 100% by weight of alumina sol and 0 to 10% by weight of zirconia sol or titania sol, 0.5 to 10 parts by weight of an organic acid and 0.1 to 0.1 parts of a water-soluble polymer with respect to 100 parts by weight of the mixed solution. A first step of preparing a composite carrier by coating a surface of a high-density ceramic oxide with an alumina mixed solution containing 5 parts by weight;
0.1 to 10 parts by weight of platinum chloride dissolved in alcohol, 0.1 to 20 parts by weight of tin chloride and 1 to 10 parts by weight of an inorganic acid are added to 100 parts by weight of the composite carrier in the first stage. Then, the second stage of reacting at a temperature of 25 to 80 ° C. to form a platinum-tin complex compound solution; and the first stage composite carrier supported on the platinum-tin complex compound solution of the second stage 100. A third stage of heat treatment by irradiating with microwaves for 30 seconds to 10 minutes in a power range of ˜1500 W;
A process for producing a platinum-based catalyst for use in a dehydrogenation process for straight-chain paraffins .
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| CN104588008B (en) * | 2013-11-01 | 2017-03-01 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation catalyst and preparation method thereof |
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