1,3-부타디엔의 제조방법
The present invention refers to 3 including ethanol (trimetallic catalyst) metal catalyst component is separated from the presence of 1,3-butadiene method for producing relates to. Said lanthanide on the microcarriers, methods silica catalyst, includes zirconium and zinc. Furthermore, the present invention refers to novel supported catalyst (supported catalyst) process for manufacturing thereof and relates to supported catalyst thereof. Finally, the present invention refers to zirconium and zinc further including catalyst in of catalysed reactions a used to increase the selectivity, from ethanol 1,3-in catalyst for for producing polybutadiene relates to the use of lanthanum. 1,3-butadiene is goods chemical, synthetic rubber for the manufacture of significant interest of wet liquid to flow down. Current, this produced from renewable resources, speed ball mainly.. 1,3-from ethanol renewable resources also synthesis catalyst of polybutadiene disclosure in the prior to. Most recently, m. D. Literature such as Jones ( WO 2012/015340 A1 has silver, gold or copper the group consisting of a metal selected from the, and magnesium, titanium, zirconium, and tantalum oxide, selectively alkali modified metal and/or cerium, tin or antimony-oxide selected from the group consisting of metal oxide containing ethanol in the presence of a catalyst that scavenges acetaldehyde and optionally including 1,3-butadiene is separated from the master model for producing describes (one-step) method. JP 2006/218395 A and JP 2005/206472 A organic compounds from the dispersion by (ammoxidation) relates to preparation of. Improved selectivity and/or conversion of polybutadiene a 1,3-a request for manufacturing method of wet liquid to flow down is sustained. According to the present invention, as catalyst metals on carrier including silica, lanthanum, zirconium and zinc catalyst including 1,3-butadiene to better conversion rate and selectivity it has been discovered that the found to provide. Therefore, in a first aspect, the present invention refers to i) and the support and then drying and including silica, lanthanum, zirconium, including zinc step supported catalyst for a fuel cell, and ii) ethanol (feed) raw material including said supported catalyst a contact with which includes directing an, including raw product 1,3-butadiene which is emitted from the light (raw product) a 1,3-relates to manufacturing method of polybutadiene. In a second aspect, the present invention refers to a) silica step the lignocellulosic material is impregnated salt including lanthanum carrier; b) a step) of drying the carrier; and c) step b) for drying impregnated carrier including supported catalyst composition as the glass powder is relates to the fabrication process for. Said supported catalyst as well as of lanthanum zirconium and zinc further includes a. Furthermore, third in one aspect, the present invention refers to an electrochemical method for process of a second aspect, can be or manufacturing a thin film or wafer relates to supported catalysts. Finally, in fourth, the present invention refers to ethanol is separated from that scavenges acetaldehyde and optionally including in method for producing 1,3-butadiene, 1,3-butadiene to said for increasing the selectivity of catalysed reactions use of the lanthanides, zirconium and zinc further including said catalyst a, relates to the use of lanthanum. 1) manufacturing process of supported catalyst As described above, the present invention refers to step a) to c) including a supported catalyst is relates to the fabrication process for. Step a) in, is impregnated salt lanthanum carrier including silica. Step b) in, step a) of dried carrier. Step c) in, step b) for drying impregnated carrier fired. A preferred in one embodiment, steps further process of the present invention, i.e. D) step c) control device of rotation range drying impregnated carrier step impregnating a zirconium and the zinc salt; E) step d) of drying the carrier; and F) step e) for drying impregnated carrier includes of firing the laminate, i.e. the process preferably is conducted whenever (two-step) a method of endpoint detection can. Alternative process the present invention according to a preferred in one embodiment, carrier a step) in lanthanum salt, of a zirconium salt, compo-nent impregnated stage cost for facility, and zinc, is conducted whenever producing master model this. Lanthanides suitable for example salt, inorganic acid salts of lanthanum, is preferably inorganic acid salts of La (III). A preferred inorganic acid is sulfuric acid, nitric acid and hydrochloric acid during and wherein the polymer is selected from, more preferably, the one at which a nitrate La (III). Most preferably, step a) lanthanum salt used in La (III) nitrate 6 hydrate, La (NO3)3/6H2 O is. Used in process for manufacturing of supported catalyst in stage cost for facility, zirconium, zirconium examples of a suitable salt, preferably, organic or non-organic inorganic salt Zr (IV). A preferred inorganic acid is sulfuric acid, nitric acid and hydrochloric acid is selected in. The most preferred zirconium salt e.g. Zr (O2 CCH3)4 and ZrO (NO3)2/xH2 O is. Acetylacetonate (acetylacetonate) salt, Zr (C2 H7 O2)4 preferably also use of. Zinc used in process for manufacturing of supported catalyst in stage cost for facility, , a suitable salt of zinc examples of. salt organic and inorganic acids. Most preferably salts are Zn (NO3)2/6H2 O and Zn (O2 CCH3)2/6H2 O is. 2) supported catalyst Of lanthanum supported catalyst of the present invention, zirconium, includes and zinc. The silica carrier, i.e. is supported on carrier including silica. Lanthanum for the quality of, entire of the present invention in metal La on carrier preferably comprises controls, 0.1 to 20 weight %, preferably 0.5 to 10 weight %, in particular 1 to 5 weight %, e.g. 2.0 to 3.0 weight % Na:K is preferably. Entire according to one aspect of the present invention the amount of a desired carrier on controls metal Zr, 0.1 to 5 weight %, preferably 0.5 to 3 weight %, in particular 1 to 2 weight %, e.g. preferably is 1.5 weight %. Entire desirable according to one aspect of the present invention the amount of zinc metal Zn on carrier controls, preferably 0.1 to 2 weight %, in particular 0.3 to 1.0 weight %, e.g. preferably is 0.5 weight %. The supported catalyst in terms of its entire of the present invention include silica which the carrier. Silica addition, carrier ceria, magnesia or alumina may comprise an. Most preferably, . positive photosensitive anionic a carrier (i.e., . silica having essentially). Suitable BET surface area a catalyst carrier include e.g. 50 to 800 m2 g-1 range SiO2 is. Preferably, pore diameter 40 to 2000 Å, preferably 100 to 600 Å, preferably in particular 150 to 500 Å in silica. Most in a preferred embodiment, a supported catalyst process of a first aspect of the present invention or produced thereby. can be obtained. Manufacturing method of polybutadiene 3) 1,3- Of the present invention 1,3-of polybutadiene manufacturing method including the following steps: I) and the support and then drying and including silica, lanthanum, zirconium, including zinc step supported catalyst for a fuel cell, and Ii) ethanol (feed) raw material including a contact with said supported catalyst including obtain 1,3-butadiene. Preferably, contacting steps ii) the 200 to 600 °C, preferably is carried out at a temperature range of 300 to 425 °C. Furthermore, ii contacting steps) the 0.2 to 7 h-1 space velocity per hour weight of preferably carried out in (weight hourly space velocity). Gas phase raw material includes ethanol 85 to 98 volume %, preferably 95 to 90 volume %, such as in the range of about 92 may include volume % (is raw ethanol remainder of the liquid). However, the preferably the present invention according to method, gas phase then, the raw materials further including in addition to ethanol to acetaldehyde is connected to the semiconductor layer.. In the embodiment, as shown in, literature in addition ( Therefore, maximum preferably that scavenges acetaldehyde then, the raw materials until 40 volume %, until maximum more preferably less than about 30 volume %, in particular maximum preferably includes until 20 volume %. Preferably the present invention according to method, Iii) raw product that scavenges acetaldehyde fraction and including number 1 1,3-butadiene grain fractions including number 2 includes further includes separating an RFID circuit. In the present invention according to method, step iii) at least a portion of the fraction obtained at the number 2. raw material. I.e., generated from at least a portion of the acetaldehyde is recycling. Hereinafter, embodiment show advantages of the present invention relate. Long as no described alternatively, all. given, based on the weight percentage. In the embodiment 1. Supported catalyst for manufacturing In the embodiment 1 to 4 and 5 to 10 for each manufacture of supported catalyst been carried out as follows. 1a) in the embodiment 1 to 4, and 11 In the embodiment 1 and 11 the literature such as Jones ( 1b) in the embodiment 5 to 10 and 12 to 28 A is divided into two by impregnated performed for all the production of supported catalyst: first, lanthanum nitrate-salt using the appropriate amount of silica impregnated comprises lanthanum at the adaptation. After impregnated, the n bit parallel data inputted drying impregnated carrier to of heating lamps 5 °C/min 500 °C it does, firing until the, two time was 5 to the temperature. Metal layer is, Zr (IV) and impregnating a Zn (II) salts, drying, and 500 °C to of heating lamps 5 °C/min until the firing section. The wall 5 was two time said catalyst temperature. 2. Catalyst test 325 to 375 °C, in gaseous phase, wherein said atmospheric weight per hour space velocity (WHSV) 0.3 to 5 h-1 test is performed for all the catalyst. Feedstock a, listed in tables so that individual asset, as shown, ethanol 96% volume % volume 4 and water (in the embodiment 1 to 12), ethanol 92 volume % volume % and water (in the embodiment 13 to 17) or 8, or purity ethanol (ethanol 92% volume % volume 8 and water) and that scavenges acetaldehyde raw ethanol: 9:1 is volumetric ratio of acetaldehyde (in the embodiment 14, 16, 19 and 23), 8:2 (27 to 24 and in the embodiment 15), and is a mixture mixed the is 7:3 (in the embodiment 28). Argon carrier gas was used. Reaction is 3-4 been is performed over time, after the period to the result obtained with the showed listed in tables so that individual asset. Meaning of number and abbreviation in said table which can be mass-produced. ET = ethanol AA = acetaldehyde 1,3BTD = 1,3-butadiene Comp. = composition Conv. Conversion rates= Sel. Selectivity= 1) SiO2 on 1.5 wt % Zr and 0.5 wt % Zn. [Wt %] La percentage displayed. amount of. Digits is % weight of metal on the microcarriers, methods. Metal etching selectively the metal oxide layer catalyst ZnO, ZrO2, and La2 O3. non-volatile memory elements is considered to exist substantially. 2) weight per hour space velocity 3) displayed is acetaldehyde/ethanol volume ratio ratio. 4) 92% 92% volume ethanol and H2 O 8 volume %. mixture by the addition of an initiator. Therefore, the volumetric ratio 2:8 20 volume % acetaldehyde, 73.6% volume ethanol, and H2 O. mixture by the addition of an initiator such as 6.4% volume. 5) conversion and selectivity such as Jones ( In the embodiment 1 a than that in a radial direction in the embodiment 2-10, silica-supported Zr/Zn lanthanide catalyst when used along with 1,3-butadiene to enhance to selectivity for,. In the embodiment 11 in the embodiment 12-28 and compares the. can be observed from a different visual result. Of which are held in any particular theory when it wishes to, the addition of lanthanum, Ag, Au, co, the acidity of carrier, through a column that is at the ethylenically unsaturated and ethanol as a result a plate having a, as a result increase the selectivity for the 1,3-butadiene is considered that. Furthermore, lanthanum the two molecular aldol condensation and to promote the reaction is considered to.. Specific in the embodiment (17 contrast 15,16) in, adding that scavenges acetaldehyde raw material 1,3-butadiene in selectivity for the since advantageous results, may be recycling byproduct is as well as, the recycling such in addition 1,3-butadiene selectivity for the on the first dielectric. Temperature (in the embodiment 20 contrast 22 ; 21 contrast 23 ; 26 contrast 24 ; 25 reference 27 contrast) for the, + acetaldehyde 1,3-butadiene in selectivity for the minimal effect, but having, the increased conversion. Of the present invention are several books of hereinafter relates preferred embodiment. 1. I) and the support and then drying and including silica, lanthanum, zirconium, including zinc step supported catalyst for a fuel cell; and Ii) ethanol including raw material contacting said supported catalyst Including, 1,3-butadiene which is emitted from the light product raw including a 1,3-manufacturing method of polybutadiene. 2. Number 1 in several books, ii contacting steps) the 300 to 425 °C characterized by method carried out at a temperature range of. 3. Number 1 number 2 or several books in several books, ii contacting steps) the 0.2-7 h-1 space velocity per hour weight of carried out in (weight hourly space velocity) characterized by method. 4. As described in claim one of a preceding aborts, then, the raw materials to further including acetaldehyde characterized by method. 5. A preceding several books in one of the several books, Iii) 1,3-butadiene product raw said that scavenges acetaldehyde fraction and including number 1 including number 2 including grain fractions to characterized by method further includes separating an RFID circuit. 6. Number 5 in several books, at least a portion of the fraction number 2 to a raw material characterized by method. 7. A preceding several books in one of the several books, ii contacting steps) according to the number 12 several books supported catalyst characterized by method carried out in the presence of. 8. Process for manufacturing supported catalyst, A) silica carrier including step impregnating a lanthanum salt; B) step a) of drying the carrier; and C) step b) composition as the glass powder carrier impregnated for drying Includes, In addition to said supported catalyst of lanthanum zirconium and zinc further including a process. 9. Number 8 in several books, said process D) step c) control device of rotation range drying impregnated carrier step impregnating a zirconium and the zinc salt; E) step d) of drying the carrier; and F) step e) composition as the glass powder carrier impregnated for drying To further including characterized by process. 10. Number 8 in several books, a step carrier) in lanthanum salt, of a zirconium salt, CMOS Image sensor having a self-impregnating a zinc salt and characterized by process. 11. Number 8 number 10 to several books in several books one of several books, characterized by process to silica-alumina carrier. 12. Number 8 number 11 to several books one of several books an electrochemical method for process of several books which can be manufactured with or a supported catalyst. 13. Ethanol is separated from that scavenges acetaldehyde and optionally including in catalyst for producing 1,3-butadiene, 1,3-butadiene to said of catalysed reactions use lanthanides for increasing the selectivity. The invention relates to the use of a novel silica-supported trimetallic (La/Zr/Zn) catalyst in the production of 1,3-butadiene from ethanol. The presence of lanthanum in the catalyst further comprising zirconium and zinc increases the catalyst's yield and selectivity to 1,3-butadiene. I) and the support and then drying and including silica, lanthanum, zirconium, zinc step supported catalyst for a fuel cell including; and ii) ethanol (feed) raw material including said supported catalyst a contact with which includes directing an, including raw product 1,3-butadiene which is emitted from the light (raw product) 1,3-a manufacturing method of polybutadiene. According to Claim 1, ii contacting steps) the 300 to 425 °C characterized by method carried out at a temperature range of. According to Claim 1 or Claim 2, ii contacting steps) the 0.2-7 h-1 space velocity per hour weight of carried out in (weight hourly space velocity) characterized by method. As described in claim one of a preceding aborts, then, the raw materials to further including acetaldehyde characterized by method. As described in claim one of a preceding aborts, iii) 1,3-butadiene product raw said that scavenges acetaldehyde fraction and including number 1 including number 2 including grain fractions to characterized by method further includes separating an RFID circuit. According to Claim 5, at least a portion of the fraction number 2 to a raw material characterized by method. As described in claim one of a preceding aborts, ii contacting steps) the, a) silica step the lignocellulosic material is impregnated salt including lanthanum carrier; b) a step) of drying the carrier; and c) step b) for drying impregnated carrier according to process including composition as the glass powder can be produced either extemporaneously prepared or in the presence of supported catalysts is performed, of lanthanum supported catalyst said further and zinc zirconium in addition to including characterized by method. According to Claim 7, said d process) step c) control device of rotation range drying impregnated carrier zirconium and the zinc salt step impregnating a; e) step d) of drying the carrier; and f) step e) for drying impregnated carrier to characterized by method further including composition as the glass powder. According to Claim 7, said process a step carrier) in lanthanum salt, of a zirconium salt, CMOS Image sensor having a self-impregnating a zinc salt and characterized by method. Ethanol is separated from that scavenges acetaldehyde and optionally including in catalyst for producing 1,3-butadiene, 1,3-butadiene to said for increasing the selectivity of catalysed reactions use of the lanthanides, zirconium and zinc further including said catalyst a, lanthanum use. In the embodiment Conditions Result5 Catalyst composition [wt %]1 [°C] T WHSV2 [h-1] AA/ET3 T Pore diameter ET4 comp. Conv. [%] 1,3BTD Sel for. [%] For 1,3BTD+AA Sel. [%] 1 ZrZn 375 5.25 0 3 500 96 21 5 88 2 ZrZn-La (0.5%) 375 5.25 0 3 500 96 13 10 89 3 ZrZn-La (1%) 375 5.25 0 3 500 96 22 16 87 4 ZrZn-La (5%) 375 5.25 0 3 500 96 15 10 95 5 ZrZn-La (0.5%) 375 5.25 0 3 500 96 12 12 90 6 ZrZn-La (1%) 375 5.25 0 3 500 96 30 15 88 7 ZrZn-La (2%) 375 5.25 0 3 500 96 12 24 88 8 ZrZn-La (3%) 375 5.25 0 3 500 96 12 19 91 9 ZrZn-La (5%) 375 5.25 0 3 500 96 14 15 92 10 ZrZn-La (10%) 375 5.25 0 3 500 96 26 16 92 11 ZrZn 325 0.3 0 4 500 96 43 27 39 12 ZrZn-La (3%) 325 0.3 0 4 500 96 42 70 79 13 ZrZn-La (3%) 325 0.3 0 4 150 92 21 68 76 14 ZrZn-La (3%) 325 0.3 1/9 4 150 92 24 71 78 15 ZrZn-La (3%) 325 0.3 2/8 4 150 92 21 74 80 16 ZrZn-La (2%) 325 0.3 1/9 4 150 92 17 73 79 17 ZrZn-La (2%) 325 0.3 0 4 150 92 33 62 73 19 ZrZn-La (2%) 340 0.3 1/9 4 150 92 17 71 77 20 ZrZn-La (3%) 340 0.3 1/9 4 250 92 36 65 72 21 ZrZn-La (3%) 340 0.45 1/9 4 250 92 29 62 77 22 ZrZn-La (3%) 360 0.3 1/9 4 250 92 39 65 73 23 ZrZn-La (3%) 360 0.45 1/9 4 250 92 34 60 75 24 ZrZn-La (3%) 340 0.3 2/8 4 250 92 36 68 79 25 ZrZn-La (3%) 340 0.45 2/8 4 250 92 23 66 82 26 ZrZn-La (3%) 360 0.3 2/8 4 250 92 41 66 77 27 ZrZn-La (3%) 360 0.45 2/8 4 250 92 31 61 78 28 ZrZn-La (3%) 340 0.3 3/7 4 250 92 23 69 81