TR201905518A2 - HIGHLY SELECTIVE BENZYL ALCOHOL PRODUCTION - Google Patents
HIGHLY SELECTIVE BENZYL ALCOHOL PRODUCTION Download PDFInfo
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 229910001603 clinoptilolite Inorganic materials 0.000 claims abstract description 55
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims abstract description 52
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010457 zeolite Substances 0.000 claims abstract description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 23
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 41
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002082 metal nanoparticle Substances 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 3
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 claims 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 claims 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 claims 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 20
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000001308 synthesis method Methods 0.000 description 7
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 4
- 229940073608 benzyl chloride Drugs 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QDMCHWCVLPVAES-UHFFFAOYSA-N 2-benzylbenzaldehyde Chemical compound O=CC1=CC=CC=C1CC1=CC=CC=C1 QDMCHWCVLPVAES-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- DTZRLFJKQHIVQA-UHFFFAOYSA-N palladium(2+);dinitrate;hydrate Chemical compound O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DTZRLFJKQHIVQA-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Mevcut buluş, yüksek seçimlilikte benzil alkol elde edilmesi için bir yöntem ile ilgilidir. Daha spesifik olarak mevcut buluş, doğal zeolit klinoptilolit destekli paladyum katalizör ve moleküler hidrojenin kullanıldığı bir fotohidrojenasyon reaksiyonu ile kısa sürede ve ılımlı koşullar altında benzaldehitten benzil alkol elde edilmesi için bir yöntem sağlamaktadır. Mevcut buluş ayrıca, söz konusu zeolit destekli amin fonksiyonel katalizörlerin sentezi için bir yöntem sunmaktadırThe present invention relates to a method for obtaining highly selective benzyl alcohol. More specifically, the present invention provides a method for obtaining benzyl alcohol from benzaldehyde in a short time and under mild conditions by a photohydrogenation reaction using natural zeolite clinoptilolite supported palladium catalyst and molecular hydrogen. The present invention also provides a method for the synthesis of said zeolite supported amine functional catalysts.
Description
Tarifname YÜKSEK SEÇIMLILIKTE BENZIL ALKOL ÜRETIMI Bulusun Ilgili Oldugu Alan Mevcut bulus, benzaldehidin hidrojenasyonu ile benzil alkol elde edilmesi için bir yöntem ile ilgilidir. Daha spesifik olarak mevcut bulus, dogal zeolit klinoptilolit destekli paladyum katalizör ve moleküler hidrojenin kullanildigi bir fotohidrojenasyon reaksiyonu ile kisa sürede ve ilimli kosullar altinda benzil alkol elde edilmesi için bir yöntem saglamaktadir. Buna ek olarak, söz konusu zeolit destekli amin fonksiyonel katalizörlerin sentezi için bir yöntem de mevcut bulusun kapsami dahilindedir. specification PRODUCTION OF HIGH SELECTION OF BENZYL ALCOHOL Field of Invention The present invention relates to a method for obtaining benzyl alcohol by hydrogenation of benzaldehyde. is relevant. More specifically, the present invention is a natural zeolite clinoptilolite supported palladium catalyst. and with a photohydrogenation reaction using molecular hydrogen in a short time and moderately provides a method for obtaining benzyl alcohol under certain conditions. In addition, the word There is also a method for the synthesis of the subject zeolite supported amine functional catalysts. is within its scope.
Teknigin Bilinen Durumu Benzil alkol, CAS numarasi 100-51-6 ve kimyasal formülü C7H80 olan, yumusak ve tatli kokulu yagli bir sivi formundaki birincil aromatik bir alkoldür. Benzil alkolün 20°C'de sudaki çözünürlügü mg/mL iken, ayni sicaklikta nitrofenoldeki çözünürlügü 50 mg/mL'dir. Kaynama noktasi boya, vernik ve yaglarin temizlenmesine birçok alanda yaygin olarak kullanilmaktadir. Bunlara ek olarak, ilaç endüstrisinde bakteriyostatik ajan olarak kullanimi da mevcuttur. State of the Art Benzyl alcohol, CAS number 100-51-6 and chemical formula C7H80, with a mild and sweet smell It is a primary aromatic alcohol in the form of an oily liquid. Solubility of benzyl alcohol in water at 20°C mg/mL, while its solubility in nitrophenol is 50 mg/mL at the same temperature. Boiling point It is widely used in many areas for cleaning paint, varnish and oil. In addition to these It is also used as a bacteriostatic agent in the pharmaceutical industry.
Benzil alkolün standart endüstriyel üretim prosedürü alkalin ortamda benzil klorürün hidrolize ugratilmasidir. Ancak bu yöntemde klorun uzaklastirilmasi ile dibenzil eter açiga çiktigi için, yöntemin uygulanabilirligini kisitlayan ciddi dezavantajlar bulunmaktadir. US 5728897 sayili patent dokümani, benzil klorürün hidrolizi ile benzil alkol hazirlanmasina yönelik yeni bir proses ile ilgilidir. Söz konusu patent dokümanina ait olan ve alkali metal hidroksit ve alkali metal benzil alkol elde edilmistir. Ancak yukarida da belirtildigi gibi, dokümana konu bu proseste dibenzil eter açiga çikmasi yöntemin dezavantaji olarak görülmektedir. The standard industrial production procedure of benzyl alcohol is the hydrolysis of benzyl chloride in an alkaline medium. is to be carried. However, since dibenzyl ether is released with the removal of chlorine in this method, There are serious disadvantages that limit the applicability of the method. US no. 5728897 The patent document describes a new process for the preparation of benzyl alcohol by the hydrolysis of benzyl chloride. It is related to. Alkali metal hydroxide and alkali metal benzyl alcohol was obtained. However, as stated above, in this process, which is the subject of the document, The release of dibenzyl ether is seen as a disadvantage of the method.
Benzil alkol üretiminde standart endüstriyel prosedürün bu dezavantajlarinin ortadan kaldirilmasi ve daha çevreci ve ekonomik bir metodun gelistirilmesi için farkli prosedürler kesfedilmistir. Benzaldehidin moleküler hidrojen ile direkt hidrojenasyonu ve hidrojen donörü sekonder bir alkolün kullanildigi transfer hidrojenasyonu da bu avantajli yöntemler arasindadir. These disadvantages of the standard industrial procedure in the production of benzyl alcohol are eliminated. different procedures for the removal and the development of a more environmentally friendly and economical method has been discovered. Direct hydrogenation of benzaldehyde with molecular hydrogen and hydrogen donor Transfer hydrogenation using a secondary alcohol is among these advantageous methods.
Hidrojenasyon yöntemi kapsaminda, benzaldehidin uygun katalizörler ile indirgenmesi yoluyla tek kademede benzil alkol üretilebilmektedir. Benzaldehit gibi aromatik aldehitlerin kullanildigi indirgenme reaksiyonlari genellikle kolay sekilde gerçeklestirilebilmektedir. Ancak bu tip redoks tepkimelerinde reaksiyonun gerçeklesmesinden ziyade istenilen ürüne olan seçimlilik önem kazanmaktadir. Bu nedenle, aromatik aldehitlerin indirgenmesine iliskin çalismalarin odak noktasi seçimliligi arttirmak olmustur. Seçimliligi arttirmak için genellikle yüksek sicaklik ve basinçli kaplar kullanilarak uzun süreli ve maliyetli denemeler yapilmaktadir. Dolayisiyla, benzil klorürün hidrolizine alternatifbir yöntem olan benzaldehit hidrojenasyonu daha çevreci bir metot olmasinin yani sira, daha ilimli kosullar altinda kisa sürede yüksek seçimlilik ile benzil alkol elde edilmesi de önemlidir. Within the scope of the hydrogenation method, by reduction of benzaldehyde with suitable catalysts. Benzyl alcohol can be produced in one step. Use of aromatic aldehydes such as benzaldehyde Reduction reactions can usually be carried out easily. However, this type of redox In reactions, the selectivity for the desired product is important rather than the realization of the reaction. is winning. Therefore, the focus of studies on the reduction of aromatic aldehydes is The point was to increase selectivity. To increase selectivity, high temperature and Long-term and costly trials are carried out using pressure vessels. Therefore, benzyl Benzaldehyde hydrogenation, which is an alternative method to the hydrolysis of chloride, is a more environmentally friendly method. Besides, benzyl alcohol can be obtained with high selectivity in a short time under more moderate conditions. is also important.
CN 107442149 sayili patent dokümani, benzaldehitten hidrojenasyon yoluyla benzil alkol elde etmeye yönelik bir reaksiyonda kullanilan köpük yapili bir katalizör ve söz konusu katalizörün hazirlanmasi için bir yöntem ile ilgilidir. Hidrojenasyon reaksiyonu sivi fazda gerçeklestirilmektedir. Elde edilen benzil alkolün seçimliliginin %986, reaksiyon sicakliginin ise 90°C oldugu ifade edilmektedir. Buna ek olarak, “Hydrodeoxygenati'on ofaldehydes catalyzed by supported palladi'um catai'ysts" isimli yayin, benzaldehit olarak da seçilebilen aldehitlerin hidrojenasyonu ve hidrodeoksijenasyonu ile ilgilidir. Söz konusu reaksiyonlar zeolit veya aktif karbon bazli paladyum katalizörleri ile gerçeklestirilmistir [Prochazkovâ, D., Zâmostný, P., Bejblovâ, M., Gervený, L., & Gejka, I. [2007). Hydrodeoxygenation of aldehydes catalyzed by supported palladi'um catai'ysts. Applied Catalysis A: General, 332(1), 56-64). Patent document numbered CN 107442149, benzyl alcohol is obtained from benzaldehyde by hydrogenation. a foamed catalyst used in a reaction to relates to a method for preparing the catalyst. The hydrogenation reaction is in the liquid phase is carried out. The selectivity of the obtained benzyl alcohol was 986%, the reaction temperature was It is stated to be 90°C. In addition, “Hydrodeoxygenati'on ofaldehydes catalyzed by The publication named "supported palladi'um catai'ysts" states that aldehydes that can also be selected as benzaldehyde related to hydrogenation and hydrodeoxygenation. These reactions are zeolite or active carried out with carbon-based palladium catalysts [Prochazkovâ, D., Zâmostný, P., Bejblovâ, M., Gervený, L., & Gejka, I. [2007). Hydrodeoxygenation of aldehydes catalyzed by supported palladi'um catai'ysts. Applied Catalysis A: General, 332(1), 56-64 ).
Benzaldehit hidrojenasyonu reaksiyonunda, reaksiyon kosullarinin yani sira katalizör seçimi de önemlidir. Benzaldehidin hidrojenasyonu reaksiyonunda tanimlanan problemlerin giderilmesi ancak prosese uygun ve kararli katalizörlerin gelistirilmesi ile gerçeklestirilebilir. Bu sebeple, reaksiyon aktivasyon enerjisini ve ürün seçimliligini kontrol altina alacak katalizörlerin gelistirmesi büyük önem tasimaktadir. Benzaldehidin benzil alkole seçici bir sekilde dönüsümünü saglayan heterojen katalizörlerin sentezi son yillarda yaygin olarak çalisilmaktadir. Katalizör sentezinde destek seçimi önem arz etmektedir. Örnegin platin bazli katalizörler için metal organik kafeslerin (MDF) destek olarak kullanilmasi aktiviteyi arttirmaktadir. Katalizörlerin seçimliligini etkileyen faktörlerden bir digeri, metal destek yüzeyinde bulunan bosluklardir. Örnegin karbon nanotüp üzerine immobilize edilen paladyum katalizörler dogasi itibariyle anyoniktir ve alkol olusumu için seçicilik göstermektedir. Seçimliligi etkileyen bir diger faktör, katalizörde bulunan metallerin sayisidir. Örnegin bimetalik katalizörler monometalik katalizörlere kiyasla daha iyi katalitik özellik sergilemektedirler. Bunlara ek olarak, yapilan çalismalar son ürün olarak alkol elde edilmesi için soy metallerin kullanilabilecegini göstermistir (Bhanushali, 1. T., Kainthla, l., Keri, R. S., 8; Nagaraja, B. M. (2016]. Catalyti'c Hydrogenati'on ofBenzaldehydeforSelective Synthesis Yukaridaki açiklamalar isiginda görülmektedir ki, benzaldehit basta olmak üzere aldehitlerin hidroliz reaksiyonlarina alternatif olan hidrojenasyon reaksiyonlari ve bu reaksiyonlarda kullanilan katalizörlerin sentezi yogunlukla çalisilan bir alandir. Dolayisiyla, ilimli kosullarda yüksek seçimlilikle alkol eldesine imkan saglayacak katalizörlerin sentezlenmesi ve hidrojenasyon reaksiyonu için yeni yöntemlerin sunulmasi bu alanda bir gelisme saglayacaktir. In the benzaldehyde hydrogenation reaction, besides the reaction conditions, the choice of catalyst is also important. is important. Elimination of the problems described in the hydrogenation reaction of benzaldehyde it can only be realized by the development of process-appropriate and stable catalysts. Therefore, catalysts to control reaction activation energy and product selectivity. development is of great importance. Selective conversion of benzaldehyde to benzyl alcohol The synthesis of heterogeneous catalysts that provide catalyst The choice of support is important in the synthesis. For example, metal-organic catalysts for platinum-based catalysts The use of cages (MDF) as a support increases the activity. Selectivity of catalysts Another factor affecting the metal support surface is the gaps. For example, carbon Palladium catalysts immobilized on the nanotube are anionic in nature and shows selectivity for its formation. Another factor affecting selectivity is the is the number of metals. For example, bimetallic catalysts perform better than monometallic catalysts. exhibit catalytic properties. In addition to these, studies have shown alcohol as the final product. showed that noble metals can be used to obtain Keri, R. S., 8; Nagaraja, B. M. (2016]. Catalyti'c Hydrogenati'on of BenzaldehydeforSelective Synthesis In the light of the above explanations, it can be seen that aldehydes, especially benzaldehyde, hydrogenation reactions, which are alternatives to hydrolysis reactions and in these reactions The synthesis of the catalysts used is an intensively studied area. Therefore, in moderate conditions synthesis of catalysts that will enable alcohol production with high selectivity and Presentation of new methods for the hydrogenation reaction will provide an improvement in this field.
Bulusun Kisa Açiklamasi Mevcut bulus bir yönüyle, aldehitlerin hidrojenasyonu ile alkol elde edilmesi için bir yöntem saglamaktadir. Bulusa ait yönteme göre olan hidrojenasyon reaksiyonunda dogal zeolit klinoptilolit destekli katalizörler kullanilmaktadir. Brief Description of the Invention One aspect of the present invention is a method for obtaining alcohol by hydrogenation of aldehydes. it provides. Natural zeolite in the hydrogenation reaction according to the method of the invention Clinoptilolite supported catalysts are used.
Mevcut bulusa ait yöntemin tercih edilen bir yapilanmasinda, söz konusu yöntem benzaldehidin hidrojenasyonu ile benzil alkol elde edilmesine yönelik bir yöntemdir. In a preferred embodiment of the method of the present invention, said method is benzaldehyde It is a method for obtaining benzyl alcohol by hydrogenation.
Mevcut bulusa ait yöntemin tercih edilen yapilanmalarinda, söz konusu hidrojenasyon reaksiyonunda moleküler hidrojen kullanilmaktadir. In preferred embodiments of the method of the present invention, said hydrogenation Molecular hydrogen is used in the reaction.
Mevcut bulusa ait yöntemin tercih edilen diger bir yapilanmasinda, söz konusu hidrojenasyon reaksiyonu halojen lamba isimasi altinda oda sicakliginda gerçeklestirilmektedir. Mevcut bulusa ait yöntemin tercih edilen bir diger yapilanmasinda, söz konusu hidrojenasyon reaksiyonu kuartz kesikli bir reaktörde atmosferik basinçta gerçeklestirilmektedir. In another preferred embodiment of the method of the present invention, said hydrogenation The reaction is carried out at room temperature under the name of a halogen lamp. To the present invention In another preferred embodiment of the method, said hydrogenation reaction is carried out with quartz. carried out in a batch reactor at atmospheric pressure.
Mevcut bulus bir yönüyle, amin fonksiyonel dogal zeolit klinoptilolit destekli bir katalizör saglamaktadir. Bulusa göre olan söz konusu katalizör, bulusun tercih edilen bir yapilanmasinda klinoptilolite immobilize edilmis bir metal nanopartikülü ihtiva etmektedir. Tercih edilen yapilanmalarda, söz konusu metal nan0partikülü Pd, Pt, Rh nanOpartikülleri ile bunlarin ikili kombinasyonlarindan olusan bir gruptan seçilmektedir. In one aspect, the present invention provides an amine functional natural zeolite clinoptilolite supported catalyst. it provides. Said catalyst according to the invention is in a preferred embodiment of the invention. It contains a metal nanoparticle immobilized in clinoptilolite. Preferred In configurations, the metal nanoparticle in question is composed of Pd, Pt, Rh nanoparticles and their binary selected from a group of combinations.
Mevcut bulus diger bir yönüyle, bulusa ait katalizörün sentezi için bir yöntem sunmaktadir. Söz konusu yöntem asagidaki adimlari ihtiva etmektedir: - klinoptilolitin (CLT) yikanmasi, süzülmesi ve kurutulmasi, - kuruyan CLT'nin ögütülmesi ve elekten geçirilmesi, - kurutulmus CLT içeren sulu bir çözelti veya harca aminosilan gruplarinin eklenmesi, - amin fonksiyonel CLT'ye Pd[0], Pt(0], Rh(0] ve bunlarin ikili kombinasyonlarindan olusan bir gruptan seçilen nanopartiküllerin immobilizasyonu, ve - karistirma, filtrasyon ve kurutma islemleri sonrasinda klinoptilolit destekli katalizörün elde edilmesi. In another aspect, the present invention provides a method for the synthesis of the catalyst of the invention. Promise The method in question includes the following steps: - washing, filtering and drying of clinoptilolite (CLT), - grinding and sieving of the dried CLT, - adding aminosilane groups to an aqueous solution or mortar containing dried CLT, - amine functional CLT from Pd[0], Pt(0], Rh(0] and binary combinations thereof immobilization of nanoparticles selected from a group consisting of - Clinoptilolite supported after mixing, filtration and drying processes obtaining the catalyst.
Mevcut bulusa ait katalizör sentezi yönteminin tercih edilen bir yapilanmasinda, kurutulmus CLT içeren sulu bir çözelti veya harca eklenen söz konusu aminosilan gruplari, [3- Aminopropi1)trimetoksisilan (APTMS), 3-Aminopropil(dietoksi]metilsilan (APDEMS) ve [3- Aminopropil)trietoksisilan [APTES] arasindan seçilmektedir. In a preferred embodiment of the catalyst synthesis method of the present invention, dried CLT said aminosilane groups added to an aqueous solution or mortar containing [3- Aminopropyl)trimethoxysilane (APTMS), 3-Aminopropyl(diethoxy]methylsilane (APDEMS), and [3- Aminopropyl)triethoxysilane [APTES].
Mevcut bulusa ait katalizör sentezi yönteminin tercih edilen diger bir yapilanmasinda, CLT'ye immobilize edilen söz konusu nanopartiküller Pd(0) nanopartikülleridir. In another preferred embodiment of the catalyst synthesis method of the present invention, the CLT The immobilized nanoparticles are Pd(0) nanoparticles.
Mevcut bulus bir diger yönüyle, bulusa göre olan katalizörün aldehitlerin hidrojenasyonu ile alkol elde edilmesinde kullanimini saglamaktadir. In another aspect of the present invention, the catalyst according to the invention is alcohol by hydrogenation of aldehydes. provides its use in obtaining it.
Sekillerin Kisa Açiklamasi Sekil 1, bulus kapsaminda sentezlenen katalizörlerin kullanildigi hidrojenasyon reaksiyonu sirasinda benzaldehidin zamana bagli degisimini veren grafigi göstermektedir. Brief Description of Figures Figure 1, hydrogenation reaction using catalysts synthesized within the scope of the invention The graph shows the time dependent change of benzaldehyde during
Bulusun Ayrintili Açiklamasi Bu ayrintili açiklamada, mevcut bulusa konu olan benzil alkol üretimi yöntemi ve söz konusu yöntemde kullanilan katalizörlerin sentezi konunun daha iyi anlasilmasi için tarif edilmektedir. Detailed Description of the Invention In this detailed description, the benzyl alcohol production method of the present invention and the The synthesis of the catalysts used in the method is described for a better understanding of the subject.
Kimyasal formülü C7H80 olan benzil alkol birçok alanda kullanimi bulunan sivi formdaki birincil aromatik bir alkoldür. Standart endüstriyel üretim prosedürü benzil klorürün alkalin ortamda hidrolize ugratilmasidir. Ancak bu yöntem sirasinda klorun uzaklastirilmasi ile dibenzil eter açiga çikmasi, yöntemi dezavantajli hale getirmektedir. Benzyl alcohol, whose chemical formula is C7H80, is used in many areas and is a primary liquid form. It is an aromatic alcohol. Standard industrial production procedure is the use of benzyl chloride in an alkaline medium. is hydrolysis. However, dibenzyl ether is released by removal of chlorine during this method. This makes the method disadvantageous.
Benzil klorürün hidrolizine alternatif bir benzil alkol üretim yöntemi benzaldehidin moleküler hidrojen ile direkt hidrojenasyonu veya hidrojen donörü sekonder bir alkolün kullanildigi transfer hidrojenasyonudur. Hidrojenasyon reaksiyonu ile, benzaldehidin katalizörler esliginde indirgenmesi yoluyla benzil alkol üretilebilmektedir. Bu yöntemde önemli olan istenilen ürüne olan seçimlilik ve dönüsümdür. Seçimlilik istenilen ürünün agirliginin dönüsüm sonucu olusan ürün agirligina bölümünün 100 ile çarpilmasindan elde edilmektedir. Dönüsüm ise reaksiyon sonucu olusan ürün agirliginin toplam yüklenen agirliga bölümünün 100 ile çarpilmasindan elde edilmektedir. Dolayisiyla, hidrojenasyon reaksiyonunda ulasilmak istenen tam dönüsümde elde edilecek maksimum seçimliliktir. Bu amaçla genellikle yüksek sicaklik ve basinç kosullari tercih edilmektedir. Bu kosullarin ilimli hale getirilmesi ile benzil alkol elde edilmesi bu alanda bir gelisme saglayacaktir. An alternative benzyl alcohol production method to the hydrolysis of benzyl chloride is the molecular weight of benzaldehyde. direct hydrogenation with hydrogen or transfer using a hydrogen donor secondary alcohol hydrogenation. By hydrogenation reaction, accompanied by benzaldehyde catalysts Benzyl alcohol can be produced by reduction. The important thing in this method is the desired product. is selectivity and transformation. Selectivity is the result of the transformation of the weight of the desired product. It is obtained by multiplying the product weight division by 100. The transformation is the reaction obtained by multiplying the product weight resulting from the product weight to the total loaded weight by 100. is being done. Therefore, the desired full conversion to be achieved in the hydrogenation reaction is obtained. is the maximum selectivity. For this purpose, high temperature and pressure conditions are generally preferred. is being done. Obtaining benzyl alcohol by making these conditions mild is a problem in this field. will make progress.
Benzaldehit hidrojenasyonunda, reaksiyon kosullarinin yani sira katalizör seçimi de önemli bir parametredir. Katalizörlerin reaksiyon aktivasyon enerjisi ve seçimliligi kontrol edebilmesi tercih edilmektedir. Katalizör yüzeylerinde aktif sitelerin yaygin bulunmasi ve yüzeye homojen sekilde dagilmalari, heterojen katalizörlerde yüzey reaksiyonlarinin etkili sekilde gerçeklesmesinde önemlidir. Zeolitlerde hem Lewis hem de Bronsted asit siteleri olusmaktadir. Buna ek olarak, zeolitlerin moleküler elek yapisi asit sitelerin çogunun yüzeyde degil mikrogözeneklerin içinde olusmasini saglamaktadir. Bu sebeple, asit siteler moleküler elek yapisinin tamamlayici bir parçasidir. Disosiyatif adsorpsiyon ile üretilen hidroksil gruplarin (Bronsted asit siteleri) konsantrasyonu, katalizörün hazirlanma kosullari ve termal islemler ile dogrudan iliskilidir. Zeolit toplam asit sitelerin konsantrasyonu arttikça reaksiyona girecek madde daha çok adsorplanir ve asit siteler ile reaktan arasindaki hidrojen transferi daha kolay gerçeklesir. Hidrojenasyon reaksiyonlarinin hidrojenasyon-hidroliz yarismali sekilde gerçeklesen reaksiyonlar oldugu düsünüldügünde, hidrojen transferinin kolaylasmasinin reaksiyonu hidrojenasyon yönünde etkileyecegi görülmektedir. Bu sayede fotohidrojenasyon reaksiyonlari, yüksek sicaklik ve basinç kosullarina gerek duyulmadan daha ilimli kosullarda yüksek verim ile katalizlenebilmektedir. In benzaldehyde hydrogenation, besides the reaction conditions, the choice of catalyst is also an important factor. is the parameter. It is preferred that the catalysts can control the reaction activation energy and selectivity. is being done. The widespread presence of active sites on the catalyst surfaces and homogeneously dispersion is important in the effective realization of surface reactions in heterogeneous catalysts. is important. Both Lewis and Bronsted acid sites occur in zeolites. In addition, The molecular sieve structure of zeolites allows most of the acid sites to be inside the micropores rather than at the surface. makes it happen. Therefore, acid sites are an integral part of the molecular sieve structure. is part of it. Hydroxyl groups (Bronsted acid sites) produced by dissociative adsorption concentration is directly related to catalyst preparation conditions and thermal processes. Zeolite As the concentration of the total acid sites increases, the reactant is adsorbed more and The hydrogen transfer between the acid sites and the reactant occurs more easily. hydrogenation reactions are hydrogenation-hydrolysis competitive reactions. Considering that, the reaction of facilitating hydrogen transfer is in the direction of hydrogenation. appears to be affected. In this way, photohydrogenation reactions, high temperature and pressure It can be catalyzed with high efficiency in more moderate conditions without the need for conditions.
Dolayisiyla mevcut bulus bir yönüyle, aldehitlerin hidrojenasyonu ile alkol elde edilmesi için bir yöntem sunmaktadir. Söz konusu yönteme göre olan hidrojenasyon reaksiyonunda, dogal zeolit klinoptilolit destekli katalizörler kullanilmaktadir. Therefore, in one aspect, the present invention is a method for obtaining alcohol by hydrogenation of aldehydes. offers a method. In the hydrogenation reaction according to the method in question, natural zeolite Clinoptilolite supported catalysts are used.
Mevcut bulusa göre olan yöntemin tercih edilen bir yapilanmasinda, söz konusu yöntem benzaldehidin hidrojenasyonu ile benzil alkol elde edilmesine yöneliktir. In a preferred embodiment of the method according to the present invention, said method It is intended to obtain benzyl alcohol by hydrogenation of benzaldehyde.
Mevcut bulusa ait yöntemin tercih edilen diger bir yapilanmasinda, söz konusu hidrojenasyon reaksiyonu moleküler hidrojen ile gerçeklestirilmektedir. In another preferred embodiment of the method of the present invention, said hydrogenation The reaction is carried out with molecular hydrogen.
Mevcut bulusa ait yöntemin tercih edilen bir diger yapilanmasinda, söz konusu hidrojenasyon reaksiyonu halojen lamba isimasi altinda oda sicakliginda gerçeklestirilmektedir. Mevcut bulusa ait yöntemin tercih edilen diger bir yapilanmasinda, söz konusu hidrojenasyon reaksiyonu kuartz kesikli bir reaktörde atmosferik basinçta gerçeklestirilmektedir. In another preferred embodiment of the method of the present invention, said hydrogenation The reaction is carried out at room temperature under the name of a halogen lamp. To the present invention In another preferred embodiment of the method, said hydrogenation reaction is carried out with quartz. carried out in a batch reactor at atmospheric pressure.
Mevcut bulus diger bir yönüyle, amin fonksiyonel dogal zeolit klinoptilolit destekli bir katalizör sunmaktadir. Bulusa göre olan söz konusu katalizör tercih edilen yapilanmalarda klinoptilolite immobilize edilmis bir metal nanopartikülü ihtiva etmektedir. Söz konusu metal nanopartikülü Pd, Pt, Rh nanopartikülleri ve bunlarin ikili kombinasyonlarindan olusan bir gruptan seçilmektedir. In another aspect of the present invention, an amine functional natural zeolite clinoptilolite supported catalyst. offers. Said catalyst according to the invention is clinoptilolite in preferred embodiments. It contains an immobilized metal nanoparticle. The metal nanoparticle in question From a group of Pd, Pt, Rh nanoparticles and their binary combinations is selected.
Mevcut bulus bir diger yönüyle, bulusa göre olan katalizörün sentezi için bir yöntem saglamaktadir. Söz konusu yöntem asagidaki adimlari ihtiva etmektedir: - klinoptilolitin (CLT) yikanmasi, süzülmesi ve kurutulmasi, - kuruyan CLT'nin ögütülmesi ve elekten geçirilmesi, - amin fonksiyonel CLT'ye Pd[0], Pt(0], Rh(0] ve bunlarin ikili kombinasyonlarindan olusan bir gruptan seçilen nanopartiküllerin immobilizasyonu, ve - karistirma, filtrasyon ve kurutma islemleri sonrasinda klinoptilolit destekli katalizörün elde edilmesi. Another aspect of the present invention is a method for the synthesis of the catalyst according to the invention. it provides. This method includes the following steps: - washing, filtering and drying of clinoptilolite (CLT), - grinding and sieving of the dried CLT, - amine functional CLT from Pd[0], Pt(0], Rh(0] and binary combinations thereof immobilization of nanoparticles selected from a group consisting of - Clinoptilolite supported after mixing, filtration and drying processes obtaining the catalyst.
Mevcut bulusa ait katalizör sentezi yönteminin tercih edilen yapilanmasinda, kurutulmus CLT içeren sulu bir çözelti veya harca eklenen aminosilan gruplari, (3-Aminopropil]trimetoksisilan (APTMS), 3-Aminopropil[dietoksi]metilsilan (APDEMS) ve [3-AminopropiDtrietoksisilan (APTES) arasindan seçilmektedir. In the preferred embodiment of the catalyst synthesis method of the present invention, dried CLT aminosilane groups added to an aqueous solution or mortar containing (3-Aminopropyl]trimethoxysilane (APTMS), 3-Aminopropyl[diethoxy]methylsilane (APDEMS), and [3-Aminopropyl[diethoxy]methylsilane (APTES).
Mevcut bulusa ait katalizör sentezi yönteminin tercih edilen bir diger yapilanmasinda, CLT'ye immobilize edilen nanopartiküller Pd(0] nanopartikülleridir. In another preferred embodiment of the catalyst synthesis method of the present invention, the CLT The immobilized nanoparticles are Pd(0] nanoparticles.
Mevcut bulus diger bir yönüyle, hulusa göre olan katalizörün aldehitlerin hidrojenasyonu ile alkol elde edilmesinde kullanimini sunmaktadir. In another aspect of the present invention, the catalyst according to the invention is alcohol by hydrogenation of aldehydes. presents its use in obtaining it.
Bulusa ait fotohidrojenasyon ile yüksek seçimlilikte benzil alkol sentezi yönteminin ayrintili anlatimi asagidaki örneklerde saglanmaktadir. Bulus kapsaminda benzaldehitin, düsük metal içerigi (Pd, Pt ve Rh] ile hazirlanmis amin fonksiyonel klinoptilolit katalizörler varliginda kisa sürede benzil alkole tam olarak ve yüksek seçimlilikle dönüsümü gerçeklestirilmistir. Detail of the inventive method of synthesis of high selectivity benzyl alcohol by photohydrogenation The explanation is provided in the examples below. Within the scope of the invention, benzaldehyde is a low metal short-term in the presence of amine functional clinoptilolite catalysts prepared with content (Pd, Pt and Rh]. Complete and high selectivity conversion to benzyl alcohol was carried out in a short period of time.
Amin Fonksiyonel Zeolit Katalizörlerin Sentezi Bulus kapsaminda, zeolit destekli paladyum katalizör sentezi su adimlarla gerçeklestirilmistir: 1. Klinoptilolitin (CLT) deiyonize su ile yikanmasi, süzülmesi ve 105°C'de kurutulmasi, 2. Kuruyan CLT'nin ögütülmesi ve 90 mm altindaki bir elekten geçirilmesi. 3. Kurutulmus CLT içeren anhidröz diklorometan sulu harcina aminosilan gruplarinin eklenmesi, a) Homojen CLT'nin (3-Aminopropil]trimetoksisilan (APTMS) ile DCM çözeltisinde karistirilmasi b] Homojen CLT'nin 3-Aminopropil[dietoksi)metilsilan [APDEMS] ile DCM çözeltisinde karistirilmasi C] Homojen CLT'nin [3-Amin0propil)triet0ksisilan (APTES) ile DCM çözeltisinde karistirilmasi 4. Paladyum nitrat hidratin NaBH4 ile indirgenmesi, . Amin fonksiyonel CLT'nin Pd(0] nanopartikülleri ile immobilizasyonu, ve 6. 12 saat karistirma, filtrasyon ve 24 saat kurutma. Synthesis of Amine Functional Zeolite Catalysts Within the scope of the invention, zeolite supported palladium catalyst synthesis was carried out in the following steps: 1. Washing the clinoptilolite (CLT) with deionized water, filtering and drying at 105°C, 2. Grinding the dried CLT and passing it through a 90 mm sieve. 3. Addition of aminosilane groups to anhydrous dichloromethane aqueous slurry containing dried CLT adding, a) In DCM solution of homogeneous CLT (3-Aminopropyl]trimethoxysilane (APTMS) mixing b] DCM with 3-Aminopropyl[diethoxy)methylsilane [APDEMS] of homogeneous CLT mixing in solution C] Homogeneous CLT in DCM solution with [3-AminOpropyl)triethoxysilane (APTES) mixing 4. Reduction of palladium nitrate hydrate with NaBH4, . Immobilization of amine functional CLT with Pd(0] nanoparticles, and 6. 12 hours mixing, filtration and 24 hours drying.
Yukaridaki adimlarla gerçeklestirilen saf klinoptilolitten Pd[0] tutturulmus amin fonksiyonel zeolit eldesinde, dogal formda alinan klinoptilolitin safsizliklarinin giderilmesi ve homojen partiküller haline getirilmesi asamalari [1 ve 2] sentez metodunun temelini olusturmaktadir. Pd[0]-attached amine functional from pure clinoptilolite made by the above steps In obtaining zeolite, removing the impurities of the clinoptilolite taken in its natural form and homogeneous The steps of making particles into particles [1 and 2] form the basis of the synthesis method.
Aminosilan gruplarinin ilavesi asamasi [3a, 3b ve SC] diklorometan ortaminda gerçeklestirilmekte olup, karistirma süresi ve siddetinin yaninda süzme sirasindaki yikama islemlerine de dikkat edilmelidir. Paladyum nitratin sodyum bor hidrür ile indirgenmesi asamasinda ise [4] nihai süre ve indirgeyici ajan miktari iyi tespit edilmeli ve indirgemenin hemen ardindan bir sonraki basamaga geçilmelidir. Son basamaklarda (5 ve 6) indirgenmis Pd(0) çözeltisi üzerine fonksiyonel gruplarin ilavesiyle yapinin tam ve homojen sekilde metal ile baglanmasi saglanmalidir. Addition step of aminosilane groups [3a, 3b and SC] is carried out in the medium of dichloromethane. In addition to the mixing time and intensity, attention should also be paid to the washing processes during straining. should be done. In the reduction phase of palladium nitrate with sodium borohydride [4], the final time and the amount of reducing agent should be well determined and immediately after the reduction, the next step must be passed. In the last steps (5 and 6) functional on the reduced Pd(0) solution With the addition of groups, it should be ensured that the structure is fully and homogeneously bonded with the metal.
Paladyum nanopartiküllerin tutturuldugu amin fonksiyonel zeolit katalizörlerin sentez asamasinin ayrintili anlatimi iki baslik altinda incelenebilir. 1. CLT zeolitin sentezi ve amin katkisi ile fonksivanellestirilmesi Dogal zeolit klinoptilolit [CILT] ilk olarak safsizliklarin giderilmesi için deiyonize su ile iyice yikanarak beyaz bant süzgeç kagitlari ile süzdürülmüstür. Katisi ayristirilan bu CLT daha sonra 105°C'de etüVde kurutulmustur. Fonksiyonellestirmeye hazir hale gelmesi için, kafes (mesh) büyüklügü 90 um altinda olacak sekilde iyice ögütülmüstür. Ön yikama ve kurutma islemlerinden geçen dogal zeolit klinoptilolitin amin fonksiyonel hale getirilmesi için, aminosilan gruplarindan 3-Aminopropil(dietoksi)metilsilan (APDEMS), [3- Aminopropiljtrietoksisilan (APTES) ve (3-Aminopropil]trimetoksisilan [APTMS] kurutulmus CLT içeren anhidröz diklorometan sulu harcina oda sicakliginda ve atmosferik basinçta yavasça eklenmistir. Bu sulu harç kapali ve muhafazali cam kapta DCM çözeltisi ortamdan iyice uzaklasip yogun bir çökelek olusuncaya kadar karistirilmistir. Bej renkli kati filtre edilerek ayrilmis ve safsizliklardan kurtulmak için 3-5 defa diklorometan ile yikanmistir. Bej amin fonksiyonel topak (APTESCLT, APTMSCLT, APDEMSCLT) 70°C'de 24 saat kurutulmustur. Ayrica amin modifikasyonunun etkisini arastirmak için yari kat ve iki kat olarak iki farkli oranda amin fonksiyonel klinoptilolitler de hazirlanmistir. 2. Paiad um nano artikül özeltilerinin sentezi ve amin onksi one! klino tiIoIit zeolitin vüzevi üzerinde immobilizasvoniari sodyum borhidrür [NaBl-l4] ile indirgenmistir. Çözelti, bu indirgeme sonucunda gözlemlenen renk degisimi ile Pd[0) metalik nanopartiküllerin olusumlari teyit edilene kadar karistirilmistir. Bu asamadan sonra, elde edilen bu kolloidal çözeltilere hazirlanan amin fonksiyonel klinoptilolit yapilarindan (APTMSCLT, APTESCLT, APDEMSCLT] 0.01'er gram katilmis ve 12 saat manyetik karistirma altinda karistirilmistir. Reaksiyon sonunda, katinin çökmesi beklenmis ve filtrasyon islemi ile sividan ayristirilmistir. Üzerine Pd(0) nanopartiküllerinin immobilize edildigi amin fonksiyonel zeolitler yapiya bagli fazla iyonlarin ayristirilmasi için ilik su ile birkaç kez yikanmistir. Son olarak, yikanmis bu zeolitler 24- saat kurumaya birakilmistir. Synthesis of amine functional zeolite catalysts to which palladium nanoparticles are attached. The detailed explanation of the stage can be examined under two headings. 1. Synthesis of CLT zeolite and its functionalization with amine additive Natural zeolite clinoptilolite [CILT] is first thoroughly rinsed with deionized water to remove impurities. washed and filtered with white band filter papers. This CLT, whose solid was separated, was then It was dried in an oven at 105°C. To make it ready for functionalization, the mesh (mesh) It was finely ground to a size of less than 90 µm. The natural zeolite clinoptilolite, which undergoes pre-washing and drying processes, becomes amine functional. 3-Aminopropyl(diethoxy)methylsilane (APDEMS), one of the aminosilane groups, [3- Aminopropyl triethoxysilane (APTES) and (3-Aminopropyl]trimethoxysilane [APTMS] dried CLT slowly at room temperature and atmospheric pressure into anhydrous dichloromethane slurry containing has been added. In this slurry, the DCM solution is thoroughly removed from the environment in a closed and sealed glass container. mixed until a dense precipitate is formed. The beige solid was separated by filtering and It was washed 3-5 times with dichloromethane to get rid of impurities. Beige amine functional pellet (APTESCLT, APTMSCLT, APDEMSCLT) were dried at 70°C for 24 hours. Also amen In order to investigate the effect of its modification, amine in two different ratios as half and double functional clinoptilolites were also prepared. 2. Synthesis of Paiad um nano-article solutions and amine onxi one! klino tileolite zeolite immobilizasvoniari on the body reduced with sodium borohydride [NaB1-14]. The solution is the color observed as a result of this reduction. The formation of Pd[0) metallic nanoparticles was mixed until confirmed. This After this step, the amine functional clinoptilolite prepared into these obtained colloidal solutions 0.01 grams of each of their structures (APTMSCLT, APTESCLT, APDEMSCLT) were added and 12 hours magnetic mixed under stirring. At the end of the reaction, the solid was allowed to precipitate and filtration was carried out. It is separated from the liquid by the process. The amine on which Pd(0) nanoparticles are immobilized functional zeolites are washed several times with warm water to separate the excess ions due to the structure. has been washed. Finally, these washed zeolites were left to dry for 24-hours.
Katalizör sentezinin ardindan, moleküler hidrojen ve sentezlenen zeolit destekli amin fonksiyonel katalizör kullanilarak benzaldehitten benzil alkol eldesi gerçeklestirilmistir. Reaksiyon düzenegi kuartz kesikli bir reaktör ve hidrojen akisini saglayan bir gaz verme ünitesinden olusmaktadir. After catalyst synthesis, molecular hydrogen and synthesized zeolite supported amine functional Benzyl alcohol was obtained from benzaldehyde using a catalyst. reaction apparatus It consists of a quartz batch reactor and a gas supply unit that provides the hydrogen flow.
Halojen lamba isimasi altinda, oda sicakliginda ve atmosferik basinçta gerçeklestirilen fotohidrojenasyon reaksiyonu ile 20 dakika sonunda %100 verim ile benzil alkol elde edilmistir Dolayisiyla mevcut bulus, benzaldehitten benzil alkol eldesi için özgün ve avantajli bir yöntem saglamaktadir. Ilk olarak bulusa ait katalizör sentez yönteminde, teknigin bilinen durumunda yer alan benzer uygulamalardan farkli olarak baslangiç destek maddesi olarak dogal zeolit klinoptilolit (CLT) kullanilmistir. Buna ek olarak klinoptilolit yüzeyinin fonksiyonellestirilmesi sirasinda, benzer uygulamalardan farkli olarak aminosilan grubu degistirilmis ve aminosilan yüzey baglanma etkinligi incelenmistir. Ayrica bulusa ait katalizör sentezi yönteminde, Pd, Rh ve Pt metallerinin tekli kullanilmalarinin yani sira Pd-Rh ve Pd-Pt metal ikililerinin immobilizasyonu ile de katalizörler sentezlenmistir. Mevcut bulusla saglanan bir diger avantaj, hidrojenasyon reaksiyonlarinda genellikle uygulanan yüksek sicaklik ve basinç yerine reaksiyonun oda sicakliginda ve atmosferik basinçta gerçeklestirilmesidir. Bulus sahipleri bu ilimli kosullar altinda tek basamakta yüksek verimle ve tam seçimlilik ile benzil alkol elde etmislerdir. Son olarak mevcut bulus kapsaminda, sicaklik uygulamalarinin yerine halojen lamba isimasi tercih edilmistir. carried out under the name of a halogen lamp, at room temperature and atmospheric pressure. Benzyl alcohol was obtained with 100% yield at the end of 20 minutes by photohydrogenation reaction. Therefore, the present invention provides a unique and advantageous method for the preparation of benzyl alcohol from benzaldehyde. it provides. First, in the catalyst synthesis method of the invention, it was used in the state of the art. Natural zeolite as a starting support material, unlike similar applications in the field clinoptilolite (CLT) was used. In addition, functionalization of the clinoptilolite surface Unlike similar applications, the aminosilane group was changed and the aminosilane group was changed during the The surface bonding efficiency was investigated. Also, in the catalyst synthesis method of the invention, Pd, Rh and Immobilization of Pd-Rh and Pd-Pt metal binaries as well as single use of Pt metals Catalysts were synthesized with Another advantage provided by the present invention is hydrogenation. Instead of the high temperature and pressure usually applied in reactions, the reaction is in the room temperature and atmospheric pressure. Inventors under these moderate conditions They obtained benzyl alcohol with high yield and full selectivity in a single step. Finally Within the scope of the present invention, halogen lamp name is preferred instead of temperature applications.
Bu sebeple mevcut bulusa ait yöntem fotohidrojenasyon olarak nitelendirilmektedir ve lteratürde benzaldehit hidrojenasyonu üzerine ilk fotohidrojenasyon çalismasi olma özelligi tasimaktadir. For this reason, the method of the present invention is characterized as photohydrogenation and It is the first photohydrogenation study on benzaldehyde hydrogenation in the literature. carries.
Tüm bu veriler degerlendirildiginde, ilk kez bulus sahipleri tarafindan gerçeklestirilen fotohidrojenasyon ile benzilaldehitten yüksek seçimlilikte benzil alkol üretimi yöntemi hem ilimli kosullar altinda tek basamakta gerçeklestirilen bir yöntem olmasi sebebi ile hem de yöntem sonucunda yüksek verim ve tam dönüsümle benzil alkol eldesine imkan saglamasi sebebiyle avantajli ve önemlidir.When all these data are evaluated, it is seen that the first time performed by the inventors The method of producing high selectivity benzyl alcohol from benzylaldehyde by photohydrogenation Since it is a method that is carried out in a single step under conditions, both the method As a result, it provides the opportunity to obtain benzyl alcohol with high efficiency and full conversion. advantageous and important.
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