CN107398290A - 用于合成麝香草酚的催化剂 - Google Patents
用于合成麝香草酚的催化剂 Download PDFInfo
- Publication number
- CN107398290A CN107398290A CN201710481003.5A CN201710481003A CN107398290A CN 107398290 A CN107398290 A CN 107398290A CN 201710481003 A CN201710481003 A CN 201710481003A CN 107398290 A CN107398290 A CN 107398290A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hap
- thymol
- reaction
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 title abstract description 67
- 239000005844 Thymol Substances 0.000 title abstract description 34
- 229960000790 thymol Drugs 0.000 title abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 229910018182 Al—Cu Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 6
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 244000025254 Cannabis sativa Species 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- SUAUILGSCPYJCS-UHFFFAOYSA-N Musk ambrette Chemical compound COC1=C([N+]([O-])=O)C(C)=C([N+]([O-])=O)C=C1C(C)(C)C SUAUILGSCPYJCS-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052586 apatite Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 14
- 229940100630 metacresol Drugs 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 241000402754 Erythranthe moschata Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical group CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 1
- AVBKOZVDMFKBCC-UHFFFAOYSA-N 5-methyl-2-propan-2-ylphenol propan-2-ol Chemical compound CC(C)O.CC(C)C1=CC=C(C)C=C1O AVBKOZVDMFKBCC-UHFFFAOYSA-N 0.000 description 1
- 240000004784 Cymbopogon citratus Species 0.000 description 1
- 235000017897 Cymbopogon citratus Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 1
- 235000010676 Ocimum basilicum Nutrition 0.000 description 1
- 240000007926 Ocimum gratissimum Species 0.000 description 1
- 241001529744 Origanum Species 0.000 description 1
- 235000011203 Origanum Nutrition 0.000 description 1
- 240000002657 Thymus vulgaris Species 0.000 description 1
- 235000007303 Thymus vulgaris Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000001585 thymus vulgaris Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种用于合成麝香草酚的催化剂,所述催化剂为Al‑Cu/HAP催化剂,HAP为羟基磷灰石,铝原子和铜原子负载在羟基磷灰石上;催化剂中Al和Cu的摩尔比为1∶0.001~3;催化剂中Al‑Cu的负载量为1~50wt%。使用本发明的催化剂催化合成麝香草酚时,反应温度为100~200℃,大大低于现有傅‑克烷基化反应制备麝香草酚的温度;反应时间较短,仅需0.1~60min。
Description
本申请是申请号为201510192742.3,申请日为2015年4月22日,发明创造名称为“麝香草酚的制备方法”的发明专利申请的分案申请。
技术领域
本发明涉及一种用于合成麝香草酚的催化剂。
背景技术
麝香草酚(又称麝香草脑、百里酚),化学名称为 5-甲基-2-异丙基苯酚,在常温下为白色晶体或无色半透明晶体。麝香草酚用途十分广泛,是一种常用的食用调味香料、防腐剂、杀菌剂和抗氧化剂,同时也是合成许多化学品的初级原料,例如麝香草酚加氢合成薄荷醇。
麝香草酚的来源主要有两种:一种是从天然产物(百里香油、牛至油、罗勒油)中提取,另外一种是人工合成获得。由于天然资源有限且提取成本和环境压力较高,目前主要是以人工合成麝香草酚为主。
人工合成麝香草酚的方法主要有以下几种:(1)以发烟硫酸为催化剂催化间甲酚和异丙醇经过磺化和烷基化制备麝香草酚。但是发烟强酸硫酸腐蚀性太强,该工艺不够环保。(2)以十氢萘为溶剂,将α-蒎烯催化氧化后再经催化裂解制备麝香草酚。该工艺反应步骤多,而且产率低。(3)由香茅醇催化闭环后,经催化脱氢制备麝香草酚。该工艺反应步骤多,催化脱氢催化剂寿命短,同时上游原料香茅醛来源少。(4)目前研究的焦点主要集中在以间甲酚和异丙醇为原料进行傅-克烷基化反应来制备麝香草酚。
在公开报道的文献和专利中,傅-克烷基化反应制备麝香草酚需要在高温下进行,而且反应时间长。例如:专利文献DE-OS 2528303公开了在360~365 ℃下、压力为48~50×105Pa的条件下利用间甲酚和丙烯制备麝香草酚,该方法所用的催化剂为活性氧化铝,在液相中进行烷基化反应制得麝香草酚。该方法需要在高压、高温下进行。
中国专利文献CN 101402551 A(申请号200810219106.5)也公开了一种麝香草酚的制备方法,是在常压下以间甲酚和异丙基化试剂为原料,在固定床反应器中进行反应,反应温度为200~300℃,反应时间为4~7 h,惰性气体为载气。上述方法制备时,需要使用固定床反应器,固定床的催化剂的装载和替换比较费时、费力,还需要惰性气体作为载体,最重要的一点是反应仍需要在高温下进行,而且反应时间长。
发明内容
本发明所要解决的技术问题是提供一种用于合成麝香草酚的催化剂。
实现本发明目的的技术方案是一种用于合成麝香草酚的催化剂,所述催化剂为Al-Cu/HAP催化剂,HAP为羟基磷灰石,铝原子和铜原子负载在羟基磷灰石上;催化剂中Al和Cu的摩尔比为1∶0.001~3;催化剂中Al-Cu的负载量为1~50wt%。
上述Al-Cu/HAP的制备方法如下:将Al盐、Cu盐溶解于稀盐酸中,得到混合溶液;将作为载体的粒径为100~200目的羟基磷灰石粉末加入上述混合溶液,得到混合物;向上述得到的混合物中加入作为沉淀剂的NaOH溶液,搅拌均匀后,将上述物料过滤,得到的滤渣用去离子水洗涤、干燥后,煅烧后得到催化剂 Al-Cu/HAP。
其中Al盐为AlCl3、Al2(SO4)3、Al(NO3)3中的一种或一种以上的混合物,铜盐为CuCl2、CuSO4、Cu(NO3)2中的一种或一种以上的混合物。
上述催化剂 Al-Cu/HAP制备时,煅烧温度为450~550℃,煅烧时间为0.5~6h。
本发明具有积极的效果:(1)使用本发明的催化剂催化合成麝香草酚时,反应温度为100~200℃,大大低于现有傅-克烷基化反应制备麝香草酚的温度;反应时间较短,仅需0.1~60min。
(2)由于使用本发明的催化剂,麝香草酚的制备方法可在常压和低温下进行,间甲酚的转化率高,并且反应的选择率高,副反应少;生产工艺简单,反应能耗低,催化剂可以重复使用,具有较好的经济效益和社会效益。
具体实施方式
本发明合成麝香草酚的反应式如下:
上述反应式中,microwave 为微波。
Al-Cu/HAP为催化剂,Al-Cu/HAP的制备方法如下:
将Al盐、Cu盐溶解于稀盐酸中,得到混合溶液;将作为载体的粒径为100~200目的羟基磷灰石(HAP)粉末加入上述混合溶液,得到混合物;向上述得到的混合物中加入作为沉淀剂的NaOH溶液,搅拌均匀后,将上述物料过滤,得到的滤渣用去离子水洗涤、干燥后,在450~550℃下煅烧0.5~6h后得到催化剂 Al-Cu/HAP。其中Al盐为AlCl3、Al2(SO4)3、Al(NO3)3中的一种或一种以上的混合物,铜盐为CuCl2、CuSO4、Cu(NO3)2中的一种或一种以上的混合物;催化剂中Al和Cu的摩尔比为1∶0.001~3;催化剂中Al-Cu的负载量(质量百分含量)为1~50wt%。
(实施例1)
本实施例的麝香草酚的制备方法如下:
向50mL圆底烧瓶中加入0.1 mol 间甲酚和 0.1 mol 异丙醇,搅拌均匀后,向间甲酚和异丙醇的混合物中加入Al-Cu/HAP催化剂1g,再次搅拌均匀,得到反应物料。将反应物料在功率为400 W的微波辐射下、于150℃的反应温度下反应5 min,得到目标产物麝香草酚7.38g。其中间甲酚的转化率为50.36%,反应的选择率为97.57%。
上述Al-Cu/HAP催化剂的制备方法如下:将0.1 mol Al(NO3)3•••9H2O、0.01 molCuSO4•5H2O溶解于100mL的0.05 mol/L的稀盐酸中,得到混合溶液;将作为载体的5 g羟基磷灰石(HAP)加入上述混合溶液,得到固液混合物;向上述得到的固液混合物中加入1 mol/L的 NaOH溶液400mL,搅拌均匀后,将上述物料过滤,得到的滤渣用去离子水洗涤、干燥后,在500℃下煅烧2 h后得到催化剂 Al-Cu/HAP。
(实施例2)
本实施例的麝香草酚的制备方法如下:
向50mL圆底烧瓶中加入0.1 mol 间甲酚和 0.3 mol 异丙醇,搅拌均匀后,向间甲酚和异丙醇的混合物中加入Al-Cu/HAP催化剂1g,再次搅拌均匀,得到反应物料。将反应物料在功率为400 W的微波辐射下、于150℃的反应温度下反应5 min,得到目标产物麝香草酚13.34g。其中间甲酚的转化率为91.48%,反应的选择率为97.12%。
本实施例所用的催化剂与实施例1中的相同。
(实施例3)
本实施例的麝香草酚的制备方法其余与实施例1相同,不同之处在于:反应物料在功率为400 W的微波辐射下、于150℃的反应温度下反应10 min,得到目标产物麝香草酚9.51g。其中间甲酚的转化率为65.34%,反应的选择率为96.98%。
(实施例4)
本实施例的麝香草酚的制备方法其余与实施例1相同,不同之处在于:反应物料在功率为600 W的微波辐射下、于150℃的反应温度下反应5min,得到目标产物麝香草酚10.90g。其中间甲酚的转化率为75.16%,反应的选择率为96.57%。
(实施例5)
本实施例的麝香草酚的制备方法其余与实施例1相同,不同之处在于:Al-Cu/HAP催化剂的加入量为2g;反应结束得到目标产物麝香草酚8.51g。其中间甲酚的转化率为57.19%,反应的选择率为98.98%。
(实施例6)
本实施例的麝香草酚的制备方法如下:
向50mL圆底烧瓶中加入0.1 mol 间甲酚和 0.3 mol 异丙醇,搅拌均匀后,向间甲酚和异丙醇的混合物中加入Al-Cu/HAP催化剂2g,再次搅拌均匀,得到反应物料。将反应物料在功率为600 W的微波辐射下、于180℃的反应温度下反应5 min,得到目标产物麝香草酚14.30g。其中间甲酚的转化率为98.34%,反应的选择率为96.82%。
(实施例7)
本实施例的麝香草酚的制备方法其余与实施例1相同,不同之处在于所用的Al-Cu/HAP催化剂的制备方法如下:将0.05mol Al2(SO4)3•16H2O、0.01mol CuCl2•2H2O溶解于100mL的0.05 mol/L的稀盐酸中,得到混合溶液;将作为载体的5 g羟基磷灰石(HAP)加入上述混合溶液,得到固液混合物;向上述得到的固液混合物中加入1mol/L的 NaOH溶液400mL,搅拌均匀后,将上述物料过滤,得到的滤渣用去离子水洗涤、干燥后,在500℃下煅烧2 h后得到催化剂 Al-Cu/HAP。
反应结束后得到麝香草酚7.21g;间甲酚的转化率为49.53%,反应的选择率为96.85%。
以上各实施例及应用例是对本发明的具体实施方式的说明,而非对本发明的限制,有关技术领域的技术人员在不脱离本发明的精神和范围的情况下,还可以作出各种变换和变化而得到相对应的等同的技术方案,因此所有等同的技术方案均应该归入本发明的专利保护范围。
Claims (3)
1.一种用于合成麝香草酚的催化剂,其特征在于:所述催化剂为Al-Cu/HAP催化剂,HAP为羟基磷灰石,铝原子和铜原子负载在羟基磷灰石上;催化剂中Al和Cu的摩尔比为1∶0.001~3;催化剂中Al-Cu的负载量为1~50wt%。
2.根据权利要求1所述的用于合成麝香草酚的催化剂,其特征在于Al-Cu/HAP的制备方法如下:
将Al盐、Cu盐溶解于稀盐酸中,得到混合溶液;将作为载体的粒径为100~200目的羟基磷灰石粉末加入上述混合溶液,得到混合物;向上述得到的混合物中加入作为沉淀剂的NaOH溶液,搅拌均匀后,将上述物料过滤,得到的滤渣用去离子水洗涤、干燥后,煅烧后得到催化剂 Al-Cu/HAP;
其中Al盐为AlCl3、Al2(SO4)3、Al(NO3)3中的一种或一种以上的混合物,铜盐为CuCl2、CuSO4、Cu(NO3)2中的一种或一种以上的混合物。
3.根据权利要求2所述的用于合成麝香草酚的催化剂,其特征在于:Al-Cu/HAP的制备时,煅烧温度为450~550℃,煅烧时间为0.5~6h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710481003.5A CN107398290B (zh) | 2015-04-22 | 2015-04-22 | 用于合成麝香草酚的催化剂 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510192742.3A CN104744219B (zh) | 2015-04-22 | 2015-04-22 | 麝香草酚的制备方法 |
CN201710481003.5A CN107398290B (zh) | 2015-04-22 | 2015-04-22 | 用于合成麝香草酚的催化剂 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510192742.3A Division CN104744219B (zh) | 2015-04-22 | 2015-04-22 | 麝香草酚的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107398290A true CN107398290A (zh) | 2017-11-28 |
CN107398290B CN107398290B (zh) | 2020-01-10 |
Family
ID=53584580
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510192742.3A Active CN104744219B (zh) | 2015-04-22 | 2015-04-22 | 麝香草酚的制备方法 |
CN201710481004.XA Active CN107382670B (zh) | 2015-04-22 | 2015-04-22 | 一种麝香草酚的制备方法 |
CN201710481003.5A Active CN107398290B (zh) | 2015-04-22 | 2015-04-22 | 用于合成麝香草酚的催化剂 |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510192742.3A Active CN104744219B (zh) | 2015-04-22 | 2015-04-22 | 麝香草酚的制备方法 |
CN201710481004.XA Active CN107382670B (zh) | 2015-04-22 | 2015-04-22 | 一种麝香草酚的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (3) | CN104744219B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105693471B (zh) * | 2016-01-21 | 2019-01-15 | 上海延安药业(湖北)有限公司 | 麝香草酚的制备方法 |
CN108911951B (zh) * | 2018-08-15 | 2021-05-14 | 漳州水仙药业股份有限公司 | 一种麝香草酚及其制备方法和药物组合物 |
CN112939739A (zh) * | 2021-01-11 | 2021-06-11 | 吴樟强 | 一种百里香酚的酸催化制备方法 |
CN114849769B (zh) * | 2022-04-25 | 2023-06-13 | 安徽海华科技集团有限公司 | 合成百里香酚用催化剂及其制备方法与应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103480401A (zh) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | 一种羟基磷灰石负载三氯化铝催化剂的制备方法 |
CN103772154A (zh) * | 2014-01-21 | 2014-05-07 | 湘潭大学 | 一种改性羟基磷灰石催化合成双酚f的方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101402551A (zh) * | 2008-11-14 | 2009-04-08 | 广东省石油化工研究院 | 麝香草酚的制备方法 |
-
2015
- 2015-04-22 CN CN201510192742.3A patent/CN104744219B/zh active Active
- 2015-04-22 CN CN201710481004.XA patent/CN107382670B/zh active Active
- 2015-04-22 CN CN201710481003.5A patent/CN107398290B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103480401A (zh) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | 一种羟基磷灰石负载三氯化铝催化剂的制备方法 |
CN103772154A (zh) * | 2014-01-21 | 2014-05-07 | 湘潭大学 | 一种改性羟基磷灰石催化合成双酚f的方法 |
Non-Patent Citations (2)
Title |
---|
ASRAF A.ALI ET AL.: ""Microwave-assisted Process Intensification of Synthesis of Thymol Using Carbonized Sulfonic Acidic Resin(CSA) Catalyst"", 《IND.ENG.CHEM.RES.》 * |
张旖旎等: ""间甲酚烷基化合成麝香草酚的研究进展"", 《材料研究与应用》 * |
Also Published As
Publication number | Publication date |
---|---|
CN107398290B (zh) | 2020-01-10 |
CN107382670A (zh) | 2017-11-24 |
CN107382670B (zh) | 2020-12-08 |
CN104744219A (zh) | 2015-07-01 |
CN104744219B (zh) | 2017-07-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104744219B (zh) | 麝香草酚的制备方法 | |
CN104602816B (zh) | 来自具有少的甲烷和co2生成的合成气选择性生成低烃c1-c5的催化剂和工艺 | |
JP2014503639A5 (zh) | ||
EP2893976B1 (en) | Copper-based catalyst precursor, method for manufacturing same, and hydrogenation method | |
Singh et al. | Tetragonal Cu 2 Se nanoflakes: synthesis using selenated propylamine as Se source and activation of Suzuki and Sonogashira cross coupling reactions | |
CN104190391B (zh) | 一种催化剂及其在制备百里香酚方法中的用途 | |
JP2018524319A (ja) | 芳香族炭化水素、p−キシレン及びテレフタル酸の製造方法 | |
CN108430620A (zh) | 制备包含氧化形式的碱金属和过渡金属的催化剂的方法 | |
CN104588089B (zh) | 一种氟化铵改性制备脱重整生成油烯烃催化剂的方法 | |
CN101869845B (zh) | 一种用于去氢异植物醇选择性加氢合成异植物醇的催化剂 | |
CN101239889B (zh) | 一种含有烷基苯酚产物的反应液的制备方法 | |
CN102557908A (zh) | 2-(环己-1'-烯基)环己酮的制备方法 | |
CN102441414B (zh) | 一种用于烷基化反应催化剂及其制备方法和应用 | |
CN101857528B (zh) | 光催化羟基化制备邻苯二酚和对苯二酚的方法 | |
CN108727172B (zh) | 一种对甲氧基苯乙酮的催化合成方法 | |
WO2009151021A1 (ja) | プロピレングリコールの製造方法 | |
CN102382272A (zh) | 一种用衣康酸制备聚羧酸减水剂的方法 | |
CN107774298A (zh) | 多孔金属/分子筛复合催化剂、其制备方法及在合成气制备低碳烯烃中的用途 | |
CN106430227B (zh) | 一种具有网状结构的硼化镍粉体及其制备方法 | |
CN101139262A (zh) | 抗氧剂2,2’-亚甲基双(4-甲基-6-叔丁基酚)的制备方法 | |
JP6652364B2 (ja) | 1,3−ブタジエンの製造方法 | |
CN108129250A (zh) | 一种用正构型碳酸酯裂解制备α-烯烃的方法 | |
CN106140147B (zh) | 一种对硝基乙苯氧化制对硝基苯乙酮用催化剂及其制备方法 | |
CN113426474B (zh) | 一种硼酸改性铁锆择形催化剂及其制备方法和应用 | |
CN103240129A (zh) | 合成邻(对)苯二酚的光催化剂及邻(对)苯二酚的合成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |