CN103240129A - Photocatalyst for synthesizing o-(p-)benzenediol, and synthetic method for o-(p-)benzenediol - Google Patents
Photocatalyst for synthesizing o-(p-)benzenediol, and synthetic method for o-(p-)benzenediol Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 14
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000010189 synthetic method Methods 0.000 title 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 36
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000033444 hydroxylation Effects 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 11
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 11
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005580 one pot reaction Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- -1 hydroxyl catechol Chemical compound 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种合成邻(对)苯二酚的光催化剂及邻(对)苯二酚的合成方法。将C.I.颜料黄154溶于溶剂二甲基亚砜中，再向其中加入TiO2粉末，再加入表面活性剂吐温-80，在180～210℃下处理；得光催化剂。通过光催化反应，以苯酚为羟基化反应底物，水和乙腈混合物为溶剂，用H2O2为羟基化反应试剂，光催化羟基化一步反应合成了邻苯二酚和对苯二酚。本发明常温即可发生羟基化反应，勿需高温耗能；激发光可能为太阳光，是清洁及廉价的反应驱动力，节省能源；H2O2可以充分利用，三废排放量少；苯酚转化率(62%以上)、产物选择性(86%以上)、邻苯二酚和对苯二酚总收率(53%以上)比较高；光催化操作工艺较易实施。The invention relates to a photocatalyst for synthesizing ortho (res)quinone and a synthesis method of ortho (res)quinone. Dissolve CI Pigment Yellow 154 in the solvent dimethyl sulfoxide, add TiO 2 powder to it, then add surfactant Tween-80, and treat at 180-210°C to obtain photocatalyst. By photocatalytic reaction, catechol and hydroquinone were synthesized by photocatalytic hydroxylation one-step reaction with phenol as substrate, water and acetonitrile mixture as solvent, and H 2 O 2 as hydroxylation reagent. The invention can produce hydroxylation reaction at room temperature, without high temperature and energy consumption; the excitation light may be sunlight, which is a clean and cheap reaction driving force and saves energy; H 2 O 2 can be fully utilized, and the discharge of three wastes is small; phenol conversion The yield (above 62%), product selectivity (above 86%), and the total yield of catechol and hydroquinone (above 53%) are relatively high; the photocatalytic operation process is easier to implement.
Description
技术领域technical field
本发明属于光催化反应领域，特别提出了合成邻(对)苯二酚的光催化剂及邻(对)苯二酚的合成方法。是一种通过光催化反应来合成邻苯二酚（简称CAL）和对苯二酚（简称HQE）的方法。The invention belongs to the field of photocatalytic reaction, and particularly proposes a photocatalyst for synthesizing o-(p-)quinone and a synthesis method of o-(p-)quinone. It is a method for synthesizing catechol (CAL for short) and hydroquinone (HQE for short) by photocatalytic reaction.
背景技术Background technique
CAL和HQE应用广泛，是重要的精细化工产品，可用于医药、农药、香料、照相、食品、染料、树脂和涂料等行业。CAL and HQE are widely used and are important fine chemical products, which can be used in industries such as medicine, pesticide, fragrance, photography, food, dye, resin and coating.
CAL主要通过邻氯苯酚或邻甲氧基苯酚等水解获得。HQE生产工艺有苯胺氧化法、对二异丙苯氧化法等。但这些已有的生产方法存在原料成本高、反应步骤多、工艺复杂、废水排放多、生产效率低、腐蚀严重、设备较多等问题。CAL is mainly obtained by hydrolysis of o-chlorophenol or o-methoxyphenol. HQE production process includes aniline oxidation method, p-dicumyl oxidation method, etc. However, these existing production methods have problems such as high raw material cost, many reaction steps, complex process, large waste water discharge, low production efficiency, serious corrosion, and many equipments.
通过热催化苯酚直接羟基化也可以制备CAL和HQE。CAL and HQE can also be prepared by thermally catalyzed direct hydroxylation of phenol.
如用Sn2MCM-41对苯酚催化羟基化，反应24h后苯酚转化率为22.8%，产物中有CAL57.8%、HQE18.4%(Journal of Catalysis，1999，183：281-291)。If Sn 2 MCM-41 is used to catalyze the hydroxylation of phenol, the conversion rate of phenol after 24 hours of reaction is 22.8%, and the product contains 57.8% CAL and 18.4% HQE (Journal of Catalysis, 1999, 183: 281-291).
若用CoNiAl三元水滑石类催化剂用于苯酚羟基化，在n(苯酚)：n(H2O2)=2：1和65℃条件下，苯酚转化率14.2%，CAL和HQE比为3.8(Journal of Catalysis，2003，220(1)：161-171)。If CoNiAl ternary hydrotalcite catalyst is used for phenol hydroxylation, under the conditions of n(phenol):n(H 2 O 2 )=2:1 and 65°C, the conversion rate of phenol is 14.2%, and the ratio of CAL and HQE is 3.8 (Journal of Catalysis, 2003, 220(1): 161-171).
Villa使用Fe-Cu-ZSM-5分子筛作为催化剂，反应4h后，苯酚的转化率达到32%左右，CAL和HQE之比为1.5(Journal of Molecular Catalysis A:Chemistry，2005，228：233-240)。Villa uses Fe-Cu-ZSM-5 molecular sieve as a catalyst. After 4 hours of reaction, the conversion rate of phenol reaches about 32%, and the ratio of CAL to HQE is 1.5 (Journal of Molecular Catalysis A: Chemistry, 2005, 228: 233-240) .
以全硅β沸石为催化剂，在80℃反应6h，苯酚的转化率为34.6%，CAL的选择性为69.8%，HQE的选择性为27%(应用化学，2007，24(7)：290-295)。Using all-silicon beta zeolite as a catalyst and reacting at 80°C for 6 hours, the conversion rate of phenol was 34.6%, the selectivity of CAL was 69.8%, and the selectivity of HQE was 27% (Applied Chemistry, 2007, 24(7): 290- 295).
也有采用CuMgAl类水滑石为催化剂，温度为60℃，苯酚转化率最高达42.8%(催化学报，2009，3(30)：201-206)；朱艳婧等以Fe(OH)3为催化剂，在60～70℃反应时苯酚转化率为64%，CAL和HQE的选择性为67.5%(石油化工，2009，7(38）：739-744)。There are also CuMgAl-like hydrotalcites used as catalysts, the temperature is 60 °C, and the conversion rate of phenol is as high as 42.8% (Acta Catalytica Sinica, 2009, 3 (30): 201-206); The conversion rate of phenol was 64% at ~70℃, and the selectivity of CAL and HQE was 67.5% (Petrochemical Industry, 2009, 7(38): 739-744).
虽然苯酚热催化一步羟基化反应能够制备CAL和HQE，但存在反应温度高、反应时间长、耗能多、苯酚转化率低、CAL和HQE收率低、副产物多、CAL和HQE选择性低等问题。因此需要开发低温反应、反应速度快、苯酚高转化率、CAL和HQE高选择性的苯酚一步法羟基化直接合成CAL和HQE新工艺。通过苯酚的光催化羟基化反应来制备CAL和HQE，反应在常温、常压进行，仅一步反应，苯酚转化率高、CAL和HQE收率高，原子利用率高，是一种非常有应用价值的酚类绿色合成工艺。Although phenol thermally catalyzed one-step hydroxylation reaction can produce CAL and HQE, but there are high reaction temperature, long reaction time, high energy consumption, low conversion rate of phenol, low yield of CAL and HQE, many by-products, low selectivity of CAL and HQE And other issues. Therefore, it is necessary to develop a new process for direct synthesis of CAL and HQE by one-step hydroxylation of phenol with low temperature reaction, fast reaction speed, high conversion rate of phenol, and high selectivity of CAL and HQE. Preparation of CAL and HQE by photocatalytic hydroxylation of phenol, the reaction is carried out at room temperature and pressure, only one step reaction, high conversion rate of phenol, high yield of CAL and HQE, high atom utilization, is a very valuable application Green synthesis process of phenols.
发明内容Contents of the invention
针对传统多步反应方法制备CAL和HQE工艺的不足，以及苯酚热催化直接羟基化存在的苯酚转化率低、CAL和HQE产率低、CAL和HQE选择性低、反应温度高、反应时间长的问题，本发明特别提出了新的光催化剂反应，将苯酚直接羟基化合成CAL和HQE的方法。In view of the shortcomings of the traditional multi-step reaction method for the preparation of CAL and HQE, as well as the low conversion rate of phenol, low yield of CAL and HQE, low selectivity of CAL and HQE, high reaction temperature and long reaction time in the direct hydroxylation of phenol Problem, the present invention especially proposes a new photocatalyst reaction, the method that phenol is directly hydroxylated into CAL and HQE.
采用有机颜料/TiO2复合物为光催化剂，在紫外光照射下，成功地由苯酚一步直接羟基化合成了CAL和HQE，转化率和选择性均较高。克服了原传统工艺污染大、流程长、工艺复杂、副产物多等缺点。苯酚的光催化羟基化反应在常温、常压进行，转化率高、收率高、反应速度快、原子利用率高，工业应用价值大。Using organic pigment/ TiO2 composites as photocatalysts, CAL and HQE were successfully synthesized by one-step direct hydroxylation of phenol under UV light irradiation with high conversion and selectivity. It overcomes the shortcomings of the original traditional process, such as large pollution, long process, complex process, and many by-products. The photocatalytic hydroxylation reaction of phenol is carried out at normal temperature and normal pressure, with high conversion rate, high yield, fast reaction speed, high atom utilization rate, and great industrial application value.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种合成CAL和HQE的光催化剂，将C.I.颜料黄154溶于溶剂二甲基亚砜中，再向其中加入TiO2粉末，再加入表面活性剂吐温-80，搅拌形成黄色的悬浊浆液；将此悬浊浆液体系转移到密闭容器中，在180～210℃下处理2～4h；自然冷却至室温。将所得悬浊液进行过滤分离，滤饼干燥完全后，得到浅黄色复合物催化剂；以PY154/TiO2催化剂说明。A photocatalyst for synthesizing CAL and HQE, dissolving CI Pigment Yellow 154 in the solvent dimethyl sulfoxide, then adding TiO2 powder to it, then adding surfactant Tween-80, stirring to form a yellow suspension slurry ; Transfer the suspension slurry system to an airtight container and treat at 180-210°C for 2-4 hours; naturally cool to room temperature. The obtained suspension was separated by filtration, and after the filter cake was completely dried, a light yellow composite catalyst was obtained; it was illustrated by PY154/TiO 2 catalyst.
原料的物质质量比为：The mass ratio of raw materials is:
TiO2：C.I.颜料黄154=1：0.05～0.1；TiO 2 : CI Pigment Yellow 154=1:0.05～0.1;
TiO2：二甲基亚砜=1：13～20；TiO 2 : dimethyl sulfoxide = 1: 13 ~ 20;
TiO2：吐温-80＝1：0.05～0.15。TiO 2 : Tween-80 = 1: 0.05-0.15.
采用本发明的催化剂合成CAL和HQE的方法，通过光催化反应，以苯酚为羟基化反应底物，水和乙腈混合物为溶剂，用H2O2为羟基化反应试剂，光催化羟基化一步反应合成了CAL和HQE。The method for synthesizing CAL and HQE using the catalyst of the present invention, through photocatalytic reaction, using phenol as the substrate for hydroxylation reaction, water and acetonitrile mixture as solvent, and using H2O2 as the reagent for hydroxylation reaction, one -step photocatalytic hydroxylation reaction CAL and HQE were synthesized.
反应物料的质量配比为：The mass ratio of reaction materials is:
苯酚：H2O2=1：1.1～2.5；Phenol: H 2 O 2 =1:1.1～2.5;
苯酚：乙腈=1：5～10；Phenol:acetonitrile=1:5～10;
苯酚：催化剂＝1：0.07～0.3；Phenol:catalyst=1:0.07～0.3;
苯酚：H2O=1：20～45。Phenol:H 2 O=1:20-45.
光催化羟基化一步反应合成的反应时间为2～4h。The reaction time of photocatalytic hydroxylation one-step reaction synthesis is 2-4 hours.
光催化羟基化一步反应合成时一直用波长为365nm的紫外光照射。Photocatalytic hydroxylation one-step reaction synthesis has been irradiated with ultraviolet light with a wavelength of 365nm.
光催化羟基化反应温度：反应温度对羟基化反应结果影响不大，通常在常温下操作就可以。Photocatalytic hydroxylation reaction temperature: The reaction temperature has little effect on the result of the hydroxylation reaction, usually it can be operated at room temperature.
本发明采用光催化剂，以苯酚为羟基化反应底物，水和乙腈混合物为溶剂，用H2O2为羟基化反应试剂，光催化羟基化一步反应合成了CAL和HQE。反应方程式如下：The invention adopts photocatalyst, takes phenol as hydroxylation reaction substrate, water and acetonitrile mixture as solvent, uses H 2 O 2 as hydroxylation reaction reagent, and synthesizes CAL and HQE through photocatalytic hydroxylation one-step reaction. The reaction equation is as follows:
光催化羟基化反应后取样，产物做液相色谱分析，确定CAL和HQE生成量，计算苯酚转化率、产物收率及反应选择性。计算方法如下：After the photocatalytic hydroxylation reaction, samples were taken, and the product was analyzed by liquid chromatography to determine the amount of CAL and HQE produced, and calculate the conversion rate of phenol, product yield and reaction selectivity. The calculation method is as follows:
本发明是合成一种新的光催化剂及羟基化合成CAL和HQE技术。采用水-乙腈混合物为溶剂，以H2O2为羟基化试剂，在PY154/TiO2复合物光催化作用下，将苯酚直接一步反应法转化为CAL和HQE。常温即可发生羟基化反应，勿需高温耗能；激发光可能为太阳光，是清洁及廉价的反应驱动力，节省能源；H2O2可以充分利用，溶剂可回收，三废排放量少；反应速度快；苯酚转化率(62%以上)、产物选择性(86%以上)、CAL和HQE总收率(53%以上)比较高；光催化操作工艺较易实施。The invention is to synthesize a new photocatalyst and hydroxylation synthesis CAL and HQE technology. Using water-acetonitrile mixture as solvent, H 2 O 2 as hydroxylation reagent, under the photocatalysis of PY154/TiO 2 composite, phenol was directly converted into CAL and HQE by one-step reaction. The hydroxylation reaction can occur at room temperature without high temperature and energy consumption; the excitation light may be sunlight, which is a clean and cheap reaction driving force and saves energy; H 2 O 2 can be fully utilized, the solvent can be recycled, and the discharge of three wastes is small; The reaction speed is fast; the phenol conversion rate (above 62%), product selectivity (above 86%), and the total yield of CAL and HQE (above 53%) are relatively high; the photocatalytic operation process is relatively easy to implement.
具体实施方式Detailed ways
以下是催化剂PY154/TiO2的制备实例。The following is the preparation example of catalyst PY154/TiO 2 .
实施例1Example 1
物料配比为：The material ratio is:
TiO2：C.I.颜料黄154=1：0.09（质量比）；TiO 2 : CI Pigment Yellow 154=1:0.09 (mass ratio);
TiO2：二甲基亚砜=1：16（质量比）；TiO 2 : dimethyl sulfoxide = 1: 16 (mass ratio);
TiO2：吐温-80＝1：0.12（质量比）；TiO 2 :Tween-80=1:0.12 (mass ratio);
在烧杯中加入0.9g C.I.颜料黄154，再加入160g二甲基亚砜，搅拌，使其溶解。再向其中加入10g TiO2（商品牌号P25），并加入1.2g吐温-80，搅拌直至形成黄色均匀的悬浊浆液。将此悬浊浆液体系转到不锈钢高压釜中，在190℃下恒温处理4h。处理完成后，自然冷却至室温。将所得悬浊浆液进行过滤分离，并将所得滤饼用蒸馏水多次洗涤，直到滤液无色。然后将所得沉淀物置于干燥箱中在100℃进行干燥，干燥完全后研磨为粉末，得到浅黄色PY154/TiO2催化剂，该催化剂可用于下述的光催化剂羟基化反应。为方便起见，将该催化剂记为PYT-A。Add 0.9 g of CI Pigment Yellow 154 to the beaker, and then add 160 g of dimethyl sulfoxide, and stir to dissolve it. 10g of TiO 2 (commercial brand P25) and 1.2g of Tween-80 were added thereto, and stirred until a yellow homogeneous suspension slurry was formed. The suspension slurry system was transferred to a stainless steel autoclave, and treated at a constant temperature of 190° C. for 4 hours. After the treatment is completed, it is naturally cooled to room temperature. The obtained suspension slurry was separated by filtration, and the obtained filter cake was washed with distilled water several times until the filtrate was colorless. The resulting precipitate was then placed in a drying oven at 100°C for drying, and after complete drying, it was ground into a powder to obtain a light yellow PY154/TiO 2 catalyst, which can be used for the following photocatalyst hydroxylation reaction. For convenience, this catalyst is referred to as PYT-A.
实施例2Example 2
物料配比为：The material ratio is:
TiO2：C.I.颜料黄154=1：0.05（质量比）；TiO 2 : CI Pigment Yellow 154=1:0.05 (mass ratio);
TiO2：二甲基亚砜=1：13（质量比）；TiO 2 : dimethyl sulfoxide = 1: 13 (mass ratio);
TiO2：吐温-80＝1：0.05（质量比）；TiO 2 :Tween-80=1:0.05 (mass ratio);
在烧杯中加入0.5g C.I.颜料黄154，再加入130g二甲基亚砜，搅拌，使其溶解。再向其中加入10g TiO2（商品牌号P25），并加入0.5g吐温-80，搅拌直至形成黄色均匀的悬浊浆液。将此悬浊浆液体系转到不锈钢高压釜中，在210℃下恒温处理3h。处理完成后，自然冷却至室温。将所得悬浊浆液进行过滤分离，并将所得滤饼用蒸馏水多次洗涤，直到滤液无色。然后将所得沉淀物置于干燥箱中在100℃进行干燥，干燥完全后研磨为粉末，得到浅黄色PY154/TiO2催化剂，该催化剂可用于下述的光催化剂羟基化反应。为方便起见，将该催化剂记为PYT-B。Add 0.5 g of CI Pigment Yellow 154 to the beaker, and then add 130 g of dimethyl sulfoxide, and stir to dissolve it. 10g of TiO 2 (commercial brand P25) and 0.5g of Tween-80 were added thereto, and stirred until a yellow homogeneous suspension slurry was formed. The suspension slurry system was transferred to a stainless steel autoclave, and treated at a constant temperature of 210° C. for 3 hours. After the treatment is completed, it is naturally cooled to room temperature. The obtained suspension slurry was separated by filtration, and the obtained filter cake was washed with distilled water several times until the filtrate was colorless. The resulting precipitate was then placed in a drying oven at 100°C for drying, and after complete drying, it was ground into a powder to obtain a light yellow PY154/TiO 2 catalyst, which can be used for the following photocatalyst hydroxylation reaction. For convenience, this catalyst is referred to as PYT-B.
实施例3Example 3
物料配比为：The material ratio is:
TiO2：C.I.颜料黄154=1：0.1（质量比）；TiO 2 : CI Pigment Yellow 154=1:0.1 (mass ratio);
TiO2：二甲基亚砜=1：20（质量比）；TiO 2 : dimethyl sulfoxide = 1: 20 (mass ratio);
TiO2：吐温-80＝1：0.15（质量比）；TiO 2 :Tween-80=1:0.15 (mass ratio);
在烧杯中加入1g C.I.颜料黄154，再加入200g二甲基亚砜，搅拌，使其溶解。再向其中加入10g TiO2（商品牌号P25），并加入1.5g吐温-80，搅拌直至形成黄色均匀的悬浊浆液。将此悬浊浆液体系转到不锈钢高压釜中，在180℃下恒温处理2h。处理完成后，自然冷却至室温。将所得悬浊浆液进行过滤分离，并将所得滤饼用蒸馏水多次洗涤，直到滤液无色。然后将所得沉淀物置于干燥箱中在100℃进行干燥，干燥完全后研磨为粉末，得到浅黄色PY154/TiO2催化剂，该催化剂可用于下述的光催化剂羟基化反应。为方便起见，将该催化剂记为PYT-C。Add 1g of CI Pigment Yellow 154 to the beaker, then add 200g of dimethyl sulfoxide, and stir to dissolve it. 10g of TiO 2 (commercial brand P25) and 1.5g of Tween-80 were added thereto, and stirred until a yellow homogeneous suspension slurry was formed. The suspension slurry system was transferred to a stainless steel autoclave, and treated at a constant temperature of 180° C. for 2 hours. After the treatment is completed, it is naturally cooled to room temperature. The obtained suspension slurry was separated by filtration, and the obtained filter cake was washed with distilled water several times until the filtrate was colorless. The resulting precipitate was then placed in a drying oven at 100°C for drying, and after complete drying, it was ground into a powder to obtain a light yellow PY154/TiO 2 catalyst, which can be used for the following photocatalyst hydroxylation reaction. For convenience, this catalyst is referred to as PYT-C.
以下是光催化羟基化反应实例。The following are examples of photocatalytic hydroxylation reactions.
实施例4Example 4
物料的配比为：The ratio of materials is:
苯酚：H2O2=1：2（质量比，含量30%）；Phenol: H 2 O 2 =1:2 (mass ratio, content 30%);
苯酚：乙腈=1：8（质量比）；Phenol: acetonitrile = 1:8 (mass ratio);
苯酚：催化剂（实施例1制备的PYT-A）＝1：0.2（质量比）；Phenol: catalyst (PYT-A prepared in Example 1) = 1:0.2 (mass ratio);
苯酚：H2O=1：30(质量比)；Phenol: H 2 O=1:30 (mass ratio);
称取0.6g的催化剂PYT-A、3g苯酚、90g去离子水和24g乙腈，加入光反应器中。搅拌状态下滴入6g H2O2（含量30%），继续搅拌20min保持吸附平衡，然后在250W高压汞灯下照射3h，波长为365nm。定时取样，离心分离，取上层清液进行液相色谱分析，由此计算出苯酚转化率63.0%、CAL收率28.7%、HQE收率27.6%和产物选择性89.3%。Weigh 0.6g of catalyst PYT-A, 3g of phenol, 90g of deionized water and 24g of acetonitrile, and add them into the photoreactor. Add 6g of H 2 O 2 (30% content) dropwise under stirring, continue stirring for 20 minutes to maintain adsorption equilibrium, and then irradiate for 3 hours under a 250W high-pressure mercury lamp with a wavelength of 365nm. Sampling was performed regularly, centrifuged, and the supernatant liquid was taken for liquid chromatography analysis. From this, the phenol conversion rate was 63.0%, the CAL yield was 28.7%, the HQE yield was 27.6%, and the product selectivity was 89.3%.
实施例5Example 5
物料的配比为：The ratio of materials is:
苯酚：H2O2=1：1.1（质量比，含量30%）；Phenol: H 2 O 2 =1:1.1 (mass ratio, content 30%);
苯酚：乙腈=1：10（质量比）；Phenol: acetonitrile = 1:10 (mass ratio);
苯酚：催化剂（实施例2制备的PYT-B）＝1：0.3（质量比）；Phenol: catalyst (PYT-B prepared in Example 2) = 1:0.3 (mass ratio);
苯酚：H2O=1：45(质量比)；Phenol: H 2 O = 1: 45 (mass ratio);
称取0.9g的催化剂PYT-B、3g苯酚、135g去离子水和30g乙腈，加入光反应器中。搅拌状态下滴入3.3g H2O2（含量30%），继续搅拌20min保持吸附平衡，然后在300W氙灯下照射2h，紫外光波长为365nm。定时取样，离心分离，取上层清液进行液相色谱分析，由此计算出苯酚转化率62.0%、CAL收率26.7%、HQE收率26.6%和产物选择性86.0%。Weigh 0.9g of catalyst PYT-B, 3g of phenol, 135g of deionized water and 30g of acetonitrile, and add them into the photoreactor. Add 3.3g of H 2 O 2 (30% content) dropwise while stirring, continue stirring for 20 minutes to maintain adsorption equilibrium, and then irradiate for 2 hours under a 300W xenon lamp with a wavelength of ultraviolet light of 365nm. Sampling was performed regularly, centrifuged, and the supernatant liquid was taken for liquid chromatography analysis. From this, the phenol conversion rate was 62.0%, the CAL yield was 26.7%, the HQE yield was 26.6%, and the product selectivity was 86.0%.
实施例6Example 6
物料的配比为：The ratio of materials is:
苯酚：H2O2=1：2.5（质量比，含量30%）；Phenol: H 2 O 2 =1:2.5 (mass ratio, content 30%);
苯酚：乙腈=1：5（质量比）；Phenol: acetonitrile = 1:5 (mass ratio);
苯酚：催化剂（实施例3制备的PYT-C）＝1：0.07（质量比）；Phenol: catalyst (PYT-C prepared in Example 3) = 1:0.07 (mass ratio);
苯酚：H2O=1：20(质量比)；Phenol:H 2 O=1:20 (mass ratio);
称取0.21g的催化剂PYT-C、3g苯酚、60g去离子水和15g乙腈，加入光反应器中。搅拌状态下滴入7.5g H2O2（含量30%），继续搅拌20min保持吸附平衡，然后在150W高压汞灯下照射4h，紫外光波长为365nm。定时取样，离心分离，取上层清液进行液相色谱分析，由此计算出苯酚转化率63.7%、CAL收率28.9%、HQE收率26.6%和产物选择性87.1%。Weigh 0.21g of catalyst PYT-C, 3g of phenol, 60g of deionized water and 15g of acetonitrile, and add them into the photoreactor. Add 7.5g of H 2 O 2 (content 30%) dropwise under stirring, continue stirring for 20 minutes to maintain adsorption equilibrium, and then irradiate for 4 hours under a 150W high-pressure mercury lamp with a wavelength of ultraviolet light of 365nm. Sampling was performed regularly, centrifuged, and the supernatant liquid was taken for liquid chromatography analysis. From this, the phenol conversion rate was 63.7%, the CAL yield was 28.9%, the HQE yield was 26.6%, and the product selectivity was 87.1%.
实施例7Example 7
对比实验。实验条件同实施例4，但不加催化剂，苯酚转化率30.7%，CAL收率3.2%、未检测到HQE生成，产物选择性10.4%。Comparative Experiment. The experimental conditions were the same as in Example 4, but no catalyst was added, the phenol conversion rate was 30.7%, the CAL yield was 3.2%, no HQE formation was detected, and the product selectivity was 10.4%.
实施例8Example 8
对比试验。实验条件同实施例4，但不用紫外光照射，苯酚转化率仅有7.4%，未检测到CAL和HQE生成。Comparative Test. The experimental conditions were the same as in Example 4, but without ultraviolet light irradiation, the conversion rate of phenol was only 7.4%, and the formation of CAL and HQE was not detected.
通过上述实施例可以明确看出：本发明的光催化剂容易制备；用于光催化羟基化合成CAL和HQE技术易于实施；常温即可发生羟基化反应；反应速度快；苯酚转化率(62%以上)、产物选择性(86%以上)、CAL和HQE总收率(53%以上)比较高。是一种比现有技术更好的新的合成CAL和HQE技术。Can clearly find out by above-mentioned embodiment: photocatalyst of the present invention is easy to prepare; Be used for photocatalytic hydroxylation and synthesize CAL and HQE technology and be easy to implement; Normal temperature can take place hydroxylation reaction; Reaction speed is fast; Phenol conversion rate (more than 62%) ), product selectivity (above 86%), CAL and HQE total yield (above 53%) are relatively high. Is a new synthetic CAL and HQE technology that is better than the existing technology.
本发明并不局限于实施例中所描述的技术，它的描述是说明性的，并非限制性的。本发明的权限由权利要求所限定，基于本技术领域人员依据本发明所能够变化、重组等方法得到的与本发明相关的技术，都在本发明的保护范围之内。The present invention is not limited to the techniques described in the examples, which are described illustratively and not restrictively. The authority of the present invention is defined by the claims, and the technologies related to the present invention obtained by those skilled in the art according to the method of changing and reorganizing according to the present invention are all within the protection scope of the present invention.
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| CN108484366A (en) * | 2018-04-11 | 2018-09-04 | 中北大学 | A kind of method that visible light catalytic phenol hydroxylation prepares hydroquinone |
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| CN101723808A (en) * | 2009-12-08 | 2010-06-09 | 天津大学 | Method for preparing 1-naphthol by using pigment green B catalysis |
| CN101857528A (en) * | 2010-06-30 | 2010-10-13 | 天津大学 | Method for preparing catechol and hydroquinone by photocatalytic hydroxylation |
| CN102199072A (en) * | 2011-04-08 | 2011-09-28 | 天津大学 | Method for preparing 2,5-dimethyl phenol through direct catalytic hydroxylation of p-xylene |
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| CN101857528A (en) * | 2010-06-30 | 2010-10-13 | 天津大学 | Method for preparing catechol and hydroquinone by photocatalytic hydroxylation |
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