CN102078808A - Catalyst used for synthesizing o-ethoxyphenol and preparation method thereof - Google Patents
Catalyst used for synthesizing o-ethoxyphenol and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 27
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910017052 cobalt Inorganic materials 0.000 claims abstract 2
- 239000010941 cobalt Substances 0.000 claims abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- 239000011733 molybdenum Substances 0.000 claims abstract 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052721 tungsten Inorganic materials 0.000 claims abstract 2
- 239000010937 tungsten Substances 0.000 claims abstract 2
- 229910052720 vanadium Inorganic materials 0.000 claims abstract 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000006266 etherification reaction Methods 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 2
- -1 homogeneous phase Chemical compound 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940073505 ethyl vanillin Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- FTWGTNVTSDGLFG-UHFFFAOYSA-N nitric acid zirconium Chemical compound [Zr].O[N+]([O-])=O FTWGTNVTSDGLFG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 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
- 235000013599 spices Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术邻域technology neighborhood
本发明涉及一种用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚的催化剂及制备方法，所述的催化剂为一种负载型的复合氧化物催化剂。The invention relates to a catalyst for monoetherifying catechol and ethanol to synthesize o-ethoxyphenol and a preparation method thereof. The catalyst is a supported composite oxide catalyst.
背景技术Background technique
邻乙氧基苯酚是有机化工的一种重要中间体，广泛用于香料、医药和燃料等领域，尤其是应用于乙基香兰素的合成，因此该产品在国内外需求量较大，有较好的商业前景。目前生产邻乙氧基苯酚的方法主要是两种，即均相、间歇法和气固相连续法。两种方法比较，后者因为环境污染少，合成工艺简易而备受青睐，许多国家已经实现了工业化。O-ethoxyphenol is an important intermediate of organic chemical industry, which is widely used in the fields of spices, medicine and fuel, especially in the synthesis of ethyl vanillin. Therefore, this product has a large demand at home and abroad. Better business prospects. At present, there are mainly two methods for producing o-ethoxyphenol, namely homogeneous phase, batch method and gas-solid phase continuous method. Compared with the two methods, the latter is favored because of less environmental pollution and simple synthesis process, and many countries have realized industrialization.
多种固体酸催化剂应用于该反应，如高岭土、混合氧化物、分子筛、负载型催化剂等，但因为邻苯二酚烷基化反应过程中会产生水，这些催化剂大都会因为水的存在而造成酸中心的流失，从而降低催化剂的活性和稳定性，因此这些催化剂在应用于该类型反应中大部分都存在着催化剂寿命短、失活速度快、稳定性差的缺点。A variety of solid acid catalysts are used in this reaction, such as kaolin, mixed oxides, molecular sieves, supported catalysts, etc., but because water is produced during the catechol alkylation reaction, most of these catalysts are caused by the presence of water. The loss of the acid center reduces the activity and stability of the catalyst, so most of these catalysts have the disadvantages of short catalyst life, fast deactivation speed and poor stability when applied to this type of reaction.
铌酸是一种独特的固体酸催化剂，它是氧化铌的水合物，分子式为Nb2O5·nH2O。作为环境友好型催化剂，铌酸的特殊之处在于，其在含水体系中仍具有较高的酸性，这是任何酸性金属氧化物催化剂所不能比拟的。由于纯的铌酸酸性相对较小，活性不稳定，失活后不易再生，因此限制该工艺的工业化应用。Niobic acid is a unique solid acid catalyst, it is a hydrate of niobium oxide, and its molecular formula is Nb 2 O 5 ·nH 2 O. As an environment-friendly catalyst, niobic acid is special in that it still has high acidity in aqueous system, which is unmatched by any acidic metal oxide catalyst. Because pure niobic acid has relatively low acidity, unstable activity, and difficult regeneration after deactivation, the industrial application of this process is limited.
发明专利(公开号CN1249297A)中提供了一种用铌酸作为催化剂制备苯酚-烷基醚化合物的方法，虽然催化剂的制备方法较简单，但催化剂的活性较差，例如在一定的反应条件下，用甲醇作醚化试剂与苯酚反应，苯酚的转化率仅为27％。另外，该专利中催化剂具有催化剂活性单一，比表面积小，孔径和孔容小等缺点。Invention patent (publication number CN1249297A) provides a method for preparing phenol-alkyl ether compounds using niobic acid as a catalyst. Although the preparation method of the catalyst is relatively simple, the activity of the catalyst is relatively poor. For example, under certain reaction conditions, Using methanol as etherification reagent to react with phenol, the conversion rate of phenol is only 27%. In addition, the catalyst in this patent has the disadvantages of single catalyst activity, small specific surface area, and small pore diameter and pore volume.
发明内容Contents of the invention
本发明的目的是开发一种应用于邻苯二酚和乙醇气固相单醚化反应制备邻乙氧基苯酚的催化剂，应用新的催化剂，可以使合成反应具有较高的转化率和较好的稳定性。具体来说，新催化剂的特点在于比普通铌酸催化剂比表面积、孔容和孔径更大，活性更高，在含水体系中仍具有较高的酸性以及良好的稳定性，解决了现有技术中诸多固体酸催化剂在含水体系中容易失活的现象。The purpose of this invention is to develop a kind of catalyst that is applied to the gas-solid phase monoetherification of catechol and ethanol to prepare o-ethoxyphenol. The application of new catalyst can make the synthesis reaction have higher conversion rate and better stability. Specifically, the new catalyst is characterized by larger specific surface area, pore volume, and pore size than ordinary niobic acid catalysts, higher activity, higher acidity and good stability in aqueous systems, which solves the problems in the prior art. Many solid acid catalysts are prone to deactivation in aqueous systems.
本发明的技术方案：Technical scheme of the present invention:
本发明所述的催化剂为一种复合氧化物催化剂，其组分和重量百分比含量如下：Catalyst described in the present invention is a kind of composite oxide catalyst, and its component and weight percent content are as follows:
氧化铌 70～99％Niobium oxide 70～99%
其他氧化物 1～30％Other oxides 1～30%
所述的催化剂中活性组分氧化铌的原料来源于市售的铌酸；其他氧化物作为助催化剂可以是氧化钼、氧化钨、氧化锆、氧化钒、氧化钴、氧化铈或氧化镧中的一种或两种。The raw material of the active component niobium oxide in the described catalyst is derived from commercially available niobic acid; other oxides can be molybdenum oxide, tungsten oxide, zirconium oxide, vanadium oxide, cobalt oxide, cerium oxide or lanthanum oxide as promoters one or two.
上述的催化剂的制备包括如下步骤：The preparation of above-mentioned catalyst comprises the steps:
市售的铌酸经水洗、抽滤和焙烧等处理后，得到氧化铌；将无机酸溶解在去离子水中制成酸浸渍液，所使用的无机酸溶液可以为盐酸、磷酸、硝酸、硫酸等，优选硝酸或磷酸。将氧化铌浸泡在该浸渍液中一定的时间，经干燥、焙烧等活化处理后，得到无机酸处理过的氧化铌；再把含助催化剂组分的硝酸盐、醋酸盐或氯化物等前驱体按比例溶解在去离子水中配制成浸渍液，将无机酸处理过的氧化铌浸泡在该浸渍液中一定的时间，经干燥、焙烧等活化处理后，得到本发明催化剂，其中焙烧温度为100～800℃，优选300～600℃，焙烧时间为2～7小时，优选3～5小时。Commercially available niobic acid is washed, filtered and roasted to obtain niobium oxide; the inorganic acid is dissolved in deionized water to make an acid dipping solution, and the inorganic acid solution used can be hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, etc. , preferably nitric acid or phosphoric acid. Soak niobium oxide in the impregnation solution for a certain period of time, and after drying, roasting and other activation treatments, obtain niobium oxide treated with inorganic acid; The body is dissolved in deionized water in proportion to prepare an impregnating solution, and the niobium oxide treated with inorganic acid is soaked in the impregnating solution for a certain period of time, and after activation treatments such as drying and roasting, the catalyst of the present invention is obtained, wherein the roasting temperature is 100 ~800°C, preferably 300~600°C, and the firing time is 2~7 hours, preferably 3~5 hours.
其中，无机酸浓度为0.1～25N，优选2～15N。助催化剂组分的硝酸盐、醋酸盐或氯化物等前驱体的水溶液的重量浓度为0.1～50％，优选2～30％。Wherein, the concentration of the inorganic acid is 0.1-25N, preferably 2-15N. The weight concentration of the aqueous solution of precursors such as nitrate, acetate or chloride of the co-catalyst component is 0.1-50%, preferably 2-30%.
使用本发明的催化剂进行邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应在固定床反应器上进行，反应温度为200～300℃，其中以260℃下效果较好。反应空速以液体体积计为0.2到3.5h-1，其中以2.0h-1效果较好。原料中乙醇和邻苯二酚的摩尔比为1～10∶1，其中以5∶1效果较好。The monoetherification of catechol and ethanol to o-ethoxyphenol by using the catalyst of the present invention is carried out in a fixed-bed reactor, and the reaction temperature is 200-300°C, and the effect is better at 260°C. The reaction space velocity is 0.2 to 3.5h -1 in terms of liquid volume, among which 2.0h -1 is better. The molar ratio of ethanol and catechol in the raw material is 1-10:1, and the effect is better with 5:1.
本发明制备的催化剂与现有技术相比优点在于，催化剂制备过程简单易行，邻苯二酚转化率高，副产物少，催化剂寿命长，稳定性与其他固体酸催化剂相比更好。使用乙醇为单醚化试剂与邻苯二酚在气固相连续流动反应装置中合成邻乙氧基苯酚，其中邻苯二酚的转化率可以达到86.2％，邻乙氧基苯酚选择性达到95.7％，催化剂寿命高达1000小时以上。Compared with the prior art, the catalyst prepared by the invention has the advantages of simple catalyst preparation process, high catechol conversion rate, less by-products, long catalyst life and better stability than other solid acid catalysts. Using ethanol as the monoetherification reagent and catechol to synthesize o-ethoxyphenol in a gas-solid phase continuous flow reaction device, the conversion rate of catechol can reach 86.2%, and the selectivity of o-ethoxyphenol can reach 95.7% %, catalyst life up to 1000 hours or more.
下面通过实例对本发明作进一步的说明。Below by example the present invention will be further described.
具体实施方式Detailed ways
下面的实施例中氧化铌预处理及催化剂用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应统一操作如下：In the following examples, niobium oxide pretreatment and catalyst are used for catechol and ethanol monoetherification to synthesize o-ethoxyphenol. The unified operation is as follows:
氧化铌预处理方法：Niobium oxide pretreatment method:
将铌酸加入到去离子水中，室温搅拌1小时后，抽滤，重复此操作3次，以尽量除去铌酸中自带的水溶性杂质，100℃烘干，压片成型，500℃焙烧，得到氧化铌。Add niobic acid into deionized water, stir at room temperature for 1 hour, then filter with suction, repeat this operation 3 times to remove the water-soluble impurities in niobic acid as much as possible, dry at 100°C, press into tablets, and bake at 500°C. to obtain niobium oxide.
催化剂用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应方法：The catalyst is used for the monoetherification of catechol and ethanol to synthesize o-ethoxyphenol. Reaction method:
将20克催化剂装入直径为20毫米的微型固定床反应器中，邻苯二酚和乙醇的混合溶液用微量泵进料，原料中乙醇和邻苯二酚的摩尔比为5∶1，控制液体空速为2.0h-1，反应温度260℃。20 grams of catalysts are packed into a micro-fixed-bed reactor with a diameter of 20 millimeters, and the mixed solution of catechol and ethanol is fed with a micro pump, and the mol ratio of ethanol and catechol in the raw material is 5: 1, controlled The liquid space velocity is 2.0h -1 , and the reaction temperature is 260°C.
实施例1Example 1
用过量的1N硝酸溶液在室温下浸渍氧化铌，抽滤后放入110～150℃的烘箱内干燥5小时；于450℃焙烧5小时，得到催化剂。用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应，邻苯二酚的转化率59.4％，邻乙氧基苯酚选择性91.3％。Impregnating niobium oxide with excess 1N nitric acid solution at room temperature, suction filtering, drying in an oven at 110-150°C for 5 hours, and roasting at 450°C for 5 hours to obtain the catalyst. It is used for the monoetherification of catechol and ethanol to synthesize o-ethoxyphenol, the conversion rate of catechol is 59.4%, and the selectivity of o-ethoxyphenol is 91.3%.
实施例2Example 2
用过量的2N硫酸溶液在室温下浸渍氧化铌，抽滤后放入110～150℃的烘箱内干燥5小时；然后将酸处理过的氧化铌加入到12％的磷钼酸和12％的硝酸铈水溶液中，静置过夜。过滤后，120℃干燥5小时；于350℃焙烧3小时，得到催化剂。用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应，邻苯二酚的转化率76.1％，邻乙氧基苯酚选择性95.2％。Use excess 2N sulfuric acid solution to impregnate niobium oxide at room temperature, filter it with suction and dry it in an oven at 110-150°C for 5 hours; then add acid-treated niobium oxide to 12% phosphomolybdic acid and 12% nitric acid In aqueous cerium solution, let it stand overnight. After filtration, it was dried at 120°C for 5 hours and calcined at 350°C for 3 hours to obtain the catalyst. It is used for the monoetherification of catechol and ethanol to synthesize o-ethoxyphenol, the conversion rate of catechol is 76.1%, and the selectivity of o-ethoxyphenol is 95.2%.
实施例3Example 3
用过量的1N磷酸溶液在室温下浸渍氧化铌，抽滤后放入110～150℃的烘箱内干燥5小时；然后将酸处理过的氧化铌加入到29％的磷钨酸和0.6％的硝酸锆水溶液中，静置过夜。过滤后，120℃干燥5小时；于600℃焙烧4小时，得到催化剂。用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应，邻苯二酚的转化率80.6％，邻乙氧基苯酚选择性90.3％。Use excess 1N phosphoric acid solution to impregnate niobium oxide at room temperature, filter it with suction and dry it in an oven at 110-150°C for 5 hours; then add acid-treated niobium oxide to 29% phosphotungstic acid and 0.6% nitric acid Zirconium aqueous solution, let stand overnight. After filtration, it was dried at 120°C for 5 hours and calcined at 600°C for 4 hours to obtain the catalyst. It is used for the monoetherification of catechol and ethanol to synthesize o-ethoxyphenol, the conversion rate of catechol is 80.6%, and the selectivity of o-ethoxyphenol is 90.3%.
实施例4Example 4
用过量的3N硝酸溶液在室温下浸渍氧化铌，抽滤后放入110～150℃的烘箱内干燥5小时；然后将酸处理过的氧化铌加入到40％的偏钒酸铵和8％的硝酸钴水溶液中，静置过夜。过滤后，120℃干燥5小时；于500℃焙烧5小时，得到催化剂。用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应，邻苯二酚的转化率86.2％，邻乙氧基苯酚选择性95.7％。在固定床反应器上进行连续催化剂的活性考察发现，邻乙氧基苯酚产率稳定在80％左右，催化剂的寿命可以达到1000小时以上。Use excess 3N nitric acid solution to impregnate niobium oxide at room temperature, filter it with suction and dry it in an oven at 110-150°C for 5 hours; then add acid-treated niobium oxide to 40% ammonium metavanadate and 8% Cobalt nitrate aqueous solution, let stand overnight. After filtration, it was dried at 120°C for 5 hours and calcined at 500°C for 5 hours to obtain the catalyst. It is used for the monoetherification of catechol and ethanol to synthesize o-ethoxyphenol, the conversion rate of catechol is 86.2%, and the selectivity of o-ethoxyphenol is 95.7%. The activity investigation of the continuous catalyst in the fixed-bed reactor shows that the yield of o-ethoxyphenol is stable at about 80%, and the life of the catalyst can reach more than 1000 hours.
实施例5Example 5
用过量的2N盐酸溶液在室温下浸渍氧化铌，抽滤后放入110～150℃的烘箱内干燥5小时；然后将酸处理过的氧化铌加入到11％的磷钨酸和33％的硝酸镧水溶液中，静置过夜。过滤后，120℃干燥5小时；于550℃焙烧6小时，得到催化剂。用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应，邻苯二酚的转化率84.7％，邻乙氧基苯酚选择性92.1％。Use excess 2N hydrochloric acid solution to impregnate niobium oxide at room temperature, filter it with suction and dry it in an oven at 110-150°C for 5 hours; then add acid-treated niobium oxide to 11% phosphotungstic acid and 33% nitric acid Lanthanum aqueous solution, let stand overnight. After filtration, it was dried at 120°C for 5 hours and calcined at 550°C for 6 hours to obtain the catalyst. It is used for the monoetherification of catechol and ethanol to synthesize o-ethoxyphenol, the conversion rate of catechol is 84.7%, and the selectivity of o-ethoxyphenol is 92.1%.
实施例6Example 6
用过量的2N硫酸溶液在室温下浸渍氧化铌，抽滤后放入110～150℃的烘箱内干燥5小时；然后将酸处理过的氧化铌加入到27％的磷钼酸和4％的硝酸铈水溶液中，静置过夜。过滤后，120℃干燥5小时；于750℃焙烧3小时，得到催化剂。用于邻苯二酚与乙醇单醚化合成邻乙氧基苯酚反应，邻苯二酚的转化率79.5％，邻乙氧基苯酚选择性89.9％。Use excess 2N sulfuric acid solution to impregnate niobium oxide at room temperature, filter it with suction and dry it in an oven at 110-150°C for 5 hours; then add acid-treated niobium oxide to 27% phosphomolybdic acid and 4% nitric acid In aqueous cerium solution, let it stand overnight. After filtration, it was dried at 120°C for 5 hours and calcined at 750°C for 3 hours to obtain the catalyst. It is used for the monoetherification of catechol and ethanol to synthesize o-ethoxyphenol, the conversion rate of catechol is 79.5%, and the selectivity of o-ethoxyphenol is 89.9%.
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| CN114349611A (en) * | 2022-01-04 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of m-ethoxyphenol |
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| CN102671671A (en) * | 2012-06-04 | 2012-09-19 | 盐城工学院 | Catalyst and application thereof to synthesis of o-hydroxyphenyl ether |
| CN104292082A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Preparation method for hydroquinone monoether compound |
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| CN114011457A (en) * | 2021-12-07 | 2022-02-08 | 万华化学集团股份有限公司 | Preparation method of p-ethoxyphenol |
| CN114011457B (en) * | 2021-12-07 | 2023-09-19 | 万华化学集团股份有限公司 | Preparation method of p-ethoxyphenol |
| CN114349611A (en) * | 2022-01-04 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of m-ethoxyphenol |
| CN114349611B (en) * | 2022-01-04 | 2023-05-26 | 万华化学集团股份有限公司 | Preparation method of m-ethoxyphenol |
| CN115197052A (en) * | 2022-07-29 | 2022-10-18 | 常州大学 | Method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis |
| CN115197052B (en) * | 2022-07-29 | 2023-11-03 | 常州大学 | Method for synthesizing o-hydroxyphenylethyl ether by catalyzing hydroxyapatite |
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