CN108435171B - A kind of preparation method of bimetallic Pt-Bi catalyst and a kind of method of selective catalytic oxidation of glycerol to prepare DHA - Google Patents
A kind of preparation method of bimetallic Pt-Bi catalyst and a kind of method of selective catalytic oxidation of glycerol to prepare DHA Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 296
- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract 3
- 235000011187 glycerol Nutrition 0.000 claims description 91
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 7
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- 238000010924 continuous production Methods 0.000 claims description 4
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- 238000011065 in-situ storage Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
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- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
本发明公开了一种双金属Pt‑Bi催化剂的制备方法,包括如下步骤:S1.在含有助剂Bi的甘油反应液中加入Pt催化剂,催化氧化甘油制1,3‑二羟基丙酮,得到含有双金属Pt‑Bi催化剂的反应液混合物;S2.分离出反应液混合物中的双金属Pt‑Bi催化剂,然后在惰性气氛、200~300℃条件下进行煅烧,制备得到双金属Pt‑Bi催化剂。本发明提供的制备方法能够利用失活的双金属Pt‑Bi催化剂制备得到高活性的双金属Pt‑Bi催化剂,制得的双金属Pt‑Bi催化剂催化活性高,能够高效选择性催化氧化甘油制DHA;通过煅烧将双金属Pt‑Bi催化剂在选择性催化氧化甘油制1,3‑二羟基丙酮中循环使用,甘油反应液中甘油的浓度及Bi的含量保持恒定,经过2~6次循环后,双金属Pt‑Bi催化剂能够保持初始高甘油转化率的DHA选择性。The invention discloses a preparation method of a bimetallic Pt-Bi catalyst, comprising the following steps: S1. adding a Pt catalyst to a glycerol reaction solution containing auxiliary Bi, catalyzing oxidation of glycerol to produce 1,3-dihydroxyacetone, and obtaining a glycerol containing The reaction liquid mixture of the bimetallic Pt-Bi catalyst; S2. Separating the bimetallic Pt-Bi catalyst in the reaction liquid mixture, and then calcining the bimetallic Pt-Bi catalyst in an inert atmosphere at 200-300° C. to prepare the bimetallic Pt-Bi catalyst. The preparation method provided by the invention can use the deactivated bimetallic Pt-Bi catalyst to prepare the highly active bimetallic Pt-Bi catalyst, the prepared bimetallic Pt-Bi catalyst has high catalytic activity, and can efficiently and selectively catalyze the oxidation of glycerol to produce DHA; the bimetallic Pt-Bi catalyst is recycled in the selective catalytic oxidation of glycerol to produce 1,3-dihydroxyacetone by calcination, the concentration of glycerol and the content of Bi in the glycerol reaction solution are kept constant, and after 2~6 cycles , the bimetallic Pt-Bi catalyst was able to maintain the DHA selectivity with the initial high glycerol conversion.
Description
技术领域technical field
本发明涉及甘油液相氧化转化技术领域,更具体地,涉及一种双金属Pt-Bi催化剂的制备方法及一种选择性催化氧化甘油制DHA的方法。The present invention relates to the technical field of liquid-phase oxidative conversion of glycerol, and more particularly, to a preparation method of a bimetallic Pt-Bi catalyst and a method for the selective catalytic oxidation of glycerol to prepare DHA.
背景技术Background technique
甘油作为生物柴油生产过程中的主要副产物,具有丰富的来源和十分低廉的价格。甘油本身是一种高度功能化的分子,其有效地利用可以转化为高附加值的精细化工产品,主要有:甘油醛、1,3-二羟基丙酮(DHA)、甘油酸、亚酒石酸等。其中DHA在化妆品、食品和制药等领域中都有着非常广泛的应用。As the main by-product in the production of biodiesel, glycerol has abundant sources and very low prices. Glycerol itself is a highly functionalized molecule, and its effective utilization can be converted into fine chemical products with high added value, mainly including: glyceraldehyde, 1,3-dihydroxyacetone (DHA), glyceric acid, tartaric acid, etc. Among them, DHA has a very wide range of applications in the fields of cosmetics, food and pharmaceuticals.
甘油具有伯位和仲位两种羟基官能团,其氧化反应也是结构敏感型反应,在一定反应条件及催化剂作用下能够被选择性催化氧化,造成氧化产物非常复杂。Glycerol has primary and secondary hydroxyl functional groups, and its oxidation reaction is also a structure-sensitive reaction, which can be selectively catalytically oxidized under certain reaction conditions and catalysts, resulting in very complex oxidation products.
Pt催化剂在该反应中有着广泛应用,单组分Pt更易选择性催化氧化甘油的伯位羟基,生成的产物主要是甘油酸和甘油醛。Pt催化剂中助剂Bi、Sb等的引入可以有效促进甘油仲位羟基的催化氧化,提高甘油转化率和DHA的选择性。Pt catalysts are widely used in this reaction, and single-component Pt is more likely to selectively catalyze the oxidation of primary hydroxyl groups of glycerol, and the generated products are mainly glyceric acid and glyceraldehyde. The introduction of promoters Bi, Sb, etc. in the Pt catalyst can effectively promote the catalytic oxidation of the secondary hydroxyl group of glycerol, and improve the conversion rate of glycerol and the selectivity of DHA.
Pt催化剂能够有效催化甘油氧化转化成高附加值的化工产品,但其在反应过程中会存在中毒、浸出、烧结等现象,造成Pt催化剂失活,极大地降低甘油转化率和产物选择性。Pt catalysts can effectively catalyze the oxidation of glycerol into high value-added chemical products, but in the reaction process, there will be poisoning, leaching, sintering and other phenomena, resulting in the deactivation of Pt catalysts and greatly reducing the conversion rate of glycerol and product selectivity.
因此,需要研发出一种利用失活后的双金属Pt-Bi催化剂制备高活性的双金属Pt-Bi催化剂的方法,该方法能够恢复双金属Pt-Bi催化剂的催化活性,使得双金属Pt-Bi催化剂在生产1,3-二羟基丙酮过程中保持初始高甘油转化率和DHA选择性。Therefore, it is necessary to develop a method for preparing a highly active bimetallic Pt-Bi catalyst by using the deactivated bimetallic Pt-Bi catalyst, which can restore the catalytic activity of the bimetallic Pt-Bi catalyst, so that the bimetallic Pt-Bi catalyst can be recovered. The Bi catalyst maintains the initial high glycerol conversion and DHA selectivity during the production of 1,3-dihydroxyacetone.
发明内容SUMMARY OF THE INVENTION
本发明为克服上述现有技术所述的催化剂失活的缺陷,提供一种双金属Pt-Bi催化剂的制备方法,提供的制备方法能够利用失活后的双金属Pt-Bi催化剂制备高活性的双金属Pt-Bi催化剂。In order to overcome the defect of catalyst deactivation described in the prior art, the present invention provides a preparation method of a bimetallic Pt-Bi catalyst, and the provided preparation method can utilize the deactivated bimetallic Pt-Bi catalyst to prepare a highly active catalyst. Bimetallic Pt-Bi catalyst.
本发明的另一目的在于提供一种选择性催化氧化甘油制DHA的方法,双金属Pt-Bi催化剂失活后通过煅烧恢复活性从而循环使用,甘油反应液中甘油浓度及助剂Bi的含量保持恒定,在双金属Pt-Bi催化剂循环使用过程时能够保持初始高甘油转化率和DHA选择性,实现连续生产。Another object of the present invention is to provide a method for producing DHA by selective catalytic oxidation of glycerol. After deactivation of the bimetallic Pt-Bi catalyst, the activity is recovered by calcination to be recycled, and the concentration of glycerin and the content of auxiliary Bi in the glycerol reaction solution are maintained Constant, the initial high glycerol conversion and DHA selectivity can be maintained during the recycling process of the bimetallic Pt-Bi catalyst, enabling continuous production.
为解决上述技术问题,本发明采用的技术方案是:In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is:
一种双金属Pt-Bi催化剂的制备方法,包括如下步骤:A preparation method of a bimetallic Pt-Bi catalyst, comprising the following steps:
S1. 在含有助剂Bi的甘油反应液中加入Pt催化剂,催化氧化甘油制1,3-二羟基丙酮,得到含有双金属Pt-Bi催化剂的反应液混合物;S1. adding a Pt catalyst to the glycerol reaction solution containing auxiliary Bi, and catalyzing oxidation of glycerol to prepare 1,3-dihydroxyacetone to obtain a reaction solution mixture containing a bimetallic Pt-Bi catalyst;
S2. 分离出反应液混合物中的双金属Pt-Bi催化剂,然后在惰性气氛、200~300℃条件下进行煅烧,制备得到双金属Pt-Bi催化剂。S2. Separating the bimetallic Pt-Bi catalyst in the reaction solution mixture, and then calcining it in an inert atmosphere at 200-300° C. to prepare a bimetallic Pt-Bi catalyst.
步骤S1.中生成原位双金属Pt-Bi催化剂,原位双金属Pt-Bi催化剂在反应结束后失活,催化活性显著降低。将失活的双金属Pt-Bi催化剂在上述条件下煅烧制得高活性的双金属Pt-Bi催化剂,制得的双金属Pt-Bi催化剂催化活性高,能够高效选择性催化氧化甘油制DHA。In step S1., an in-situ bimetallic Pt-Bi catalyst is generated, and the in-situ bimetallic Pt-Bi catalyst is deactivated after the reaction, and the catalytic activity is significantly reduced. The deactivated bimetallic Pt-Bi catalyst is calcined under the above conditions to obtain a highly active bimetallic Pt-Bi catalyst. The prepared bimetallic Pt-Bi catalyst has high catalytic activity and can efficiently and selectively catalyze the oxidation of glycerol to produce DHA.
当温度低于200℃时,失活的双金属Pt-Bi催化剂经煅烧后的催化活性不是很理想,因为温度太低不利于强吸附的中间物质的脱落。当温度太高时,会引起贵金属Pt纳米粒子的团聚,减少活性位点。When the temperature is lower than 200 °C, the catalytic activity of the deactivated bimetallic Pt-Bi catalyst after calcination is not very satisfactory, because the temperature is too low, which is not conducive to the shedding of strongly adsorbed intermediates. When the temperature is too high, it will cause the agglomeration of noble metal Pt nanoparticles and reduce the active sites.
而且,上述制备方法简单、易于操作,适合工业上推广使用。Moreover, the above-mentioned preparation method is simple and easy to operate, and is suitable for industrial promotion and use.
优选地,所述制备方法还包括如下步骤:Preferably, the preparation method further comprises the steps:
S3.在含有助剂Bi的甘油反应液中加入S2.制得的双金属Pt-Bi催化剂,催化氧化甘油制1,3-二羟基丙酮,得到含有双金属Pt-Bi催化剂的反应液混合物;分离出反应液混合物中的双金属Pt-Bi催化剂,然后在惰性气氛、200~300℃条件下进行煅烧,制备得到双金属Pt-Bi催化剂。S3. adding the bimetallic Pt-Bi catalyst prepared by S2. to the glycerol reaction solution containing auxiliary Bi, and catalyzing oxidation of glycerol to prepare 1,3-dihydroxyacetone to obtain a reaction solution mixture containing the bimetallic Pt-Bi catalyst; The bimetallic Pt-Bi catalyst in the reaction mixture is separated, and then calcined in an inert atmosphere at 200-300° C. to prepare the bimetallic Pt-Bi catalyst.
将制得的双金属Pt-Bi催化剂加入到含有助剂Bi的甘油反应液中,再次进行步骤S1.和S2.,得到煅烧两次后的双金属Pt-Bi催化剂;The prepared bimetallic Pt-Bi catalyst is added to the glycerin reaction solution containing auxiliary Bi, and steps S1. and S2. are performed again to obtain the bimetallic Pt-Bi catalyst after calcining twice;
优选地,循环进行步骤S3.,步骤S3.进行的次数为1~4次。Preferably, step S3. is performed cyclically, and the number of times that step S3. is performed is 1 to 4 times.
循环进行步骤S3.,则可以制备得到煅烧多次的双金属Pt-Bi催化剂。By cyclically performing step S3., a bimetallic Pt-Bi catalyst calcined for multiple times can be prepared.
优选地,步骤S3.进行的次数为2次。Preferably, step S3. is performed twice.
所述惰性气氛包括Ar气氛、N2气氛。The inert atmosphere includes Ar atmosphere and N 2 atmosphere.
优选地,所述惰性气氛为氩气气氛,氩气的流速为10~200mL/min。氩气气氛通过通入氩气实现。Preferably, the inert atmosphere is an argon gas atmosphere, and the flow rate of the argon gas is 10-200 mL/min. The argon atmosphere is achieved by bubbling argon.
更优选地,所述氩气的流速为20~150mL/min。More preferably, the flow rate of the argon gas is 20-150 mL/min.
进一步优选地,所述氩气的流速为100mL/min。Further preferably, the flow rate of the argon gas is 100 mL/min.
优选地,所述煅烧的时间为0.5~4 h。Preferably, the calcination time is 0.5-4 h.
更优选地,所述煅烧的时间为2 h。More preferably, the calcination time is 2 h.
优选地,所述甘油反应液中的Bi来自于氧化铋、氯化铋或硝酸铋中的一种或几种。Preferably, Bi in the glycerol reaction solution comes from one or more of bismuth oxide, bismuth chloride or bismuth nitrate.
优选地,所述甘油反应液中助剂Bi的质量为Pt的质量的10%~100%。Preferably, the mass of the auxiliary Bi in the glycerol reaction solution is 10%-100% of the mass of Pt.
优选地,所述甘油反应液中助剂Bi的质量为Pt的质量的20%~50%。Preferably, the mass of the auxiliary agent Bi in the glycerol reaction solution is 20% to 50% of the mass of Pt.
更优选地,所述甘油反应液中助剂Bi的质量为Pt的质量的20%。More preferably, the mass of auxiliary Bi in the glycerol reaction solution is 20% of the mass of Pt.
优选地,所述Pt催化剂的载体为氮掺杂碳材料。Preferably, the carrier of the Pt catalyst is a nitrogen-doped carbon material.
优选地,所述氮掺杂碳材料为氮掺杂的碳纳米管、碳纳米纤维或石墨烯中的一种或几种。Preferably, the nitrogen-doped carbon material is one or more of nitrogen-doped carbon nanotubes, carbon nanofibers or graphene.
优选地,所述Pt催化剂中Pt的负载量为2~10wt.%。Preferably, the loading of Pt in the Pt catalyst is 2˜10 wt.%.
优选地,所述Pt催化剂中Pt的负载量为5 wt.%。Preferably, the loading of Pt in the Pt catalyst is 5 wt.%.
优选地,S1. 中催化氧化甘油制1,3-二羟基丙酮的条件为:甘油反应液的甘油质量含量1wt.%~10wt.%,反应温度50~80℃,O2流量10~200 mL/min,搅拌速率100~800 r/min,反应时间1~10 h。Preferably, the conditions for catalytic oxidation of glycerol to prepare 1,3-dihydroxyacetone in S1. are: the glycerol mass content of the glycerol reaction solution is 1wt.%~10wt.%, the reaction temperature is 50~80 ° C, and the O flow rate is 10~ 200 mL /min, stirring rate 100~800 r/min, reaction time 1~10 h.
更优选地,S1.的氧化反应的条件为:甘油反应液的甘油质量含量1wt.%~10wt.%,反应温度60~80℃,O2流量50~150 mL/min,搅拌速率400~600 r/min,反应时间2~6 h。More preferably, the condition of the oxidation reaction of S1. is : the glycerol mass content of the glycerol reaction solution is 1wt.%~10wt.%, the reaction temperature is 60~80 ℃, the O flow rate is 50~150 mL/min, and the stirring rate is 400~600 ℃. r/min, the reaction time is 2~6 h.
进一步优选地,S1.的氧化反应的条件为:甘油反应液的甘油质量含量10wt.%,反应温度60℃,O2流量150 mL/min,搅拌速率600 r/min,反应时间6h。Further preferably, the conditions of the oxidation reaction of S1. are: the mass content of glycerol in the glycerol reaction solution is 10wt.%, the reaction temperature is 60°C, the flow rate of O 2 is 150 mL/min, the stirring rate is 600 r/min, and the reaction time is 6h.
优选地,甘油反应液的溶剂为水。Preferably, the solvent of the glycerol reaction solution is water.
本发明同时保护一种选择性催化氧化甘油制DHA的方法,包括如下步骤:The present invention simultaneously protects a kind of method for producing DHA by selective catalytic oxidation of glycerol, comprising the steps:
S1. 在含有助剂Bi的甘油反应液中加入Pt催化剂,催化氧化甘油制1,3-二羟基丙酮,得到含有双金属Pt-Bi催化剂的反应液混合物;S1. adding a Pt catalyst to the glycerol reaction solution containing auxiliary Bi, and catalyzing oxidation of glycerol to prepare 1,3-dihydroxyacetone to obtain a reaction solution mixture containing a bimetallic Pt-Bi catalyst;
S2. 分离出反应液混合物中的双金属Pt-Bi催化剂,然后在惰性气氛、200~300℃条件下进行煅烧,制备得到双金属Pt-Bi催化剂;S2. Separating the bimetallic Pt-Bi catalyst in the reaction mixture, and then calcining it in an inert atmosphere at 200-300 °C to prepare a bimetallic Pt-Bi catalyst;
S3.在含有助剂Bi的甘油反应液中加入步骤S2.制得的双金属Pt-Bi催化剂,催化氧化甘油制1,3-二羟基丙酮,得到含有双金属Pt-Bi催化剂的反应液混合物;然后进行步骤S2.,再次制备得到双金属Pt-Bi催化剂;S3. Add the bimetallic Pt-Bi catalyst prepared in step S2. to the glycerol reaction solution containing auxiliary Bi, and catalyze the oxidation of glycerol to prepare 1,3-dihydroxyacetone to obtain a reaction solution mixture containing the bimetallic Pt-Bi catalyst ; Then carry out step S2., prepare the bimetallic Pt-Bi catalyst again;
S4. 循环进行步骤S3.,步骤S3.进行的次数为1~5次, 所述甘油反应液中甘油浓度及助剂Bi的含量保持恒定;在进行步骤S1和循环进行步骤S3.的过程中实现连续生产1,3-二羟基丙酮。S4. cyclically carry out step S3., the number of times that step S3. is carried out is 1 to 5 times, and the glycerol concentration and the content of auxiliary Bi in the glycerin reaction solution are kept constant; in the process of carrying out step S1 and circulating step S3. Realize the continuous production of 1,3-dihydroxyacetone.
本发明提供的生产方法采用原位双金属Pt-Bi催化剂选择性催化氧化甘油制1,3-二羟基丙酮,原位双金属Pt-Bi催化剂具有高效的催化活性,甘油转化率的DHA选择性高;反应后的双金属Pt-Bi催化剂失活,失活后的双金属Pt-Bi催化剂通过上述煅烧方法再生,双金属Pt-Bi催化剂的催化活性得到恢复,实现双金属Pt-Bi催化剂的循环使用,甘油反应液中甘油浓度及助剂Bi的含量保持恒定,双金属Pt-Bi催化剂能够保持初始高甘油转化率的DHA选择性,从而实现工业上的连续生产。The production method provided by the present invention adopts an in-situ bimetallic Pt-Bi catalyst to selectively catalyze the oxidation of glycerol to produce 1,3-dihydroxyacetone. The in-situ bimetallic Pt-Bi catalyst has high catalytic activity and DHA selectivity of glycerol conversion High; the bimetallic Pt-Bi catalyst after the reaction is deactivated, the deactivated bimetallic Pt-Bi catalyst is regenerated by the above calcination method, the catalytic activity of the bimetallic Pt-Bi catalyst is recovered, and the bimetallic Pt-Bi catalyst is realized. Recycled, the glycerol concentration in the glycerol reaction solution and the content of the auxiliary Bi remain constant, and the bimetallic Pt-Bi catalyst can maintain the DHA selectivity of the initial high glycerol conversion rate, thereby realizing continuous industrial production.
与现有技术相比,本发明的有益效果是:Compared with the prior art, the beneficial effects of the present invention are:
本发明提供的制备方法能够利用失活的双金属Pt-Bi催化剂制备得到高活性的双金属Pt-Bi催化剂,制得的双金属Pt-Bi催化剂催化活性高,能够高效选择性催化氧化甘油制DHA。The preparation method provided by the present invention can utilize the deactivated bimetallic Pt-Bi catalyst to prepare the highly active bimetallic Pt-Bi catalyst, the prepared bimetallic Pt-Bi catalyst has high catalytic activity, and can efficiently and selectively catalyze the oxidation of glycerol to produce DHA.
另外,本发明提供的选择性催化氧化甘油制1,3-二羟基丙酮的方法通过煅烧将失活后的双金属Pt-Bi催化剂再生,实现双金属Pt-Bi催化剂的循环使用,甘油反应液中甘油浓度及助剂Bi的含量保持恒定,双金属Pt-Bi催化剂能够保持初始高甘油转化率的DHA选择性,从而实现工业上的连续生产。In addition, the method for producing 1,3-dihydroxyacetone by selective catalytic oxidation of glycerol provided by the present invention regenerates the deactivated bimetallic Pt-Bi catalyst through calcination, so as to realize the recycling of the bimetallic Pt-Bi catalyst, and the glycerol reaction solution The concentration of glycerol in the medium and the content of the auxiliary Bi are kept constant, and the bimetallic Pt-Bi catalyst can maintain the DHA selectivity of the initial high glycerol conversion rate, thereby realizing continuous industrial production.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例中的原料均可通过市售得到;The raw materials in the embodiment can all be obtained commercially;
除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
实施例和对比例中Pt催化剂采用如下方法制备得到:In the embodiment and the comparative example, the Pt catalyst is prepared by the following method:
将100 mg氮掺杂碳材料倒入60 ml乙二醇溶液中得到氮掺杂碳材料分散液,超声分散20 min;再将1.35 mL的H2PtCl6 (0.02 M) 溶液加入至氮掺杂碳材料分散液中;用0.04M的KOH溶液调pH至8.5,140℃下搅拌回流2h;冷却到室温后过滤,淋洗至滤液为中性,于75℃真空干燥24 h,研磨,得到新鲜的Pt催化剂,Pt催化剂的Pt负载量为5 wt.%。Pour 100 mg of nitrogen-doped carbon material into 60 ml of ethylene glycol solution to obtain a nitrogen-doped carbon material dispersion, and ultrasonically disperse for 20 min; then add 1.35 mL of H 2 PtCl 6 (0.02 M) solution to the nitrogen-doped carbon material. In carbon material dispersion; adjust pH to 8.5 with 0.04M KOH solution, stir and reflux at 140 °C for 2 h; filter after cooling to room temperature, rinse until the filtrate is neutral, vacuum dry at 75 °C for 24 h, grind to obtain fresh The Pt catalyst with a Pt loading of 5 wt.%.
实施例1Example 1
(1)催化氧化甘油制1,3-二羟基丙酮(1) Catalytic oxidation of glycerol to 1,3-dihydroxyacetone
往150mL的四颈烧瓶中加入甘油水溶液(50 g,10wt.%,Bi(mBi / mPt= 0.2))和100mg Pt催化剂,形成原位双金属Pt-Bi催化剂,以600 rpm的搅拌速率升温至60℃,然后通入氧气(150 mL/min),开始反应;6h后,停止反应。反应器内反应溶液和催化剂的混合物在反应前后都要进行称量,再过滤液固相混合物;反应液用液相色谱进行检测分析。To a 150 mL four-neck flask, an aqueous solution of glycerol (50 g, 10 wt.%, Bi (m Bi /m Pt = 0.2)) and 100 mg of Pt catalyst were added to form an in-situ bimetallic Pt-Bi catalyst with a stirring rate of 600 rpm The temperature was raised to 60 °C, and then oxygen (150 mL/min) was introduced to start the reaction; after 6 h, the reaction was stopped. The mixture of the reaction solution and the catalyst in the reactor is weighed before and after the reaction, and the liquid-solid mixture is filtered; the reaction solution is detected and analyzed by liquid chromatography.
(2)双金属Pt-Bi催化剂的再生(2) Regeneration of bimetallic Pt-Bi catalyst
将(1)中反应后的双金属Pt-Bi催化剂,经过滤,用水和酒精洗涤,真空干燥后,研磨,装入瓷舟中,放置在水平高温管式炉中煅烧,煅烧条件为温度200℃、Ar流量100mL/min,煅烧时间2h;所得催化剂标记为Pt-Bi(200)。The bimetallic Pt-Bi catalyst reacted in (1) was filtered, washed with water and alcohol, dried in vacuum, ground, loaded into a porcelain boat, and calcined in a horizontal high-temperature tube furnace at a temperature of 200 °C. ℃, Ar flow rate 100mL/min, calcination time 2h; the obtained catalyst is marked as Pt-Bi(200).
实施例2Example 2
本实施例与实施例1不同的是,(2)中煅烧的温度为300℃;其他与实施例1相同;所得催化剂标记为Pt-Bi(300)。The difference between this example and Example 1 is that the calcination temperature in (2) is 300°C; the other is the same as that of Example 1; the obtained catalyst is marked as Pt-Bi(300).
实施例3Example 3
将实施例2制得的Pt-Bi(300)再循环一次,即重复进行步骤(1)和(2),所得催化剂标记为Pt-Bi(300-2)。The Pt-Bi(300) prepared in Example 2 was recycled once, that is, the steps (1) and (2) were repeated, and the obtained catalyst was marked as Pt-Bi(300-2).
实施例4Example 4
将实施例3制得的Pt-Bi(300-2)再循环一次,即重复进行步骤(1)和(2),所得催化剂标记为Pt-Bi(300-3)。The Pt-Bi (300-2) prepared in Example 3 was recycled once, that is, the steps (1) and (2) were repeated, and the obtained catalyst was marked as Pt-Bi (300-3).
实施例5Example 5
将实施例4制得的Pt-Bi(300-3)再循环一次,即重复进行步骤(1)和(2),所得催化剂标记为Pt-Bi(300-4)。The Pt-Bi (300-3) prepared in Example 4 was recycled once, that is, the steps (1) and (2) were repeated, and the obtained catalyst was marked as Pt-Bi (300-4).
对比例1Comparative Example 1
(1)催化氧化甘油制1,3-二羟基丙酮(1) Catalytic oxidation of glycerol to 1,3-dihydroxyacetone
往150mL的四颈烧瓶中加入甘油水溶液(50 g,10wt.%)和100 mg Pt催化剂,以600rpm的搅拌速率升温至60℃,然后通入氧气(150 mL/min),开始反应;6h后,停止反应。反应器内反应溶液和催化剂的混合物在反应前后都要进行称量,再过滤液固相混合物;反应液用液相色谱进行检测分析。A glycerol aqueous solution (50 g, 10 wt.%) and 100 mg Pt catalyst were added to a 150 mL four-necked flask, and the temperature was raised to 60 °C at a stirring rate of 600 rpm, and then oxygen (150 mL/min) was introduced to start the reaction; after 6 h , stop the reaction. The mixture of the reaction solution and the catalyst in the reactor is weighed before and after the reaction, and the liquid-solid mixture is filtered; the reaction solution is detected and analyzed by liquid chromatography.
(2)Pt催化剂的分离(2) Separation of Pt catalyst
将(1)中反应后的Pt催化剂,经过滤,用水和酒精洗涤,真空干燥后,研磨,所得催化剂记为Pt(2)。The Pt catalyst reacted in (1) was filtered, washed with water and alcohol, dried in vacuo, and ground, and the obtained catalyst was denoted as Pt(2).
对比例2Comparative Example 2
(1)催化氧化甘油制1,3-二羟基丙酮(1) Catalytic oxidation of glycerol to 1,3-dihydroxyacetone
往150mL的四颈烧瓶中加入甘油水溶液(50 g,10wt.%,Bi(mBi / mPt= 0.2))和100mg Pt催化剂,形成原位双金属Pt-Bi催化剂,以600 rpm的搅拌速率升温至60℃,然后通入氧气(150 mL/min),开始反应;6h后,停止反应。反应器内反应溶液和催化剂的混合物在反应前后都要进行称量,再过滤液固相混合物;反应液用液相色谱进行检测分析。To a 150 mL four-neck flask, an aqueous solution of glycerol (50 g, 10 wt.%, Bi (m Bi /m Pt = 0.2)) and 100 mg of Pt catalyst were added to form an in-situ bimetallic Pt-Bi catalyst with a stirring rate of 600 rpm The temperature was raised to 60 °C, and then oxygen (150 mL/min) was introduced to start the reaction; after 6 h, the reaction was stopped. The mixture of the reaction solution and the catalyst in the reactor is weighed before and after the reaction, and the liquid-solid mixture is filtered; the reaction solution is detected and analyzed by liquid chromatography.
(2)双金属Pt-Bi催化剂的分离(2) Separation of bimetallic Pt-Bi catalysts
将(1)中反应后的双金属Pt-Bi催化剂,经过滤,用水和酒精洗涤,真空干燥后,研磨,所得催化剂记为Pt-Bi(2)。The bimetallic Pt-Bi catalyst reacted in (1) was filtered, washed with water and alcohol, dried under vacuum, and ground, and the obtained catalyst was denoted as Pt-Bi(2).
对比例3Comparative Example 3
本对比例与对比例2的区别在于,(2)双金属Pt-Bi催化剂的分离的步骤如下:将(1)中反应后的双金属Pt-Bi催化剂,加入丙酮(100 mg/200 mL),60℃下搅拌2 h,用80℃酒精过滤冲洗、真空干燥、研磨;其他与对比例2相同;The difference between this comparative example and comparative example 2 is that (2) the separation steps of the bimetallic Pt-Bi catalyst are as follows: add acetone (100 mg/200 mL) to the bimetallic Pt-Bi catalyst after the reaction in (1) , stirred at 60 °C for 2 h, filtered and rinsed with 80 °C alcohol, vacuum dried, and ground; the others were the same as in Comparative Example 2;
所得催化剂标记为Pt-Bi(Ace.)。The resulting catalyst was designated Pt-Bi (Ace.).
对比例4Comparative Example 4
本对比例与对比例2的区别在于,(2)双金属Pt-Bi催化剂的分离的步骤如下:将(1)中反应后的双金属Pt-Bi催化剂,加入1 M NaOH(100 mg/200 mL),室温下搅拌2 h后倾倒完碱液;加入丙酮溶液(100 mg/200 mL),60℃下搅拌1 h,用80℃酒精过滤冲洗、真空干燥、研磨;其他与对比例2相同;The difference between this comparative example and comparative example 2 is that (2) the separation steps of the bimetallic Pt-Bi catalyst are as follows: the bimetallic Pt-Bi catalyst after the reaction in (1) is added with 1 M NaOH (100 mg/200 mL), stirred at room temperature for 2 h, and then poured the lye solution; added acetone solution (100 mg/200 mL), stirred at 60 °C for 1 h, filtered and rinsed with 80 °C alcohol, vacuum-dried, and ground; others were the same as in Comparative Example 2 ;
所得催化剂标记为Pt-Bi(OH)。The resulting catalyst was designated Pt-Bi(OH).
对比例5Comparative Example 5
本对比例与实施例1不同的是,(2)中煅烧的温度为150℃;其他与实施例1相同;所得催化剂标记为Pt-Bi(150)。The difference between this comparative example and Example 1 is that the calcination temperature in (2) is 150°C; the other is the same as that of Example 1; the obtained catalyst is marked as Pt-Bi(150).
性能测试Performance Testing
采用配有紫外和示差检测器的高效液相色谱对反应液进行定性定量分析。以HPX-87H(Aminex)作为分离柱,H2SO4(0.025 M)作为流动相。测试的紫外检测器波长设置为210nm, 示差检测器温度为40℃,柱温为60℃,流动相速率为0.6 mL·min-1。本研究根据标准样品进行定性分析,反应物和产物均采用外标法进行定量分析。The reaction solution was qualitatively and quantitatively analyzed by high performance liquid chromatography equipped with UV and differential detectors. HPX-87H (Aminex) was used as the separation column, and H 2 SO 4 (0.025 M) was used as the mobile phase. The wavelength of the UV detector tested was set to 210 nm, the temperature of the differential detector was 40 °C, the column temperature was 60 °C, and the mobile phase rate was 0.6 mL·min -1 . In this study, the qualitative analysis was carried out according to the standard samples, and the external standard method was used for quantitative analysis of the reactants and products.
催化剂的甘油转化率和DHA选择性的计算方法如下:The glycerol conversion and DHA selectivity of the catalyst were calculated as follows:
(1)甘油转化率(1) Conversion rate of glycerol
甘油转化率 (%) = (反应前甘油质量-反应后甘油剩余质量) / 反应前甘油质量×100 %Conversion rate of glycerol (%) = (mass of glycerol before reaction - remaining mass of glycerol after reaction) / mass of glycerol before reaction × 100 %
(2)DHA选择性(2) DHA selectivity
DHA选择性 (%) = 反应生成的DHA的质量×92 / [(反应前甘油质量-反应后甘油剩余质量) ×90] ×100 %DHA selectivity (%) = the mass of DHA produced by the reaction × 92 / [(the mass of glycerol before the reaction - the remaining mass of glycerol after the reaction) × 90] × 100 %
实施例1~5及对比例2~5中,初次反应的催化剂记为Pt-Bi,即初始原位双金属Pt-Bi催化剂;In Examples 1 to 5 and Comparative Examples 2 to 5, the catalyst for the initial reaction is denoted as Pt-Bi, that is, the initial in-situ bimetallic Pt-Bi catalyst;
对比例1中,初次反应的催化剂记为Pt,即初始Pt催化剂。In Comparative Example 1, the catalyst for the primary reaction is denoted as Pt, that is, the initial Pt catalyst.
实施例1~5制得的催化剂的催化性能如表1所示;The catalytic properties of the catalysts prepared in Examples 1 to 5 are shown in Table 1;
对比例1~5制得的催化剂的催化性能如表2所示。The catalytic performance of the catalysts prepared in Comparative Examples 1 to 5 is shown in Table 2.
表1 实施例1~5制得的催化剂的催化性能Table 1 Catalytic performance of catalysts prepared in Examples 1 to 5
表2 对比例1~5制得的催化剂的催化性能Table 2 Catalytic performance of catalysts prepared in Comparative Examples 1~5
由表1可知,本发明提供的制备方法制得的双金属Pt-Bi催化剂催化活性高,能高效选择性催化氧化甘油制DHA。实施例1~5得到的催化剂的甘油转化率为25.2%~31.1%,DHA选择性为52.9%~62.6%,而初始原位双金属Pt-Bi催化剂的甘油转化率和DHA选择性分别为18.0%和44.7%,可见实施例1~5制得的双金属Pt-Bi催化剂的催化性能均明显优于初始原位双金属Pt-Bi催化剂。所以,本发明提供的方法不但恢复了双金属Pt-Bi催化剂的催化活性,而且提高了双金属Pt-Bi催化剂的催化活性。其中,实施例3具有最优的催化效果,甘油转化率为初始原位双金属Pt-Bi催化剂的1.73倍。DHA选择性一般会随着转化率的升高有一定程度的降低。实施例3在更高的甘油转化率下,DHA选择性仍为初始原位双金属Pt-Bi催化剂的1.30倍。It can be seen from Table 1 that the bimetallic Pt-Bi catalyst prepared by the preparation method provided by the present invention has high catalytic activity and can efficiently and selectively catalyze the oxidation of glycerol to produce DHA. The glycerol conversion of the catalysts obtained in Examples 1 to 5 was 25.2% to 31.1%, and the DHA selectivity was 52.9% to 62.6%, while the initial in-situ bimetallic Pt-Bi catalyst had a glycerol conversion and DHA selectivity of 18.0%. % and 44.7%, it can be seen that the catalytic performance of the bimetallic Pt-Bi catalysts prepared in Examples 1 to 5 is significantly better than the initial in-situ bimetallic Pt-Bi catalysts. Therefore, the method provided by the present invention not only restores the catalytic activity of the bimetallic Pt-Bi catalyst, but also improves the catalytic activity of the bimetallic Pt-Bi catalyst. Among them, Example 3 has the best catalytic effect, and the conversion rate of glycerol is 1.73 times that of the initial in-situ bimetallic Pt-Bi catalyst. The DHA selectivity generally decreases to a certain extent with the increase of the conversion rate. Example 3 At higher glycerol conversion, the DHA selectivity is still 1.30 times that of the initial in situ bimetallic Pt-Bi catalyst.
由实施例2~5可知,本发明提供的选择性催化氧化甘油制1,3-二羟基丙酮的方法通过双金属Pt-Bi催化剂循环使用,甘油反应液中甘油浓度及助剂Bi的含量保持恒定,能够保持初始高甘油转化率和DHA选择性,从而实现工业上的连续生产。而且,再生4次后,即第5次循环时,双金属Pt-Bi催化剂仍具有高效的催化活性,能够保持初始高甘油转化率和DHA选择性。It can be seen from Examples 2 to 5 that the method for the selective catalytic oxidation of glycerol to prepare 1,3-dihydroxyacetone provided by the present invention is recycled through the bimetallic Pt-Bi catalyst, and the glycerol concentration and the content of the auxiliary Bi in the glycerol reaction solution are maintained. Constant, able to maintain the initial high glycerol conversion and DHA selectivity, enabling continuous production in industry. Moreover, the bimetallic Pt-Bi catalyst still has high catalytic activity after 4 times of regeneration, i.e., the 5th cycle, and can maintain the initial high glycerol conversion and DHA selectivity.
如前所述,在Pt催化剂中引入助剂Bi,即原位双金属Pt-Bi催化剂,能够提高甘油转化率和DHA选择性,如表2所示。As mentioned before, the introduction of the promoter Bi into the Pt catalyst, i.e., the in-situ bimetallic Pt-Bi catalyst, can improve the glycerol conversion and DHA selectivity, as shown in Table 2.
对比例2~5得到的双金属Pt-Bi催化剂的催化活性较低,都难以保持初始高甘油转化率和DHA选择性。对比例2中反应后的双金属Pt-Bi催化剂不进行煅烧再生,甘油转化率和DHA选择性明显降低。对比例3采用丙酮处理,对比例4采用NaOH水溶液处理,均不进行煅烧再生,甘油转化率和DHA选择性同样明显降低。对比例5中,虽然采用了煅烧再生,但是温度较低,再生得到的双金属Pt-Bi催化剂难以保持初始高甘油转化率和DHA选择性。The bimetallic Pt-Bi catalysts obtained in Comparative Examples 2 to 5 have low catalytic activity, and it is difficult to maintain the initial high glycerol conversion and DHA selectivity. The bimetallic Pt-Bi catalyst after the reaction in Comparative Example 2 was not calcined and regenerated, and the glycerol conversion and DHA selectivity were significantly reduced. Comparative Example 3 was treated with acetone, and Comparative Example 4 was treated with NaOH aqueous solution, both without calcination and regeneration, and the glycerol conversion rate and DHA selectivity were also significantly reduced. In Comparative Example 5, although the calcination regeneration was adopted, the temperature was low, and it was difficult for the regenerated bimetallic Pt-Bi catalyst to maintain the initial high glycerol conversion and DHA selectivity.
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.
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