CN108745387B - Titania-based complex/lewis acid compositions for the preparation of allantoin and methods for the preparation thereof - Google Patents
Titania-based complex/lewis acid compositions for the preparation of allantoin and methods for the preparation thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 33
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 title claims abstract description 29
- 229960000458 allantoin Drugs 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 26
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000011949 solid catalyst Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- AYKOTYRPPUMHMT-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag] AYKOTYRPPUMHMT-UHFFFAOYSA-N 0.000 claims abstract description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 47
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 8
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 229940015043 glyoxal Drugs 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 241000336291 Cistanche deserticola Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000004920 epithelial cell of skin Anatomy 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/88—Nitrogen atoms, e.g. allantoin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a titanium dioxide-based compound/Lewis acid composition for preparing allantoin and a preparation method thereof, wherein the preparation method comprises the following steps: 1) mixing tetrabutyl titanate, graphene, dimethylformamide and ethanol to form a solution A; 2) mixing water, ethanol and acetic acid to form a solution B; 3) mixing copper salt, zinc salt, silver salt, water and ethanol to form a solution C; 4) simultaneously dripping the solution B and the solution C into the solution A, and then standing, drying and grinding to obtain a powder object; 5) calcining the powder object to prepare a titanium dioxide-based composite solid catalyst; 6) soaking the titanium dioxide-based composite solid catalyst, zinc chloride and niobium pentachloride in hydrochloric acid, and then drying to prepare the titanium dioxide-based composite/Lewis acid composition. The base compound/Lewis acid composition has excellent catalytic effect on the synthesis of allantoin, and the preparation method has the characteristics of simple process and easily obtained raw materials.
Description
Technical Field
The invention relates to allantoin, in particular to a titanium dioxide-based complex/Lewis acid composition for preparing allantoin and a preparation method thereof.
Background
Allantoin, English name, 1-ureido-m-diazamelene-2, 4-diketone, is an important fine chemical product and has wide application. Allantoin has the physiological functions of promoting the growth of skin epithelial cells, healing sores, relieving pain, softening keratin and the like, has the functions of no toxicity, no stimulation, no allergy, light protection, sterilization, corrosion prevention and oxidation resistance, and can keep the skin moist, moist and soft, so the allantoin is widely applied to the production of medicines and cosmetics. In addition, allantoin also has the function of stimulating biological growth, can be used as a plant growth regulator in agricultural production, and has the effects of fruit strengthening, ripening, yield increasing and the like.
Natural allantoin exists in excrement of some animals and some plants, and can be extracted by certain process, for example, chinese patents CN1958575A and CN1861581A report the extraction of allantoin from yam and cistanche deserticola, respectively, but the preparation of allantoin has little practical value due to the problems of low content, complicated process steps involved, and the like. Therefore, the allantoin is prepared by a chemical synthesis method at home and abroad at present.
The existing industrial production method of allantoin mainly adopts oxalic acid electrolysis method or glyoxal nitric acid oxidation method. Wherein, the oxalic acid electrolysis method has cheap and easily obtained raw materials, but has large equipment investment, complex process flow and high energy consumption. The glyoxal method is carried out in two steps, the first step involves oxidizing glyoxal into glyoxylic acid through nitric acid, and the second step is to condense the glyoxylic acid and urea to generate allantoin under the catalytic action of a catalyst, wherein the yield is about 40% generally. The existing catalyst is inorganic strong acid generally, and the inorganic strong acid serving as the catalyst can corrode equipment and pollute the environment; more importantly, the catalytic effect of the inorganic strong acid catalyst is not very excellent, so that the yield of the allantoin is generally low.
Disclosure of Invention
The invention aims to provide a titanium dioxide-based complex/Lewis acid composition for preparing allantoin and a preparation method thereof, wherein the titanium dioxide-based complex/Lewis acid composition has an excellent catalytic effect on the synthesis of the allantoin, and the preparation method has the characteristics of simple process and readily available raw materials.
In order to achieve the above object, the present invention provides a method for preparing a titanium dioxide-based complex/lewis acid composition for allantoin, comprising:
1) mixing tetrabutyl titanate, graphene, dimethylformamide and ethanol to form a solution A;
2) mixing water, ethanol and acetic acid to form a solution B;
3) mixing copper salt, zinc salt, silver salt, water and ethanol to form a solution C;
4) simultaneously dripping the solution B and the solution C into the solution A, and then standing, drying and grinding to obtain a powder object;
5) calcining the powder object to prepare a titanium dioxide-based composite solid catalyst;
6) soaking the titanium dioxide-based composite solid catalyst, zinc chloride and niobium pentachloride in hydrochloric acid, and then drying to prepare the titanium dioxide-based composite/Lewis acid composition.
The invention also provides a titanium dioxide-based complex/Lewis acid composition for preparing allantoin, which is prepared by the preparation method.
In the technical scheme, tetrabutyl titanate/graphene solution, ethanol solution and metal salt solution are prepared firstly, then the tetrabutyl titanate/graphene solution, the ethanol solution and the metal salt solution are subjected to contact reaction, standing, drying and grinding to obtain a powder object, then the powder object is fired to obtain the titanium dioxide-based composite solid catalyst, and finally the solid catalyst/Lewis acid are mixed to form the titanium dioxide-based composite/Lewis acid composition. The titanium dioxide-based compound/Lewis acid composition has excellent catalytic performance for synthesizing allantoin, and further improves the yield and the synthesis efficiency of the allantoin.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides a process for preparing a titanium dioxide-based complex/lewis acid composition for the preparation of allantoin, comprising:
1) mixing tetrabutyl titanate, graphene, dimethylformamide and ethanol to form a solution A;
2) mixing water, ethanol and acetic acid to form a solution B;
3) mixing copper salt, zinc salt, silver salt, water and ethanol to form a solution C;
4) simultaneously dripping the solution B and the solution C into the solution A, and then standing, drying and grinding to obtain a powder object;
5) calcining the powder object to prepare a titanium dioxide-based composite solid catalyst;
6) soaking the titanium dioxide-based composite solid catalyst, zinc chloride and niobium pentachloride in hydrochloric acid, and then drying to prepare the titanium dioxide-based composite/Lewis acid composition.
In step 1) of the present invention, the amount of each material may be in a wide range, but in order to further improve the catalytic efficiency of the titanium oxide-based complex/lewis acid composition, it is preferable that the weight ratio of tetrabutyl titanate, graphene, dimethylformamide, and ethanol in step 1) is 20: 5-10: 40-60: 50-70.
In step 2) of the present invention, the amount of each material may be in a wide range, but in order to further improve the catalytic efficiency of the titanium oxide-based composite/lewis acid composition, it is preferable that the weight ratio of water, ethanol and acetic acid in step 2) is 5: 20-25: 2-3.
In step 3) of the present invention, the amount of each material may be in a wide range, but in order to further improve the catalytic efficiency of the titania-based complex/lewis acid composition, it is preferable that the weight ratio of copper salt, zinc salt, silver salt, water, and ethanol in step 3) is 10: 2-4: 0.2-0.6: 20-26: 15-20.
In steps 1) to 3) of the present invention, the conditions of mixing may be in a wide range, but in order to further improve the catalytic efficiency of the titania-based composite/lewis acid composition, it is preferable that in steps 1) to 3), the mixing satisfies the following conditions: the mixing temperature is 15-35 deg.C, and the mixing time is 40-60 min.
In step 4) of the present invention, the amount of each material may be in a wide range, but in order to further improve the catalytic efficiency of the titania-based composite/lewis acid composition, it is preferable that the volume ratio of the solution a, the solution B, and the solution C in step 4) is 100: 20-25: 8-12.
In step 4) of the present invention, the conditions for standing may be in a wide range, but in order to further improve the catalytic efficiency of the titanium oxide-based composite/lewis acid composition, it is preferable that in step 4), the standing satisfies the following conditions: standing at 10-20 deg.C for 12-24 hr; the drying satisfies the following conditions: the drying temperature is 100-110 ℃, and the drying time is 6-10 h.
In step 4) of the present invention, the kinds of the respective materials may be in a wide range, but in order to further improve the catalytic efficiency of the titania-based composite/lewis acid composition, preferably, in step 4), the copper salt is selected from at least one of copper sulfate, copper chloride, copper nitrate; the zinc salt is at least one selected from zinc sulfate, zinc chloride and zinc nitrate; the silver salt is silver nitrate.
In step 5) of the present invention, the conditions of calcination may be within a wide range, but in order to further improve the catalytic efficiency of the titanium oxide-based composite/lewis acid composition, it is preferable that in step 5), the calcination is: heating from 15-35 deg.C at 2-2.5 deg.C/min to 300-.
In step 6) of the present invention, the amount of each material may be in a wide range, but in order to further improve the catalytic efficiency of the titanium oxide-based complex/lewis acid composition, it is preferable that the weight ratio of the titanium oxide-based composite solid catalyst, zinc chloride, niobium pentachloride, hydrochloric acid is 20: 4-6: 1.6-3: 60-80.
In step 6) of the present invention, the soaking time may be in a wide range, but in order to further improve the catalytic efficiency of the titanium oxide-based composite/lewis acid composition, it is preferable that the soaking time is 4 to 6 hours.
In step 6) of the present invention, the pH of hydrochloric acid may be in a wide range, but in order to further improve the catalytic efficiency of the titanium oxide-based complex/Lewis acid composition, it is preferable that the pH of hydrochloric acid is 3 to 4.
The invention also provides a titanium dioxide-based complex/Lewis acid composition for preparing allantoin, which is prepared by the preparation method.
The present invention will be described in detail below by way of examples.
Example 1
1) Tetrabutyl titanate, graphene, dimethylformamide and ethanol are mixed according to the weight ratio of 20: 8: 50: mixing at a weight ratio of 60 (the mixing temperature is 25 ℃ and the mixing time is 50 min) to form a solution A;
2) mixing water, ethanol and acetic acid according to the ratio of 5: 23: 2.5 (mixing temperature 25 ℃ and mixing time 50 min) to form a solution B;
3) mixing copper salt (copper sulfate), zinc salt (zinc sulfate), silver salt (silver nitrate), water and ethanol according to the ratio of 10: 3: 0.5: 23: 18 (mixing temperature 25 ℃ and mixing time 50 min) to form a solution C;
4) and (3) simultaneously dropwise adding the solution B and the solution C into the solution A (the volume ratio of the solution A to the solution B to the solution C is 100: 23: 10) then, standing (standing temperature 15 ℃ C., standing time 20 hours), drying (drying temperature 105 ℃ C., drying time 8 hours), and grinding to obtain a powder object;
5) the powder object was subjected to calcination (heating from 25 ℃ to 330 ℃ at 2.3 ℃/min and holding for 35min, followed by heating to 580 ℃ at 1.3 ℃/min and holding for 1.5 h) to prepare a titanium dioxide-based composite solid catalyst a 1.
Example 2
1) Tetrabutyl titanate, graphene, dimethylformamide and ethanol are mixed according to the weight ratio of 20: 5: 40: mixing at a weight ratio of 50 (the mixing temperature is 15 ℃ and the mixing time is 60 min) to form a solution A;
2) mixing water, ethanol and acetic acid according to the ratio of 5: 20: 2 (the mixing temperature is 15 ℃, the mixing time is 60 min) to form a solution B;
3) mixing copper salt (cupric chloride), zinc salt (zinc chloride), silver salt (silver nitrate), water and ethanol according to the ratio of 10: 2: 0.2: 20: 15 (the mixing temperature is 15 ℃ and the mixing time is 60 min) to form a solution C;
4) and (3) simultaneously dropwise adding the solution B and the solution C into the solution A (the volume ratio of the solution A to the solution B to the solution C is 100: 20: 8) then standing (standing temperature is 10 ℃, standing time is 24 hours), drying (drying temperature is 100 ℃, drying time is 10 hours), and grinding to obtain a powder object;
5) the powder body was calcined (from 15 ℃ at 2 ℃/min to 300 ℃ and held for 30min, then at 1 ℃/min to 550 ℃ and held for 2 h) to produce a titanium dioxide-based composite solid catalyst a 2.
Example 3
1) Tetrabutyl titanate, graphene, dimethylformamide and ethanol are mixed according to the weight ratio of 20: 10: 60: 70 (the mixing temperature is 35 ℃, the mixing time is 40 min) to form a solution A;
2) mixing water, ethanol and acetic acid according to the ratio of 5: 25: 3 (the mixing temperature is 35 ℃, the mixing time is 40 min) to form a solution B;
3) mixing copper salt (cupric nitrate), zinc salt (zinc nitrate), silver salt (silver nitrate), water and ethanol according to the ratio of 10: 4: 0.6: 26: 20 (mixing temperature 35 ℃ and mixing time 60 min) to form a solution C;
4) and (3) simultaneously dropwise adding the solution B and the solution C into the solution A (the volume ratio of the solution A to the solution B to the solution C is 100: 25: 12) then standing (standing temperature is 20 ℃, standing time is 12 hours), drying (drying temperature is 110 ℃, drying time is 6 hours), and grinding to obtain a powder object;
5) the powder object was subjected to calcination (heating from 35 ℃ to 360 ℃ at 2.5 ℃/min and holding for 40min, followed by heating to 600 ℃ at 1.6 ℃/min and holding for 1 h) to prepare a titanium dioxide-based composite solid catalyst a 3.
Comparative example 1
The titania-based composite solid catalyst B1 was obtained by following the procedure of example 1, except that graphene was not used in the step 1).
Comparative example 2
The titania-based composite solid catalyst B2 was obtained by the same method as in example 1, except that no copper salt was used in the step 1).
Comparative example 3
The titanium dioxide-based composite solid catalyst B3 was obtained by following the procedure of example 1, except that zinc salt was not used in the step 1).
Comparative example 4
The production of the titania-based composite solid catalyst B4 was carried out in the same manner as in example 1, except that no silver salt was used in step 1).
Application example 1
Soaking the titanium dioxide-based composite solid catalyst, zinc chloride and niobium pentachloride in hydrochloric acid with the pH value of 3 for 5 hours (the weight ratio of the titanium dioxide-based composite solid catalyst to the zinc chloride to the niobium pentachloride to the hydrochloric acid is 20: 5: 2: 70), and then drying (the drying temperature is 105 ℃, and the drying time is 8 hours) to prepare the titanium dioxide-based composite/Lewis acid composition, wherein the titanium dioxide-based composite solid catalyst is not added in a control group.
Reacting glyoxal with nitric acid according to a ratio of 1: 1.1 (reaction temperature 41 ℃ C., reaction time 5 hours) to produce glyoxylic acid, followed by reacting glyoxylic acid, urea, a titanium dioxide-based complex/Lewis acid composition in a molar ratio of 1: 4: performing condensation reaction at a molar ratio of 0.008 (reaction temperature of 75 ℃ and reaction time of 4 h) to obtain allantoin; finally, the allantoin yield was counted, and the specific results are shown in Table 1.
TABLE 1
| Titanium dioxide-based composite solid catalyst in composition | Yield (%) |
| A1 | 85 |
| A2 | 83 |
| A3 | 79 |
| B1 | 41 |
| B2 | 52 |
| B3 | 79 |
| B4 | 60 |
| Control group | 35 |
Application example 2
The process was carried out as in application example 1, except that the weight ratio of the titanium dioxide-based composite solid catalyst, zinc chloride, niobium pentachloride and hydrochloric acid was 20: 4: 1.6: 60.
application example 3
The process was carried out as in application example 1, except that the weight ratio of the titanium dioxide-based composite solid catalyst, zinc chloride, niobium pentachloride and hydrochloric acid was 20: 6: 3: 80.
the experimental results of application examples 2 to 3 were substantially identical to the experimental result of application example 1.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A process for preparing a titanium dioxide-based complex/lewis acid composition for the preparation of allantoin, comprising:
1) mixing tetrabutyl titanate, graphene, dimethylformamide and ethanol to form a solution A;
2) mixing water, ethanol and acetic acid to form a solution B;
3) mixing copper salt, zinc salt, silver salt, water and ethanol to form a solution C;
4) simultaneously dripping the solution B and the solution C into the solution A, and then standing, drying and grinding to obtain a powder object;
5) calcining the powder object to prepare a titanium dioxide-based composite solid catalyst;
6) soaking the titanium dioxide-based composite solid catalyst, zinc chloride and niobium pentachloride in hydrochloric acid, and then drying to prepare a titanium dioxide-based composite/Lewis acid composition; in the step 1), the weight ratio of tetrabutyl titanate, graphene, dimethylformamide and ethanol is 20: 5-10: 40-60: 50-70 parts of; in the step 2), the weight ratio of the water to the ethanol to the acetic acid is 5: 20-25: 2-3; in the step 3), the weight ratio of the copper salt, the zinc salt, the silver salt, the water and the ethanol is 10: 2-4: 0.2-0.6: 20-26: 15-20 parts of; in the step 4), the volume ratio of the solution A to the solution B to the solution C is 100: 20-25: 8-12; in step 4), the standing satisfies the following conditions: standing at 10-20 deg.C for 12-24 hr; the drying satisfies the following conditions: the drying temperature is 100-; the weight ratio of the titanium dioxide-based composite solid catalyst to the zinc chloride to the niobium pentachloride to the hydrochloric acid is 20: 4-6: 1.6-3: 60-80.
2. The production method according to claim 1, wherein, in step 1) to step 3), the mixing satisfies the following condition: the mixing temperature is 15-35 deg.C, and the mixing time is 40-60 min.
3. The production method according to claim 1, wherein, in step 4), the copper salt is selected from at least one of copper sulfate, copper chloride, and copper nitrate; the zinc salt is at least one selected from zinc sulfate, zinc chloride and zinc nitrate; the silver salt is silver nitrate.
4. The production method according to claim 1, wherein, in step 5), the calcination is: heating from 15-35 deg.C at 2-2.5 deg.C/min to 300-.
5. The method of any one of claims 1-4, wherein the soaking time is 4-6 hours.
6. The production method according to any one of claims 1 to 4, wherein the pH of the hydrochloric acid is 3 to 4.
7. A titanium dioxide-based complex/Lewis acid composition for the preparation of allantoin, which is prepared by the preparation method according to any one of claims 1 to 6.
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