CN108689940A - The method for preparing allantoin based on oxidation iron-based composite catalysis - Google Patents
The method for preparing allantoin based on oxidation iron-based composite catalysis Download PDFInfo
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- CN108689940A CN108689940A CN201810866333.0A CN201810866333A CN108689940A CN 108689940 A CN108689940 A CN 108689940A CN 201810866333 A CN201810866333 A CN 201810866333A CN 108689940 A CN108689940 A CN 108689940A
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- 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
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a kind of method preparing allantoin based on oxidation iron-based composite catalysis, which includes:1)Trivalent iron salt, bismuth source, manganese source, cobalt source, polyvinyl alcohol are dispersed in water, it is subsequently added into alkali and carries out haptoreaction, then anion surfactant is added and carries out secondary response, then system is extracted to by extractant and taken organic phase, finally removes extractant, dry obtained reaction product;2)Reaction product is calcined so that oxidation iron-based composite is made;3)The oxidation iron-based composite, sulfuric acid solution, boric acid solution are mixed, then filter to take filter cake so that oxidation iron-based composite/sulfuric acid/boric acid composition is made;4)Glyoxal and nitric acid are subjected to oxidation reaction so that glyoxalic acid is made, glyoxalic acid, urea, oxidation iron-based composite/sulfuric acid/boric acid composition are then subjected to condensation reaction so that allantoin is made.This method can efficiently prepare allantoin, while the preparation method has the advantages that process is simple and raw material is easy to get.
Description
Technical field
The present invention relates to allantoins, and in particular, to a kind of side preparing allantoin based on oxidation iron-based composite catalysis
Method.
Background technology
Allantoin, English name Allantion, chemical name Allantio are a kind of important
Fine chemical product, purposes are extremely wide.Allantoin, which has, promotes skin epithelial cell growth, wound healing, analgesic, softening angle
The physiological functions such as matter albumen, and it is nontoxic, non-stimulated, without anaphylaxis, be protected from light, sterilization and anticorrosion, antioxidation, skin can be made
Moisture content is kept, is moistened and soft, thus is widely used in medicine and Cosmetic Manufacture.In addition, allantoin also has stimulation life
The function of object growth, can be used as plant growth regulator in agricultural production, there is solid fruit, accelerate the ripening, increase production and other effects.
Natural allantoin is present in excreta and some plants of certain animals, and certain technique may be used and carried
It takes, for example, Chinese patent CN1958575A and CN1861581A are reported respectively from Chinese yam and extracting allantoin in Herba Cistanches,
But the problems such as complicated because of the low processing step with involved by of content, almost without practical value for the preparation of allantoin.Therefore,
Being all made of chemical synthesis process both at home and abroad prepares allantoin at present.
Existing industrialized production allantoin method mainly uses oxalic acid electrolysis or glyoxal nitric acid oxidation method.Its
In, oxalic acid electrolysis raw material is cheap and easy to get, but equipment investment is big, technological process is complicated, high energy consumption.Glyoxal method in two steps into
Row, the first step relate to glyoxal through nitric acid oxidation be glyoxalic acid, second step be under the catalytic action of catalyst glyoxalic acid with
Urea condensation generates allantoin, yield generally about 40%.Existing catalyst is generally inorganic acid, and inorganic acid is as catalysis
On the one hand agent can cause to corrode to equipment, pollute the environment simultaneously;The significantly catalytic effect of strong inorganic acid catalyst
It is not very superior, causes the yield of allantoin generally low.
Invention content
The object of the present invention is to provide a kind of method preparing allantoin based on oxidation iron-based composite catalysis, this method energy
It is enough efficiently to prepare allantoin, while the preparation method has the advantages that process is simple and raw material is easy to get.
To achieve the goals above, the present invention provides a kind of sides preparing allantoin based on oxidation iron-based composite catalysis
Method, including:
1)Trivalent iron salt, bismuth source, manganese source, cobalt source, polyvinyl alcohol are dispersed in water, alkali is subsequently added into and carries out haptoreaction, so
Anion surfactant is added afterwards and carries out secondary response, then system is extracted to by extractant and taken organic phase, finally
Remove extractant, dry obtained reaction product;
2)Reaction product is calcined so that oxidation iron-based composite is made;
3)The oxidation iron-based composite, sulfuric acid solution, boric acid solution are mixed, then filter to take filter cake so that oxidation iron-based is made
Compound/sulfuric acid/boric acid composition;
4)Glyoxal and nitric acid are subjected to oxidation reaction so that glyoxalic acid is made, then answer glyoxalic acid, urea, the oxidation iron-based
It closes object/sulfuric acid/boric acid composition and carries out condensation reaction so that allantoin is made.
Through the above technical solutions, the present invention first using polyvinyl alcohol as template, passes through trivalent iron salt, bismuth source, manganese source, cobalt
Haptoreaction is carried out between source and alkali and generates sediment, is subsequently added into the charge on anion surfactant neutralization precipitation object surface
Coating is formed, coating is then extracted and obtains oxidation iron-based composite by post-processings such as drying, calcinings, then passes through oxygen
The combination for changing iron-based composite and sulfuric acid and boric acid forms composition;Allantoin is prepared finally by the composition catalysis.The party
Method can efficiently prepare allantoin, while the preparation method has the advantages that process is simple and raw material is easy to get.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that specific implementation described herein
Mode is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of methods preparing allantoin based on oxidation iron-based composite catalysis, including:
1)Trivalent iron salt, bismuth source, manganese source, cobalt source, polyvinyl alcohol are dispersed in water, alkali is subsequently added into and carries out haptoreaction, so
Anion surfactant is added afterwards and carries out secondary response, then system is extracted to by extractant and taken organic phase, finally
Remove extractant, dry obtained reaction product;
2)Reaction product is calcined so that oxidation iron-based composite is made;
3)The oxidation iron-based composite, sulfuric acid solution, boric acid solution are mixed, then filter to take filter cake so that oxidation iron-based is made
Compound/sulfuric acid/boric acid composition;
4)Glyoxal and nitric acid are subjected to oxidation reaction so that glyoxalic acid is made, then answer glyoxalic acid, urea, the oxidation iron-based
It closes object/sulfuric acid/boric acid composition and carries out condensation reaction so that allantoin is made.
In the step 1 of above-mentioned preparation method)In, the dosage of each material can select in a wide range, but in order into
One step improves yield, it is preferable that in step 1)In, trivalent iron salt, bismuth source, manganese source, cobalt source, polyvinyl alcohol, alkali, anionic surface
Activating agent, water weight ratio be 10:0.06-0.1:2-3:0.5-1.5:4-8:8-12:10-15:60-100.
In the step 1 of above-mentioned preparation method)In, catalytic condition can select in a wide range, but in order to
Further increase yield, it is preferable that in step 1)In, haptoreaction meets the following conditions:Reaction temperature is 15-35 DEG C, reaction
Time is 1-2h.
In the step 1 of above-mentioned preparation method)In, the condition of secondary response can select in a wide range, but in order to
Further increase yield, it is preferable that in step 1)In, secondary response meets the following conditions:Reaction temperature is 60-80 DEG C, reaction
Time is 3-5h.
In the step 1 of above-mentioned preparation method)In, the dosage of extractant can select in a wide range, but in order into
One step improves yield, it is preferable that in step 1)In, in extraction process, the volume ratio of system and extractant is 1:3-5.
In the step 1 of above-mentioned preparation method)In, the type of various salt or source metal can select in a wide range,
But in order to further increase yield, it is preferable that in step 1)In, trivalent iron salt is selected from ferric trichloride, ferric sulfate and ferric nitrate
At least one of, bismuth source is selected from least one of lauric acid bismuth, isooctyl acid bismuth and bismuth naphthenate;Cobalt salt is selected from aphthenic acids
At least one of cobalt, cobaltous octadecanate, new cobalt decanoate and cobalt boracylate;Manganese source in manganese nitrate, manganese acetate, manganese sulfate extremely
Few one.
In the step 1 of above-mentioned preparation method)In, the type of anion surfactant can select in a wide range,
But in order to further increase yield, it is preferable that in step 1)In, anion surfactant is selected from dodecyl benzene sulfonic acid
At least one of sodium, lauryl sodium sulfate, myristyl benzene sulfonic acid sodium salt, sodium tetradecyl sulfate.
In the step 1 of above-mentioned preparation method)In, the type of extractant can select in a wide range, but in order into
One step improves yield, it is preferable that extractant is selected from least one of chloroform, carbon tetrachloride and acetone.
In the step 2 of above-mentioned preparation method)In, the condition of calcining can select in a wide range, but in order into one
Step improves yield, it is preferable that in step 1)In, it calcines and is:From 15-35 DEG C 260-300 DEG C is warming up to 1.8-2.2 DEG C/min simultaneously
40-60min is kept the temperature, then 520-540 DEG C is warming up to 0.7-1.2 DEG C/min and keeps the temperature 3-5h.
In the step 3 of above-mentioned preparation method)In, the dosage of each material can select in a wide range, but in order into
One step improves yield, in step 3)In, it is described oxidation iron-based composite, sulfuric acid solution, boric acid solution weight ratio be 10:
10-15:3-5, and a concentration of 8-12 weight % of the sulfuric acid solution, a concentration of 3-8 weight % of the boric acid solution.
In the step 3 of above-mentioned preparation method)In, mixed condition can select in a wide range, but in order into one
Step improves yield, it is preferable that in step 3)Described in time for mixing be 20-30h.In the step 4 of the present invention)In, glyoxal
It can in a wide range, but in order to further increase the yield of allantoin, in step 4 with the molar ratio of nitric acid)In, second two
The molar ratio of aldehyde and nitric acid is 1:1.05-1.2.
In the step 4 of the present invention)In, the condition of oxidation reaction can in a wide range, but in order to further increase
The yield of allantoin, it is preferable that oxidation reaction meets the following conditions:Reaction temperature is 40-42 DEG C, reaction time 4-6h.
In the step 4 of the present invention)In, glyoxalic acid, urea, the molar ratio for aoxidizing iron-based composite/sulfuric acid/boric acid composition
It can in a wide range, but in order to further increase the yield of allantoin, it is preferable that glyoxalic acid, urea, oxidation iron-based are multiple
The molar ratio for closing object/sulfuric acid/boric acid composition is 1:3-5:0.005-0.01.
In the step 4 of the present invention)In, the condition of condensation reaction can in a wide range, but in order to further increase
The yield of allantoin, it is preferable that condensation reaction meets the following conditions:Reaction temperature is 70-80 DEG C, reaction time 3-5h.
The present invention will be described in detail by way of examples below.
Embodiment 1
1)By trivalent iron salt(Ferric trichloride), bismuth source(Lauric acid bismuth), manganese source(Manganese nitrate), cobalt source(Cobalt naphthenate), polyethylene
Alcohol is dispersed in water, and is subsequently added into alkali and is carried out haptoreaction(Reaction temperature is 25 DEG C, reaction time 1.5h), then it is added cloudy
Ionic surface active agent(Neopelex)Carry out secondary response(Reaction temperature is 70 DEG C, reaction time 4h, trivalent
Molysite, bismuth source, manganese source, cobalt source, polyvinyl alcohol, alkali, anion surfactant, water weight ratio be 10:0.08:2.5:1:6:
10:13:80), then system passed through into extractant(Chloroform)It is extracted(System and the volume ratio of extractant are 1:4)And it takes organic
Phase finally removes extractant, dry obtained reaction product;
2)Reaction product is calcined(280 DEG C are warming up to 2 DEG C/min from 25 DEG C and keep the temperature 50min, then with 0.9 DEG C/min liters
Temperature is to 530 DEG C and keeps the temperature 4h)Oxidation iron-based composite A1 is made.
Embodiment 2
1)By trivalent iron salt(Ferric sulfate), bismuth source(Isooctyl acid bismuth), manganese source(Manganese acetate), cobalt source(Cobaltous octadecanate), polyvinyl alcohol
It is dispersed in water, is subsequently added into alkali and carries out haptoreaction(Reaction temperature is 15 DEG C, reaction time 2h), anion is then added
Surfactant(Lauryl sodium sulfate)Carry out secondary response(Reaction temperature is 60 DEG C, reaction time 5h, trivalent iron salt,
Bismuth source, manganese source, cobalt source, polyvinyl alcohol, alkali, anion surfactant, water weight ratio be 10:0.06:2:0.5:4:8:10:
60), then system passed through into extractant(Carbon tetrachloride)It is extracted(System and the volume ratio of extractant are 1:3)And it takes organic
Phase finally removes extractant, dry obtained reaction product;
2)Reaction product is calcined(260 DEG C are warming up to 1.8 DEG C/min from 15 DEG C and keep the temperature 40min, then with 0.7 DEG C/min
It is warming up to 520 DEG C and keeps the temperature 3h)Oxidation iron-based composite A2 is made.
Embodiment 3
1)By trivalent iron salt(Ferric nitrate), bismuth source(Bismuth naphthenate), manganese source(Manganese sulfate), cobalt source(Cobalt boracylate), polyvinyl alcohol
It is dispersed in water, is subsequently added into alkali and carries out haptoreaction(Reaction temperature is 35 DEG C, reaction time 1h), anion is then added
Surfactant(Sodium tetradecyl sulfate)Carry out secondary response(Reaction temperature is 80 DEG C, reaction time 3h, trivalent iron salt,
Bismuth source, manganese source, cobalt source, polyvinyl alcohol, alkali, anion surfactant, water weight ratio be 10:0.1:3:1.5:8:12:15:
100), then system passed through into extractant(Acetone)It is extracted(System and the volume ratio of extractant are 1:5)And organic phase is taken, most
Extractant, dry obtained reaction product are removed afterwards;
2)Reaction product is calcined(300 DEG C are warming up to 2.2 DEG C/min from 35 DEG C and keep the temperature 60min, then with 1.2 DEG C/min
It is warming up to 540 DEG C and keeps the temperature 5h)Oxidation iron-based composite A3 is made.
Application examples 1
By sulfuric acid solution that above-mentioned oxidation iron-based composite, mass fraction are 10%, mass fraction be 5% boric acid solution according to
10:13:4 weight ratio mixing for 24 hours, then filters to take filter cake so that oxidation iron-based composite/sulfuric acid/boric acid composition is made.
By glyoxal and nitric acid according to 1:1.1 molar ratio carries out oxidation reaction(Reaction temperature is 41 DEG C, and the reaction time is
5h)Glyoxalic acid is made, then by glyoxalic acid, urea, oxidation iron-based composite/sulfuric acid/boric acid composition according to 1:4:0.008
Molar ratio carry out condensation reaction(Reaction temperature is 75 DEG C, reaction time 4h)Allantoin is made;Final statistics allantoin
Yield, concrete outcome is shown in Table 1;Oxidation iron-based composite/sulfuric acid/boric acid composition is not used wherein in control group, and uses
Etc. weight mass fraction be 10% sulfuric acid solution and mass fraction be 5% boric acid solution mixture(Sulfuric acid solution, boric acid
The weight ratio of solution is 13:4).
Table 1
| Catalyst | Yield(%) |
| A1/ sulfuric acid/boric acid composition | 86 |
| A2/ sulfuric acid/boric acid composition | 83 |
| A3/ sulfuric acid/boric acid composition | 85 |
| Control group | 38 |
The preferred embodiment of the present invention has been described above in detail, still, the tool during present invention is not limited to the embodiments described above
Body details can carry out a variety of simple variants, these letters to technical scheme of the present invention within the scope of the technical concept of the present invention
Monotropic type all belongs to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method preparing allantoin based on oxidation iron-based composite catalysis, which is characterized in that including:
1)Trivalent iron salt, bismuth source, manganese source, cobalt source, polyvinyl alcohol are dispersed in water, alkali is subsequently added into and carries out haptoreaction, so
Anion surfactant is added afterwards and carries out secondary response, then system is extracted to by extractant and taken organic phase, finally
Remove extractant, dry obtained reaction product;
2)The reaction product is calcined so that oxidation iron-based composite is made;
3)The oxidation iron-based composite, sulfuric acid solution, boric acid solution are mixed, then filter to take filter cake so that oxidation iron-based is made
Compound/sulfuric acid/boric acid composition;
4)Glyoxal and nitric acid are subjected to oxidation reaction so that glyoxalic acid is made, then answer glyoxalic acid, urea, the oxidation iron-based
It closes object/sulfuric acid/boric acid composition and carries out condensation reaction so that allantoin is made.
2. preparation method according to claim 1, wherein in step 1)In, the trivalent iron salt, bismuth source, manganese source, cobalt
Source, polyvinyl alcohol, alkali, anion surfactant, water weight ratio be 10:0.06-0.1:2-3:0.5-1.5:4-8:8-12:
10-15:60-100.
3. preparation method according to claim 1, wherein in step 1)In, the haptoreaction meets the following conditions:Instead
It is 15-35 DEG C to answer temperature, reaction time 1-2h.
4. preparation method according to claim 1, wherein in step 1)In, the secondary response meets the following conditions:Instead
It is 60-80 DEG C to answer temperature, reaction time 3-5h.
5. preparation method according to claim 1, wherein in step 1)In, in the extraction process, the system with
The volume ratio of extractant is 1:3-5.
6. preparation method according to claim 1, wherein in step 1)In, the trivalent iron salt is selected from ferric trichloride, sulphur
At least one of sour iron and ferric nitrate, the bismuth source are selected from least one of lauric acid bismuth, isooctyl acid bismuth and bismuth naphthenate;
The cobalt salt is selected from least one of cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate and cobalt boracylate;The manganese source is selected from nitric acid
At least one of manganese, manganese acetate, manganese sulfate.
7. preparation method according to claim 1, wherein in step 1)In, the anion surfactant is selected from ten
At least one of dialkyl benzene sulfonic acids sodium, lauryl sodium sulfate, myristyl benzene sulfonic acid sodium salt, sodium tetradecyl sulfate;
Preferably, the extractant is selected from least one of chloroform, carbon tetrachloride and acetone.
8. preparation method according to claim 1, wherein in step 2)In, the calcining is:From 15-35 DEG C with 1.8-
2.2 DEG C/min is warming up to 260-300 DEG C and keeps the temperature 40-60min, be then warming up to 520-540 DEG C with 0.7-1.2 DEG C/min and protect
Warm 3-5h.
9. preparation method according to claim 1, wherein in step 3)In, the oxidation iron-based composite, sulfuric acid
Solution, boric acid solution weight ratio be 10:10-15:3-5, and a concentration of 8-12 weight % of the sulfuric acid solution, the boron
A concentration of 3-8 weight % of acid solution;
Preferably, in step 3)Described in time for mixing be 20-30h.
10. according to the preparation method described in any one of claim 1-8, wherein in step 4)In, the glyoxal and nitre
The molar ratio of acid is 1:1.05-1.2;
Preferably, the oxidation reaction meets the following conditions:Reaction temperature is 40-42 DEG C, reaction time 4-6h;
It is highly preferred that the molar ratio of the glyoxalic acid, urea, oxidation iron-based composite/sulfuric acid/boric acid composition is 1:3-5:
0.005-0.01;
It is further preferred that the condensation reaction meets the following conditions:Reaction temperature is 70-80 DEG C, reaction time 3-5h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898376A (en) * | 2012-10-08 | 2013-01-30 | 北京桑普生物化学技术有限公司 | Allantoin synthesis method |
| CN107915682A (en) * | 2017-11-30 | 2018-04-17 | 芜湖华海生物科技股份有限公司 | The preparation method of high yield allantoin |
-
2018
- 2018-08-01 CN CN201810866333.0A patent/CN108689940A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898376A (en) * | 2012-10-08 | 2013-01-30 | 北京桑普生物化学技术有限公司 | Allantoin synthesis method |
| CN107915682A (en) * | 2017-11-30 | 2018-04-17 | 芜湖华海生物科技股份有限公司 | The preparation method of high yield allantoin |
Non-Patent Citations (3)
| Title |
|---|
| CARLOS CATIVIELA等: "Heterogeneous catalysis in the synthesis and reactivity of allantoin", 《GREEN CHEMISTRY》 * |
| 董兰芬: "固体超强酸催化合成尿囊素的研究", 《河北科技大学硕士学位论文》 * |
| 裴蕾等: "尿囊素的合成工艺", 《青岛科技大学学报(自然科学版)》 * |
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Application publication date: 20181023 |