CN101475453A - Method for preparing glyoxal by oxidizing acetaldehyde - Google Patents
Method for preparing glyoxal by oxidizing acetaldehyde Download PDFInfo
- Publication number
- CN101475453A CN101475453A CNA2009100282721A CN200910028272A CN101475453A CN 101475453 A CN101475453 A CN 101475453A CN A2009100282721 A CNA2009100282721 A CN A2009100282721A CN 200910028272 A CN200910028272 A CN 200910028272A CN 101475453 A CN101475453 A CN 101475453A
- Authority
- CN
- China
- Prior art keywords
- acetaldehyde
- selenium
- oxalic dialdehyde
- simple substance
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 38
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 title abstract description 32
- 229940015043 glyoxal Drugs 0.000 title abstract description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 55
- 239000011669 selenium Substances 0.000 claims abstract description 55
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 47
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000002829 reductive effect Effects 0.000 claims abstract description 7
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 58
- -1 tin anhydride Chemical class 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 abstract 10
- 229940000207 selenious acid Drugs 0.000 abstract 4
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- UHEQUEPSIOPIRJ-UHFFFAOYSA-N acetaldehyde;nitric acid Chemical compound CC=O.O[N+]([O-])=O UHEQUEPSIOPIRJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 2
- 229960003868 paraldehyde Drugs 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- BXUKAXFDABMVND-UHFFFAOYSA-L disodium;1,2-dihydroxyethane-1,2-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C(O)C(O)S([O-])(=O)=O BXUKAXFDABMVND-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing glyoxal by oxidizing acetaldehyde. Selenium dioxide is prepared into selenious acid aqueous solution to be used as an oxidant, the selenium dioxide selectively oxidizes acetaldehyde to generate glyoxal, and meanwhile, the selenium dioxide is reduced to elemental selenium to be separated out; separating the reaction product to obtain glyoxal solution and elemental selenium; the elemental selenium separated out by the oxidation of hydrogen peroxide is selenium dioxide to generate selenious acid solution which is returned to be used for preparing glyoxal by oxidizing acetaldehyde. Or using commercially available solid selenium as a raw material, firstly oxidizing elemental selenium by hydrogen peroxide to prepare selenium dioxide, oxidizing acetaldehyde by using the prepared selenious acid solution to prepare glyoxal, and then recycling the selenium. Under the optimized condition, the yield and the selectivity of the glyoxal and the yield of the selenious acid are both more than 85 percent. The preparation method of glyoxal has the advantages of mild reaction conditions, high selectivity and yield, and wide industrial application prospect, and selenium can be recycled in a system.
Description
Technical field:
The present invention relates to a kind of oxidizing acetaldehyde prepare oxalic dialdehyde method, relate in particular to the tin anhydride oxidizing acetaldehyde and prepare oxalic dialdehyde and two kinds of technology bonded of hydrogen peroxide oxidation simple substance selenium system tin anhydride method.Belong to the chemical process technology field in the chemical industry.
Background technology
Oxalic dialdehyde is the simplest binary aliphatic aldehyde of molecular structure, except that the general character with alkanoic, also has some special chemical property, is a kind of important chemical material and intermediate, is widely used in fields such as weaving, medicine, metallurgy, environmental protection.Industrial main employing ethylene glycol air oxidation process and acetaldehyde nitric acid oxidation method are produced oxalic dialdehyde.Wherein, ethylene glycol air oxidation process process is simple, and product yield is higher, but raw materials cost is higher relatively, and contains more formaldehyde in the product, is difficult to satisfy the specification of quality of industries such as medicine; Acetaldehyde nitric acid oxidation method material cost is low, and the reaction conditions gentleness does not contain formaldehyde in the product, but selectivity is relatively poor, yield lower (30%～40%), a large amount of acetic acid of by-product, and separation and processing are comparatively complicated, and " three wastes " problems such as NOx pollution are arranged.
The oxalic dialdehyde production level of China is compared with external advanced production level, all there is certain distance at aspects such as industrial scale, quality product and output, the market competitiveness a little less than, the present most of dependence on import of the oxalic dialdehyde of high quality (not containing formaldehyde) on the domestic market.Therefore, the research and development of acceleration production oxalic dialdehyde novel process and new technology, raising China produce the oxalic dialdehyde level and quality product is that China produces the current top priority of oxalic dialdehyde industry.
Tin anhydride has stronger selective oxidation effect to carbonyl adjacent methyl and methylene radical, can be used for allylic oxidation, Riley oxidizing reaction, pimelinketone oxidation system 1, organic reactions such as 2-cyclohexanedione.People (Ronzio R. such as Ronzio R., Waugh T.D.Glyoxal Bisulfite.Organic syntheses, 1944,24:61.) reported tin anhydride oxidation paraldehyde system oxalic dialdehyde experimental result, in hot water bath, the mol ratio of tin anhydride and paraldehyde is 1.2:1, is solvent with the dioxane, reacted 6 hours, oxalic dialdehyde yield be about 63% (in the tin anhydride mole).But not seeing has follow-up report, does not also see industrial applications.This technological process oxalic dialdehyde yield is apparently higher than the acetaldehyde nitric acid oxidation method, but the oxygenant of its use and solvent price are all than higher, particularly use tin anhydride as oxygenant, tin anhydride is reduced into simple substance selenium in oxidation reaction process, this simple substance selenium is not recycled, the oxalic dialdehyde product cost is too high, and is uneconomical.Therefore, if manage to recycle reductive simple substance selenium in the reaction process, and use cheap solvent, can utilize the selective oxidation performance of tin anhydride to the methyl of acetaldehyde, the oxidizing acetaldehyde that exploitation has industrial application value prepares the oxalic dialdehyde novel process.
At present, the method of studying more recovery selenium generation tin anhydride is concentrated nitric acid or vitriol oil oxidation style, as Wang Jinling (Wang Jinling, Liu Dengcai. the oxidation utilization of trade waste selenium. environmental science and management, 2006,31 (6): 82,109.) be raw material with the selenium that generates in the building-up reactions, mixture with the concentrated nitric acid and the vitriol oil carries out oxidizing reaction, and it is oxidized to can reusable tin anhydride, and yield is 94%.Yet concentrated nitric acid and vitriol oil corrodibility are stronger, and the NO that generates in oxidising process, NO
2And SO
2Can pollute environment.
Hydrogen peroxide is a kind of green oxidation agent, and reduzate is a water, and product separates easily, and is nontoxic, pollution-free.If generate tin anhydride with hydrogen peroxide oxidation simple substance selenium, use it for oxidizing acetaldehyde system glyoxal reaction, can realize that tin anhydride recycles intrasystem, for oxidizing acetaldehyde prepare oxalic dialdehyde new process development solved key issue.
Summary of the invention
The objective of the invention is provides the preparation of biformyl by oxidizing acetaldehyde of a kind of high yield, highly selective in order to improve low, the high deficiency of cost of oxalic dialdehyde yield that existing acetaldehyde nitric acid oxidation law technology exists.With water is solvent, prepares oxalic dialdehyde and hydrogen peroxide oxidation simple substance selenium by the tin anhydride oxidizing acetaldehyde and prepares two technological processs of tin anhydride and organically combine, realize oxidizing acetaldehyde that selenium recycles in system prepare oxalic dialdehyde method.
The technical solution used in the present invention is as follows: a kind of oxidizing acetaldehyde prepare oxalic dialdehyde method, its concrete steps are:
A, with the tin anhydride is raw material, it is dissolved in suitable quantity of water, and to be formulated as concentration expressed in percentage by weight be 5%～40% selenous acid solution, in being connected to the reactor R1 of condensing works and device for absorbing tail gas, adding is (0.4～6) with the mol ratio of tin anhydride: 1 concentration expressed in percentage by weight is 40%～99% acetaldehyde solution, stir, drip selenous acid solution, under 5～85 ℃, reacted 0.5～12 hour, tin anhydride selective oxidation acetaldehyde prepares oxalic dialdehyde, and simultaneously, tin anhydride is reduced to solid simple substance selenium, obtain oxalic dialdehyde product solution and simple substance selenium after the solid-liquid separation respectively, oxalic dialdehyde product solution obtains the oxalic dialdehyde product through separation system;
B, with in the steps A reaction gained solid simple substance selenium place reactor R2, add suitable quantity of water (can fully stir and get final product), stir, add concentration expressed in percentage by weight and be 20%～70% hydrogen peroxide solution and carry out oxidizing reaction, the mol ratio of hydrogen peroxide and simple substance selenium is (0.1～5.0): 1, temperature of reaction is 5～70 ℃, reaction times is 1～36 hour, generation contains the aqueous solution of tin anhydride, be selenous acid solution, this selenous acid solution returns the tin anhydride oxidizing acetaldehyde that is used for steps A and prepares the oxalic dialdehyde process;
Perhaps concrete steps are:
A1, be raw material with solid simple substance selenium, in reactor R2, the described method of B with its oxidation, makes selenous acid solution with hydrogen peroxide set by step;
B1, in reactor R1, steps A 1 prepared selenous acid solution is prepared oxalic dialdehyde according to the described method oxidizing acetaldehyde of steps A, simultaneously, tin anhydride is reduced to solid simple substance selenium, obtains the oxalic dialdehyde product through separation system; This simple substance selenium returns the hydrogen peroxide oxidation simple substance selenium that is used for steps A 1 and prepares the tin anhydride process.
The mol ratio of acetaldehyde and tin anhydride is (0.5～2.0) among preferred above-mentioned steps A and the B1: 1; Selenous acid is concentration expressed in percentage by weight 10%～35% aqueous solution; Temperature of reaction is 30～70 ℃; Reaction times is 1～8 hour.
The mol ratio of hydrogen peroxide and simple substance selenium is (0.5～3.0) among preferred steps B and the A1: 1; Temperature of reaction is 10～65 ℃; Reaction times is 2～12 hours.
Separation system is separated when obtaining the oxalic dialdehyde product, also obtains unreacted acetaldehyde and selenous acid reaction solution, and acetaldehyde that the preferable separation system is separating obtained and selenous acid reaction solution Returning reactor R1 recycle.Separation system described in the present invention comprises operations such as distillation, ion-exchange, reduction vaporization, activated carbon decolorizing.
In conjunction with the accompanying drawings preparation technology of the present invention is described in detail:
With commercially available tin anhydride is initial feed, and technical scheme is as follows: the first step, and carry out the tin anhydride oxidizing acetaldehyde and prepare the oxalic dialdehyde process, separate out simple substance selenium simultaneously; In second step, the simple substance selenium of separating out with hydrogen peroxide oxidation the first step process prepares tin anhydride; The 3rd goes on foot, and second tin anhydride that goes on foot preparation is returned be used for the first step reaction process.Be prepared oxalic dialdehyde process, preparation tin anhydride process then successively, so circulation, idiographic flow is seen accompanying drawing 1.
With commercially available solid selenium is initial feed, and technical scheme is as follows: the first step, and carry out hydrogen peroxide oxidation simple substance selenium and prepare the tin anhydride process; Second step, utilize the tin anhydride oxidizing acetaldehyde of the first step preparation to prepare oxalic dialdehyde, separate out simple substance selenium simultaneously; In the 3rd step, the second step simple substance selenium of separating out is returned the first step be used to prepare tin anhydride.Be prepared oxalic dialdehyde process, preparation tin anhydride process then successively, so circulation, idiographic flow is seen accompanying drawing 2.
Beneficial effect:
Provided by the present invention recycle the tin anhydride oxidizing acetaldehyde prepare oxalic dialdehyde novel process, be that a kind of equipment is simple, easy to operate, energy consumption is low, be rich in the vanguard technology of characteristics such as the market competitiveness.Employing can the selective oxidation methyl tin anhydride be oxygenant, with water solvent, the reaction conditions gentleness, oxalic dialdehyde yield and selectivity are more than 85%; The agent of employing green oxidation---hydrogen peroxide oxidation prepares the selenium that glyoxal reaction is separated out, and it is recycled; The reactive system solution circulated is used.Oxidizing acetaldehyde provided by the invention prepare oxalic dialdehyde technology have efficiently, the economic dispatch characteristics, for promote China produce high quality oxalic dialdehyde product technology level, promote China's oxalic dialdehyde production technique to international most advanced level stride forward, improve the business economic benefit and the market competitiveness significant.
Description of drawings
Accompanying drawing 1 is that the oxidizing acetaldehyde of initial feed prepares the oxalic dialdehyde process flow diagram with the tin anhydride.
Accompanying drawing 2 is that the oxidizing acetaldehyde of initial feed prepares the oxalic dialdehyde process flow diagram with solid selenium.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment, so that therefore the understanding of the present invention does not limit the present invention.
[embodiment 1]
12.6g tin anhydride (commercially available) is water-soluble, and being made into concentration expressed in percentage by weight is 20% selenous acid solution; The adding concentration expressed in percentage by weight is 40% acetaldehyde solution 10g in reactor R1, stir, drip selenous acid solution, under 65 ℃ of temperature, reacted 4 hours, tin anhydride selective oxidation acetaldehyde generates the oxalic dialdehyde product through solid-liquid separation, obtain liquid product solution and solid simple substance selenium respectively, analyze the liquid phase product component, getting the oxalic dialdehyde yield is 85.86%, and selectivity is 86.15%.
[embodiment 2]
The simple substance selenium of embodiment 1 gained is added among the reactor R2, add water, fully stir, drip concentration expressed in percentage by weight then and be 30% hydrogen peroxide solution, oxidation simple substance selenium is tin anhydride, generates the aqueous solution of tin anhydride, i.e. selenous acid solution.Mol ratio at hydrogen peroxide and selenium is under 1: 1, the 25 ℃ conditions, reacts 4 hours, and the selenous acid yield is 88.65%.
[embodiment 3]
The selenous acid solution Returning reactor R1 of embodiment 2 gained is carried out oxidizing acetaldehyde prepare glyoxal reaction, condition is with embodiment 1, the oxalic dialdehyde yield be 84.92%, selectivity is 86.03%.
[embodiment 4]
15g tin anhydride (commercially available) is water-soluble, and being made into concentration expressed in percentage by weight is 40% selenous acid solution; The adding concentration expressed in percentage by weight is 60% acetaldehyde solution 6.5g in reactor R1, stir, drip selenous acid solution, under 55 ℃ of temperature, reacted 5 hours, tin anhydride selective oxidation acetaldehyde prepares the glyoxal reaction product through solid-liquid separation, obtain liquid product solution and solid simple substance selenium respectively, analyze the liquid phase product component, getting the oxalic dialdehyde yield is 90.79%, and selectivity is 90.95%.
[embodiment 5]
The simple substance selenium of embodiment 4 gained is added among the reactor R2, add water, fully stir, drip concentration expressed in percentage by weight then and be 40% hydrogen peroxide solution, mol ratio at hydrogen peroxide and selenium is under 0.9: 1, the 20 ℃ conditions, reacts 8 hours, and oxidation simple substance selenium generates the aqueous solution of tin anhydride, be selenous acid solution, yield is 90.65%.
[embodiment 6]
The selenous acid solution Returning reactor R1 of embodiment 5 gained is carried out oxidizing acetaldehyde prepare glyoxal reaction, condition is with embodiment 4, the oxalic dialdehyde yield be 89.56%, selectivity is 90.10%.
[embodiment 7]
15.5g tin anhydride (commercially available) is water-soluble, and being made into concentration expressed in percentage by weight is 25% selenous acid solution; The adding concentration expressed in percentage by weight is 99% acetaldehyde solution 5g in reactor R1, stir, drip selenous acid solution, under 35 ℃ of temperature, reacted 2 hours, tin anhydride selective oxidation acetaldehyde prepares the oxalic dialdehyde product through solid-liquid separation, obtain liquid product solution and solid simple substance selenium respectively, analyze the liquid phase product component, getting the oxalic dialdehyde yield is 87.40%, and selectivity is 88.58%.
[embodiment 8]
The simple substance selenium of embodiment 7 gained is added among the reactor R2, add water, fully stir, drip concentration expressed in percentage by weight then and be 60% hydrogen peroxide solution, mol ratio at hydrogen peroxide and selenium is under 0.9: 1, the 40 ℃ conditions, reacts 3 hours, and oxidation simple substance selenium generates the aqueous solution of tin anhydride, be selenous acid solution, yield is 90.15%.
[embodiment 9]
The selenous acid solution Returning reactor R1 of embodiment 8 gained is carried out oxidizing acetaldehyde prepare glyoxal reaction, condition is with embodiment 7, the oxalic dialdehyde yield be 86.82%, selectivity is 88.75%.
[embodiment 10]
Being 70% hydrogen peroxide solution oxidation with concentration expressed in percentage by weight prepares selenous acid by the simple substance selenium of embodiment 1 gained, and method and condition be with embodiment 2, the selenous acid yield be 90.59%.
[embodiment 11]
Getting the commercially available solid selenium of 10g, is that 30% hydrogen peroxide prepares selenous acid solution with its oxidation with concentration expressed in percentage by weight, and method and condition are with embodiment 2; Mol ratio at hydrogen peroxide and selenium is under 1: 1, the 35 ℃ conditions, reacts 5 hours, and the selenous acid yield is 89.52%.
[embodiment 12]
Carry out oxidizing acetaldehyde with the selenous acid solution of embodiment 11 gained and prepare glyoxal reaction, get concentration expressed in percentage by weight and be 80% acetaldehyde solution 5g, additive method, step are with embodiment 1; Under 10 ℃ of conditions, reacted 12 hours, the oxalic dialdehyde yield is 90.24%, selectivity is 89.32%.
[embodiment 13]
Simple substance selenium with embodiment 12 gained prepares selenous acid, and reaction conditions is with embodiment 11, and getting the selenous acid yield is 91.94%.
Claims (4)
1, a kind of oxidizing acetaldehyde prepare oxalic dialdehyde method, its concrete steps are:
A, with the tin anhydride is raw material, with its water-soluble concentration expressed in percentage by weight that is formulated as is 5%～40% selenous acid solution, in being connected to the reactor R1 of condensing works and device for absorbing tail gas, the adding concentration expressed in percentage by weight is 40%～99% acetaldehyde solution, wherein the mol ratio of acetaldehyde and tin anhydride is (0.4～6): 1, stir, under 5～85 ℃, reacted 0.5～12 hour, tin anhydride selective oxidation acetaldehyde prepares oxalic dialdehyde, and simultaneously, tin anhydride is reduced to simple substance selenium, reaction solution obtains oxalic dialdehyde product solution and solid simple substance selenium respectively through solid-liquid separation, and oxalic dialdehyde product solution obtains the oxalic dialdehyde product through separation system;
B, with in the steps A reaction gained solid simple substance selenium place reactor R2, adding entry stirs, add concentration expressed in percentage by weight and be 20%～70% hydrogen peroxide solution and carry out oxidizing reaction, the mol ratio of hydrogen peroxide and simple substance selenium is (0.1～5.0): 1, temperature of reaction is 5～70 ℃, 1～36 hour reaction times generated selenous acid solution, and this selenous acid solution returns the tin anhydride oxidizing acetaldehyde that is used for steps A and prepares the oxalic dialdehyde process;
Perhaps concrete steps are:
A1, be raw material with solid simple substance selenium, in reactor R2, the described method of B with its oxidation, makes selenous acid solution with hydrogen peroxide set by step;
B1, in reactor R1, steps A 1 prepared selenous acid solution is prepared oxalic dialdehyde according to the described method oxidizing acetaldehyde of steps A, simultaneously, tin anhydride is reduced to simple substance solid selenium, obtains the oxalic dialdehyde product through separation system; This simple substance selenium returns the hydrogen peroxide oxidation simple substance selenium that is used for steps A 1 and prepares the tin anhydride process.
2, according to the described oxidizing acetaldehyde of claim 1 prepare oxalic dialdehyde method, it is characterized in that the mol ratio of acetaldehyde and tin anhydride among steps A and the B1 is (0.5～2.0): 1; The concentration expressed in percentage by weight of the selenous acid aqueous solution is 10%～35%; Temperature of reaction is 30～70 ℃; Reaction times is 1～8 hour.
3, according to the described oxidizing acetaldehyde of claim 1 prepare oxalic dialdehyde method, it is characterized in that the mol ratio of hydrogen peroxide and simple substance selenium among step B and the A1 is (0.5～3.0): 1; Temperature of reaction is 10～65 ℃; Reaction times is 2～12 hours.
4, according to the described oxidizing acetaldehyde of claim 1 prepare oxalic dialdehyde method, it is characterized in that acetaldehyde and selenous acid reaction solution Returning reactor R1 that separation system is separating obtained recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100282721A CN101475453B (en) | 2009-02-05 | 2009-02-05 | Method for preparing glyoxal by oxidizing acetaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100282721A CN101475453B (en) | 2009-02-05 | 2009-02-05 | Method for preparing glyoxal by oxidizing acetaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475453A true CN101475453A (en) | 2009-07-08 |
| CN101475453B CN101475453B (en) | 2012-05-30 |
Family
ID=40836244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100282721A Expired - Fee Related CN101475453B (en) | 2009-02-05 | 2009-02-05 | Method for preparing glyoxal by oxidizing acetaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101475453B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653733B (en) * | 2009-08-28 | 2012-02-22 | 中国石油化工股份有限公司 | Catalyst for preparing glyoxal by oxidizing aldehyde and preparation method thereof |
| CN104892403A (en) * | 2015-06-08 | 2015-09-09 | 扬州大学 | Synthetic method of benzoic anhydride |
| CN111969194A (en) * | 2020-08-27 | 2020-11-20 | 广东工业大学 | Battery positive electrode material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB376306A (en) * | 1931-04-08 | 1932-07-08 | Ici Ltd | Oxidation of ethylenic compounds |
-
2009
- 2009-02-05 CN CN2009100282721A patent/CN101475453B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653733B (en) * | 2009-08-28 | 2012-02-22 | 中国石油化工股份有限公司 | Catalyst for preparing glyoxal by oxidizing aldehyde and preparation method thereof |
| CN104892403A (en) * | 2015-06-08 | 2015-09-09 | 扬州大学 | Synthetic method of benzoic anhydride |
| CN111969194A (en) * | 2020-08-27 | 2020-11-20 | 广东工业大学 | Battery positive electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475453B (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102336643B (en) | Process for synthesizing benzoquinones by direct oxidation of phenols | |
| CN108276364A (en) | A kind of preparation and application of porous hexa metaphosphoric acid Zr catalyst | |
| CN101475453B (en) | Method for preparing glyoxal by oxidizing acetaldehyde | |
| CN104817520B (en) | Method for preparing cyclohexene oxide by adopting micro-flow field reaction technology | |
| CN103553004A (en) | Method for continuous preparation of sodium azide | |
| CN100586922C (en) | Preparation method of acrylic acid | |
| CN101863738B (en) | Method for preparing neopentyl glycol | |
| CN105348189A (en) | Continuous 2,2,4-trimethyl-1,2-dihydroquinoline preparation method | |
| CN102311420B (en) | Method for synthesizing epsilon-caprolactone | |
| CN102167686A (en) | Method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen | |
| CN102643185A (en) | Green and simple preparation method for 2,3,5-trimethylbenzoquinone (TMBQ) | |
| CN101519415A (en) | Liquid-phase catalytic oxidation cycle method for preparing humic acid from coal residue | |
| CN102924282A (en) | Process for producing alkyl nitrite | |
| CN102503801A (en) | Method for producing formic acid from glycerol by hydrothermal oxidation | |
| CN103304838B (en) | Extraction method for recycling and reusing waste liquid from production of polyaniline by electrochemical process | |
| CN103030699A (en) | Preparation method of canna edulis ker oxidized starch | |
| CN105566278A (en) | Method for continuously preparing caprolactone by using micro-reaction device | |
| CN101898953A (en) | Technological research for producing sodium acetate by comprehensively utilizing chemical waste liquid | |
| CN104803951A (en) | Method for preparing high-quality epoxy cyclohexane by adopting micro-flow field reaction technology | |
| CN101148406B (en) | Method for preparing carboxylic acid ester by using aldehyde, alcohol and oxidizing agent as raw material | |
| CN106748678A (en) | The process unit and method of a kind of highly concentrated Formaldehyde Production and gaseous formaldehyde method polymethoxy dimethyl ether Joint Production | |
| CN102617309A (en) | Process for preparing acetaldehyde | |
| Cooper et al. | Destruction of organic wastes by ammonium peroxydisulfate with electrolytic regeneration of the oxidant | |
| Zeng et al. | Production of formic acid and acetic acid by hydrothermal oxidation of alkali lignin | |
| CN103351366B (en) | Method for continuous production of epoxy chloropropane through reaction-separation coupling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120530 Termination date: 20150205 |
|
| EXPY | Termination of patent right or utility model |