CN101475453B - Method for preparing glyoxal by oxidizing acetaldehyde - Google Patents
Method for preparing glyoxal by oxidizing acetaldehyde Download PDFInfo
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- CN101475453B CN101475453B CN2009100282721A CN200910028272A CN101475453B CN 101475453 B CN101475453 B CN 101475453B CN 2009100282721 A CN2009100282721 A CN 2009100282721A CN 200910028272 A CN200910028272 A CN 200910028272A CN 101475453 B CN101475453 B CN 101475453B
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- acetaldehyde
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- oxalic dialdehyde
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 43
- 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 60
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 56
- 239000011669 selenium Substances 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 50
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 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 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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 57
- 239000000126 substance Substances 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 150000002978 peroxides Chemical class 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 7
- 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
- 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
- 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
- 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
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- 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 with 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 particular chemical character, is a kind of important chemical material and midbody, is widely used in fields such as weaving, medicine, metallurgy, environmental protection.Main terepthaloyl moietie air oxidation process and the acetaldehyde nitric acid oxidation method of adopting produced oxalic dialdehyde in the industry.Wherein, terepthaloyl moietie 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 reaction conditions is gentle, do 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 home 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., Waugh T.D.Glyoxal Bisulfite.Organic syntheses, 1944 such as Ronzio R.; 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, and 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, tin anhydride promptly capable of using is to the selective oxidation performance of the methyl of acetaldehyde, and the oxidizing acetaldehyde that exploitation has industrial application value prepares the oxalic dialdehyde novel process.
At present, the method for studying more recovery selenium generation tin anhydride is concentrated nitric acid or vitriol oil oxidation style, like 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 in oxidising process, generates, NO
2And SO
2Can pollute environment.
Ydrogen peroxide 50 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 through the tin anhydride oxidizing acetaldehyde and prepares two technological processs of tin anhydride with hydrogen peroxide oxidation simple substance selenium and organically combine, realize oxidizing acetaldehyde that selenium recycles in system prepare oxalic dialdehyde method.
The technical scheme that the present invention adopts is following: a kind of oxidizing acetaldehyde prepare oxalic dialdehyde method, its concrete steps are:
A, be raw material with the tin anhydride, 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 drum 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, stirs, and drips selenous acid solution; Under 5～85 ℃, reacted 0.5～12 hour, tin anhydride selective oxidation acetaldehyde prepares oxalic dialdehyde; Simultaneously; Tin anhydride is reduced to solid simple substance selenium, obtains oxalic dialdehyde product solution and simple substance selenium after the solid-liquid separation respectively, 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 drum 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 ydrogen peroxide 50 and simple substance selenium is (0.1～5.0): 1, and temperature of reaction is 5～70 ℃; Reaction times is 1～36 hour; Generation contains the aqueous solution of tin anhydride, i.e. 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 drum R2, the described method of B with its oxidation, makes selenous acid solution with ydrogen peroxide 50 set by step;
B1, in reactor drum 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 ydrogen peroxide 50 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 preferably 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, IX, reduction vaporization, activated carbon decolorizing.
In conjunction with accompanying drawing preparation technology of the present invention is done detailed introduction:
With commercially available tin anhydride is initial feed, and technical scheme is following: 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; In the 3rd step, the tin anhydride of the second step preparation returned be used for the first step reaction process.Prepare 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 following: 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.Prepare 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, reaction conditions is gentle, 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
Below in conjunction with specific embodiment the present invention is further described, so that, therefore do not limit the present invention understanding of 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 drum R1, stirs, and drips 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 drum 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 ydrogen peroxide 50 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 drum R1, stirs, and drips 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 drum R2, add water, fully stir; Drip concentration expressed in percentage by weight then and be 40% hydrogen peroxide solution; Mol ratio at ydrogen peroxide 50 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 drum R1, stirs, and drips 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 drum R2, add water, fully stir; Drip concentration expressed in percentage by weight then and be 60% hydrogen peroxide solution; Mol ratio at ydrogen peroxide 50 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]
To use concentration expressed in percentage by weight be 70% hydrogen peroxide solution oxidation prepares selenous acid by the simple substance selenium of embodiment 1 gained, and method and condition must the selenous acid yield be 90.59% with embodiment 2.
[embodiment 11]
Get the commercially available solid selenium of 10g, using concentration expressed in percentage by weight is that 30% ydrogen peroxide 50 prepares selenous acid solution with its oxidation, and method and condition are with embodiment 2; Mol ratio at ydrogen peroxide 50 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)
- An oxidizing acetaldehyde prepare oxalic dialdehyde method, its concrete steps are:A, being raw material with the tin anhydride, is 5%～40% selenous acid solution with its water-soluble concentration expressed in percentage by weight that is formulated as, in being connected to the reactor drum R1 of condensing works and device for absorbing tail gas; The adding concentration expressed in percentage by weight is 40%～99% acetaldehyde solution, and wherein the mol ratio of acetaldehyde and tin anhydride is (0.4～6): 1, stir; In acetaldehyde solution, drip selenous acid solution; Under 5～85 ℃, reacted 0.5～12 hour, tin anhydride selective oxidation acetaldehyde prepares oxalic dialdehyde; Simultaneously; Tin anhydride is reduced to simple substance selenium, and 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 drum R2; Add entry and stir, add concentration expressed in percentage by weight and be 20%～70% hydrogen peroxide solution and carry out oxidizing reaction, the mol ratio of ydrogen peroxide 50 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 drum R2, add entry and stir, add concentration expressed in percentage by weight and be 20%～70% hydrogen peroxide solution and carry out oxidizing reaction; The mol ratio of ydrogen peroxide 50 and simple substance selenium is (0.1～5.0): 1; Temperature of reaction is 5～70 ℃, in 1～36 hour reaction times, makes selenous acid solution;B1, in reactor drum R1, add concentration expressed in percentage by weight and be 40%～99% acetaldehyde solution, wherein the mol ratio of acetaldehyde and tin anhydride is (0.4～6): 1; Stir, in acetaldehyde solution, drip steps A 1 prepared selenous acid solution, under 5～85 ℃; Reacted 0.5～12 hour, tin anhydride selective oxidation acetaldehyde prepares oxalic dialdehyde, 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.
- 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.
- According to the described oxidizing acetaldehyde of claim 1 prepare oxalic dialdehyde method, it is characterized in that the mol ratio of ydrogen peroxide 50 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.
- 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.
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|---|---|---|---|---|
| US1999576A (en) * | 1931-04-08 | 1935-04-30 | Ici Ltd | Production of glyoxals |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1999576A (en) * | 1931-04-08 | 1935-04-30 | Ici Ltd | Production of glyoxals |
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