USRE23001E - Oxidation of acrolein to - Google Patents
Oxidation of acrolein to Download PDFInfo
- Publication number
- USRE23001E USRE23001E US23001DE USRE23001E US RE23001 E USRE23001 E US RE23001E US 23001D E US23001D E US 23001DE US RE23001 E USRE23001 E US RE23001E
- Authority
- US
- United States
- Prior art keywords
- acrolein
- oxidation
- acrylic acid
- acid
- oxygen
- 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.)
- Expired
Links
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title description 15
- 238000007254 oxidation reaction Methods 0.000 title description 15
- 230000003647 oxidation Effects 0.000 title description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N Mercury(II) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- JJCFRYNCJDLXIK-UHFFFAOYSA-N Cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N Sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
Definitions
- This invention is for improvements in or relating to the oxidation of acrolein to acrylic acid.
- the oxidation of acrolein is carried out by reaction with molecular oxygen, that is oxygen itself, or gases containing oxygen, in the presence of the acidic compounds of vanadium such as vanadic acid.
- molecular oxygen that is oxygen itself, or gases containing oxygen
- the catalyst is prelerably freshly prepared from the corresponding salts by hydrolysis or by the action of acids.
- vanadic acid as catalyst not only considerably reduces the reaction time, but also permits the use oi lower temperatures than has been possible hitherto with a consequent diminution in the tendency to polymerisation.
- the tempenature should preferably not be allowed to exceed 45 C. during the oxidationand generally speaking-a temperature of 20-30 C. will beiound to give most satisfactory results. Though the solution contains a considerable amount of peracid and peroxide the monomeric acrylic acid is obtained in very good yields. 1
- the oxidation may be carried out in the presence of solvents preferably water-miscible solvents such as the lower organic acids, e. g., acetic acid or acrylic acid, alcohols or -ketones. It is also possible to carry out the oxidation in the presence of water and a satisfactory method of operation is to use the catalyst, e. g., vanadic acid, in the form oi! its aqueous solution or suspension. It is possible according to the process of the present invention to carry the-oxidation substantially to completion, without undue polymerisation taking place.
- solvents preferably water-miscible solvents such as the lower organic acids, e. g., acetic acid or acrylic acid, alcohols or -ketones.
- the catalyst e. g., vanadic acid
- the oxidation is normally carried out at ordinary pressure but, if desirable, increased pressure may be treated with acetylene in the presence of suitable catalysts, 'such as mercuric oxide, and the acrylic acid converted directly into vinyl acrylate. Alternatively, the reaction mixture may be treated with an'alcohol and an esterification catalyst. Yet another method is to cause esterification of the acrylic acid to take place simultaneously with the oxidation by carrying out the oxidation in the presence of an alcohol. If in the latter process the temperature is maintained at a low level. the formation of acroiein acetal can be substantially avoided.
- the process is applicable not only to the oxidation or acrolein but also to the oxidation oi achloro-acrolein.
- Example 1 Oxygen was introduced into '40 grams of acrolein dissolved in 50 grams of acetic acid containing 4 cc. of a 1% solution oi! freshly prepared vanadic acid in water. The oxygen is introduced 32 grams of acrolein were dissolved in 40 cc.-
- Example 3 A mixture containing 50 grams absolute alcohol, 43 grams acrolein, 5 cc. acetic acid and i 2 cc. of a 1% aqueous vanadic acid solution was treated with oxygen at about 30 C. After a short induction period the absorption of oxygen increased so markedly that intensive cooling was necessary. The reactin product contained 32% acrylic acid and 62% of ethyl acrylate. No polymerisation was observed.
- Example 4 The voluminous precipitate obtained by heating sodium-vanadate with acetic acid was redispersed in acetic acid and added to an acetic acid solution containing 40% by weight of acrolein. This solution was oxidised at 10 C. by
- Example 5 A 40% solution of acrolein in xylene was oxidised for 5 hours at 32 C. in the presence of a catalyst, made by heating solid vanadium pentoxide which is dispersed in acetic acid with small amounts of hydrogen peroxideI so that the solid vanadium pentoxide partially dissolves. By adding the calculated amount of acetic anhydride the water in the catalyst solution is removed. The yield of monomeric acrylic acid was 92%.
- a process for the manufacture of acrylic acid which comprises treating acrolein in solu-- tion in a water-soluble carboxylic acid havin no more than three carbon atoms with an oxygencontaining gas in the presence of a catalyst comprising an. aqueous solution of vanadic acid at a temperature not exceeding 45 reaction product containing monomeric acrylic acid and peroxidic compounds.
- a process for the manufacture of acrylic acid comprising treating acroiein in presence oi acetic acid with an oxygen-containing gas in the presence of a catalyst comprising an aqueous solution of vanadic acid at a temperature not exceeding 45 C. to produce a. reaction product containing monomeric acrylic acid and peroxidic compounds.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Reissueii May 18, 1948 OXIDATION OF ACROLEIN T ACRYLIC ACID Hanna Peter Staudinger, Ewell, and Karl Heinrich Walter Tuerck, Banstead, England, asslgn- V ore to The Distillers Company Limited, Edinburgh, Scotland, at British company No Drawing.
Original No. 2,341,339, dated February 8, 1944, Serial No. 411,758, September 20,
1941. Application for reissue February 12,
1946, Serial No. 647,186. In Great Britain September 21, 1940 4 Claims. 1
This invention is for improvements in or relating to the oxidation of acrolein to acrylic acid.
Several processes for oxidising acrolein to acrylic acid have been described in theliterature, but all these processes have suilered from the factthat the oxidation, as hitherto practised, has been slow and polymerisation of both the acrolein and the acrylic acid produced by the process takes place at a rapid rate. This poly: merisation is thought to be due either to the prolonged action oi! the oxygen itself, or more probably to the action of per compounds formed as intermediate compounds during the reaction.
According to the present invention, the oxidation of acrolein is carried out by reaction with molecular oxygen, that is oxygen itself, or gases containing oxygen, in the presence of the acidic compounds of vanadium such as vanadic acid. The catalyst is prelerably freshly prepared from the corresponding salts by hydrolysis or by the action of acids.
The use of vanadic acid as catalyst not only considerably reduces the reaction time, but also permits the use oi lower temperatures than has been possible hitherto with a consequent diminution in the tendency to polymerisation. The tempenature should preferably not be allowed to exceed 45 C. during the oxidationand generally speaking-a temperature of 20-30 C. will beiound to give most satisfactory results. Though the solution contains a considerable amount of peracid and peroxide the monomeric acrylic acid is obtained in very good yields. 1
, The oxidation may be carried out in the presence of solvents preferably water-miscible solvents such as the lower organic acids, e. g., acetic acid or acrylic acid, alcohols or -ketones. It is also possible to carry out the oxidation in the presence of water and a satisfactory method of operation is to use the catalyst, e. g., vanadic acid, in the form oi! its aqueous solution or suspension. It is possible according to the process of the present invention to carry the-oxidation substantially to completion, without undue polymerisation taking place.
We have round that polymerisation oi the unsaturated acid produced by the process can be prevented during the recovery or the product by the use 0! substances which decompose the formed peroxides which promote polymerisation. An example oi such a substance is. sulphur dioxide, As the rate of oxidation is high the process may be carried out in a continuous manner. also possible to carry out the oxidation under such condition that the acid anhydride is termed.
. The oxidation is normally carried out at ordinary pressure but, if desirable, increased pressure may be treated with acetylene in the presence of suitable catalysts, 'such as mercuric oxide, and the acrylic acid converted directly into vinyl acrylate. Alternatively, the reaction mixture may be treated with an'alcohol and an esterification catalyst. Yet another method is to cause esterification of the acrylic acid to take place simultaneously with the oxidation by carrying out the oxidation in the presence of an alcohol. If in the latter process the temperature is maintained at a low level. the formation of acroiein acetal can be substantially avoided.
The process is applicable not only to the oxidation or acrolein but also to the oxidation oi achloro-acrolein.
The following examples illustrate the manner in which the invention is carried into effect in the production of acrylic acid.
Example 1 Oxygen was introduced into '40 grams of acrolein dissolved in 50 grams of acetic acid containing 4 cc. of a 1% solution oi! freshly prepared vanadic acid in water. The oxygen is introduced 32 grams of acrolein were dissolved in 40 cc.-
oi' acetoneand 5 cc. of acetic acid. The solution was then treated with oxygen in the presence of 2 cc. of a 1% aqueous vanadic' acid solution at 30 C. Alter five hours 64% of the acrolein was oxidised to acrylic acid while 30% remained lachanged. No polymerisation was observed.
Example 3 A mixture containing 50 grams absolute alcohol, 43 grams acrolein, 5 cc. acetic acid and i 2 cc. of a 1% aqueous vanadic acid solution was treated with oxygen at about 30 C. After a short induction period the absorption of oxygen increased so markedly that intensive cooling was necessary. The reactin product contained 32% acrylic acid and 62% of ethyl acrylate. No polymerisation was observed.
Example 4 The voluminous precipitate obtained by heating sodium-vanadate with acetic acid was redispersed in acetic acid and added to an acetic acid solution containing 40% by weight of acrolein. This solution was oxidised at 10 C. by
passing in oxygen under a pressure of 1300 mm. Hg. The yield of monomeric acrylic acid was 93.2%, 87.0% oi the acrolein initially present having undergone reaction.
Example 5 A 40% solution of acrolein in xylene was oxidised for 5 hours at 32 C. in the presence of a catalyst, made by heating solid vanadium pentoxide which is dispersed in acetic acid with small amounts of hydrogen peroxideI so that the solid vanadium pentoxide partially dissolves. By adding the calculated amount of acetic anhydride the water in the catalyst solution is removed. The yield of monomeric acrylic acid was 92%.
What we claim is:
4 aliprocessaccordingtoclaimlwhereinthe catalystisn mredinsitubyreactionbetween vanadium pentoxlde, acetic acid and hydrogen peroxide.
4. A process for the manufacture of acrylic acid which comprises treating acrolein in solu-- tion in a water-soluble carboxylic acid havin no more than three carbon atoms with an oxygencontaining gas in the presence of a catalyst comprising an. aqueous solution of vanadic acid at a temperature not exceeding 45 reaction product containing monomeric acrylic acid and peroxidic compounds. HANNS PETER. BTAUDINGER. KARL HEINRICH WALTER TUERCK.
REFERENCES CITED The following references are oi record in the flle of this patent:
1. A process for the manufacture of acrylic acid comprising treating acroiein in presence oi acetic acid with an oxygen-containing gas in the presence of a catalyst comprising an aqueous solution of vanadic acid at a temperature not exceeding 45 C. to produce a. reaction product containing monomeric acrylic acid and peroxidic compounds.
2. A process according to claim 1 wherein the 1 reaction is carried out at a temperature of 20 to 30 C. and in presence 01' ganic solvent.
9. water-miscible or- UNITED s'ra'ms iA'l'ENT-S Number Name Date 1,081,959 Gi'lmstein Dec. 23, 1913 2,153,406 Bauer Apr. 4, 1939 2,183,325 Staudinger Dec. 12, 1939 2,210,469 Staudlllger A113. 6, 1940 2,212,900 Groll et a1. Aug. 27, 1940 FOREIGN PATENTS Number Country Date 369,963 Great Britain Mar. 17, 1932 OTHER REFERENCES Mellor, "Comprehensive Treatise on Inorg. and Theoretical Chemistry," vol. 9 (Longman's et aL, 1929) pages 743-755. and 794-795.
CQto produce a
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE23001E true USRE23001E (en) | 1948-05-18 |
Family
ID=2089978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US23001D Expired USRE23001E (en) | Oxidation of acrolein to |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE23001E (en) |
-
0
- US US23001D patent/USRE23001E/en not_active Expired
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