US2378501A - Process for manufacturing acrylic esters and other unsaturated compounds by thermal decomposition - Google Patents
Process for manufacturing acrylic esters and other unsaturated compounds by thermal decomposition Download PDFInfo
- Publication number
- US2378501A US2378501A US497344A US49734443A US2378501A US 2378501 A US2378501 A US 2378501A US 497344 A US497344 A US 497344A US 49734443 A US49734443 A US 49734443A US 2378501 A US2378501 A US 2378501A
- Authority
- US
- United States
- Prior art keywords
- thermal decomposition
- unsaturated compounds
- pyrolysis
- acrylic esters
- iron
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title description 7
- 238000000034 method Methods 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 title description 6
- 238000005979 thermal decomposition reaction Methods 0.000 title description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000000197 pyrolysis Methods 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 12
- -1 acrylic esters Chemical class 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000004035 construction material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QTFFGYLLUHQSAS-UHFFFAOYSA-N methyl 2-acetyloxypropanoate Chemical compound COC(=O)C(C)OC(C)=O QTFFGYLLUHQSAS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
Definitions
- This invention relates to the production of unsaturated compounds by the thermal decomposition of carboxylic acid esters, and more particularly to the manufacture of acrylic esters by passing vapors of lactic acid derivatives through pyrolysis tubes vated temperatures.
- esters are formed when certain lactic acid derivatives. such as methyl or chambers maintained at 816- alpha-acetoxypropionate, are passed through tubes maintained at temperatures ranging from 400 to 600 C. (Ritchie, Jones and Burns, U. S. 2,265,814, December 9, 1941; Smith and coworkers, Ind. Eng. Chem. 34, 473 (1942).)
- esters of carboxylic acids generally decompose on pyrolysis into carboxylic acids, olefins, diolefins, and other unsaturated compounds.
- a diiiiculty attending the use of these pyrogenic methods is that, when certain metals and alloys are used as contact and construction materials, corrosion occurs and undesirable by-products are formed.
- An object of this invention is to provide a commercial process for manufacturing various unsaturated compounds, including esters such as acrylic esters, by passing esters, including lactic esters, through a hot tube or pyrolysis chamber.
- esters such as acrylic esters
- a further object is to provide inexpensive and readily availableconstruction materials for the pyrolysis tube or chamber which will increase conversion per pass, increase throughput for a given plant, and decrease productioncosts and capital investment.
- a further object is to provide a method for inactivating or modifying contact and construction materials so that undesirable by-products, particularly gases and carbonaceous materials, are formed in only small and negligible quantities.
- the lactic acid derivative, methyl alpha-acetoxypropionate was pyrolyzed under many different conditions in equipment constructed of ordinary iron.
- the diameter of the iron pipe was one inch and the heated portion was 12 inches long.
- the temperature, which was controlled automatically, was measured by a thermocouple located in a well extending through the center of the iron pipe.
- inactivation of the iron was caused by dissolving water in the methyl acetoxypropionate prior to the pyrolysis.
- esters of this type we are not limited to the particular materials or procedures disclosed above. The general applicability of our process to the production of esters of this type will readily be seen by those skilled in the art.
- water may be dissolved in the ester to be pyrolyzed and the mixture passed into the pyrolysis unit, or the ester and water, as liquid or vapor, may be passed individually into the pyrolysis unit.
- Materials such as tertiary butyl alcohol, methyl hydracrylate, diacetone alcohol and hydrogen peroxide which readily d compose into water or oxygen.
- Oxygen analogs such as hydrogen sulfide, mercaptans, sulfur, ammonia, amines about 400 to 600 C. in pyrolysis equipment having iron as the principal ingredient, the step which comprises treating the metal surfaces in the reaction zone at a temperature of the order of the pyrolysis temperature with a mixture of steam and air immediately prior to pyrolyzing the methyl -alpha-acetoxypropionate.
- the step which comprises treating the metal surface in the reaction zone at a temperature of the order of the pyrolysis temperature with water vapor immediately prior to pyrolyzing the methyl alpha-acetoxypropionate.
Description
Patented June 19,1945
ESTERS AND OTHER UNSATURATED COM- POUNDS BY THERMAL DECOMPOSITION William P. Ratchford, Willow Grove, and Charles H. Fisher, Abington, Pa., assignors to Claude R. Wickard, as Secretary of Agriculture of the United States of America No Drawing. Application August 4, 1943,
Serial No. 497,344
3 Claims. (Cl. 260-486)v (Granted under the act or March 3, 1883, as
amended April 30, 1928; 370 0. G. 757) This application is made under the .act of March 3, 1883, as amended by the act of April 30, 1928, and the invention herein described, if patented, may be manufactured and used by or for the Government of the .United States of America for governmental purposes without the payment to us of any royalty thereon.
This invention relates to the production of unsaturated compounds by the thermal decomposition of carboxylic acid esters, and more particularly to the manufacture of acrylic esters by passing vapors of lactic acid derivatives through pyrolysis tubes vated temperatures.
It is known that acrylic esters are formed when certain lactic acid derivatives. such as methyl or chambers maintained at 816- alpha-acetoxypropionate, are passed through tubes maintained at temperatures ranging from 400 to 600 C. (Ritchie, Jones and Burns, U. S. 2,265,814, December 9, 1941; Smith and coworkers, Ind. Eng. Chem. 34, 473 (1942).) Moreover, it is known that esters of carboxylic acids generally decompose on pyrolysis into carboxylic acids, olefins, diolefins, and other unsaturated compounds. A diiiiculty attending the use of these pyrogenic methods is that, when certain metals and alloys are used as contact and construction materials, corrosion occurs and undesirable by-products are formed.
An object of this invention is to provide a commercial process for manufacturing various unsaturated compounds, including esters such as acrylic esters, by passing esters, including lactic esters, through a hot tube or pyrolysis chamber.
A further object is to provide inexpensive and readily availableconstruction materials for the pyrolysis tube or chamber which will increase conversion per pass, increase throughput for a given plant, and decrease productioncosts and capital investment.
A further object is to provide a method for inactivating or modifying contact and construction materials so that undesirable by-products, particularly gases and carbonaceous materials, are formed in only small and negligible quantities. I Other objects will appear from the following description.
The conversion of carboxylic acid esters into carboxylic acid and unsaturated compounds is highly dependent upon the nature of the packing of the hot tube and the nature of the material used in construction of the pyrolysis chamber. Stainless steel of the 18-8 type (18 percent chromium and 8 percent nickel) is a suitable construction material, but it is relatively expensive and inaccessible. Ordinary iron and steel tubes and pipes are more readily available, but these materials catalyze or cause. the formation of undesired by-products, chiefly gases and carbonaceous materials, during the pyrolysis.
We have found that thisdeleterious effect, that is, the formation of undesired by-products, can be decreased by the use of inhibitors or materials which diminish or destroy the catalytic activity.
Thus, we have found that the undesired catalytic effect of iron and its alloys can be diminished by the use of inhibitors, such as oxygen, sulfur, and nitrogen compounds. The invention described" herein makes possible th use of iron and iron alloy chambers Or tubes in the pyrolysi 'of esters, decreases the yield of undesirable byproducts, and increases the yield of the desired unsaturated compounds and organic acid.
Our invention is'illustrated by the following experimental procedure: a
The lactic acid derivative, methyl alpha-acetoxypropionate, was pyrolyzed under many different conditions in equipment constructed of ordinary iron. The diameter of the iron pipe was one inch and the heated portion was 12 inches long. The temperature, which was controlled automatically, was measured by a thermocouple located in a well extending through the center of the iron pipe.
The pyrolysis experiments showed that iron catalyzes or causes the formation of normally gaseous products and carbonaceous materials, particularly at the higher temperatures. At any given temperature the catalytic formation of byproducts increased with time. For example, at
545 C. and a contact time of '15 seconds, ap-
proximately 50 percent of the methyl alpha-acetoxypropionate was converted into products which are gases at normal temperature and pressure. Under these conditions, the yields of methyl acrylate and acetic acid are very low. This un-,
desired catalytic activity of the iron, however, was virtually eliminated by passing steam and air through the pyrolysis equipment for a short time while the temperature was kept at 525 C.
' acrylate and acetic acid were obtained in high yields by the thermal decomposition of methyl alpha-acetoxypropionate.
In another case, inactivation of the iron was caused by dissolving water in the methyl acetoxypropionate prior to the pyrolysis.
We are not limited to the particular materials or procedures disclosed above. The general applicability of our process to the production of esters of this type will readily be seen by those skilled in the art. For example, water may be dissolved in the ester to be pyrolyzed and the mixture passed into the pyrolysis unit, or the ester and water, as liquid or vapor, may be passed individually into the pyrolysis unit. Materials such as tertiary butyl alcohol, methyl hydracrylate, diacetone alcohol and hydrogen peroxide which readily d compose into water or oxygen.
also may be passed into the pyrolysis unit to prevent or decrease the formation of undesirable by-products. Oxygen analogs such as hydrogen sulfide, mercaptans, sulfur, ammonia, amines about 400 to 600 C. in pyrolysis equipment having iron as the principal ingredient, the step which comprises treating the metal surfaces in the reaction zone at a temperature of the order of the pyrolysis temperature with a mixture of steam and air immediately prior to pyrolyzing the methyl -alpha-acetoxypropionate.
2. In the process of manufacturing methyl aorylate by the thermal decomposition of methyl alpha-acetoxypropionate at a temperature of about 400 to 600 C. in pyrolysis equipment having iron as its principal ingredient, the step which comprises treating the metal surface in the reaction zone at a temperature of the order of the pyrolysis temperature with water vapor immediately prior to pyrolyzing the methyl alpha-acetoxypropionate. v
3. In the process of manufacturing methyl acrylate by the thermal decomposition of methyl alpha-acetoxypropionate at a temperature of about 400 to 600 C. in pyrolysis equipment having iron as its principal ingredient, the steps which comprise mixin the methyl alphaacetoxypropionate with water, and then pyrolyzing said mixture.
WILLIAM P. RATCHFORD. CHARLES H. FISHER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US497344A US2378501A (en) | 1943-08-04 | 1943-08-04 | Process for manufacturing acrylic esters and other unsaturated compounds by thermal decomposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US497344A US2378501A (en) | 1943-08-04 | 1943-08-04 | Process for manufacturing acrylic esters and other unsaturated compounds by thermal decomposition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2378501A true US2378501A (en) | 1945-06-19 |
Family
ID=23976481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US497344A Expired - Lifetime US2378501A (en) | 1943-08-04 | 1943-08-04 | Process for manufacturing acrylic esters and other unsaturated compounds by thermal decomposition |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2378501A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2531512A (en) * | 1946-11-05 | 1950-11-28 | Union Carbide & Carbon Corp | Process for making sorbic acid esters |
| DE1008282B (en) * | 1955-03-24 | 1957-05-16 | Wacker Chemie Gmbh | Process for the production of acrylic acid nitrile by thermal cleavage of acetylated lactic acid nitrile |
| US2807633A (en) * | 1955-01-21 | 1957-09-24 | Organico S A | Pyrolysis of ricinoleates |
| DE1033656B (en) * | 1953-08-12 | 1958-07-10 | Knapsack Ag | Process for the production of ª ‡, ª ‰ -unsaturated carboxylic acids and / or their derivatives |
| DE1062696B (en) * | 1952-11-06 | 1959-08-06 | Minnesota Mining & Mfg | Process for the production of acrylic acid or its alkyl esters from lactic acid or lactic acid alkyl esters |
| DE1118193B (en) * | 1957-09-17 | 1961-11-30 | Knapsack Ag | Process for the production of methacrylic acid esters by catalytic elimination of water from ª ‡ -oxyisobutyric acid esters |
| DE1129154B (en) * | 1956-04-04 | 1962-05-10 | Minnesota Mining & Mfg | Process for the preparation of acrylic acid, methacrylic acid or their alkyl esters by splitting off hydrogen halide from ª ‡ -chloropropionic acid and their esters |
-
1943
- 1943-08-04 US US497344A patent/US2378501A/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2531512A (en) * | 1946-11-05 | 1950-11-28 | Union Carbide & Carbon Corp | Process for making sorbic acid esters |
| DE1062696B (en) * | 1952-11-06 | 1959-08-06 | Minnesota Mining & Mfg | Process for the production of acrylic acid or its alkyl esters from lactic acid or lactic acid alkyl esters |
| DE1033656B (en) * | 1953-08-12 | 1958-07-10 | Knapsack Ag | Process for the production of ª ‡, ª ‰ -unsaturated carboxylic acids and / or their derivatives |
| US2807633A (en) * | 1955-01-21 | 1957-09-24 | Organico S A | Pyrolysis of ricinoleates |
| DE1008282B (en) * | 1955-03-24 | 1957-05-16 | Wacker Chemie Gmbh | Process for the production of acrylic acid nitrile by thermal cleavage of acetylated lactic acid nitrile |
| DE1129154B (en) * | 1956-04-04 | 1962-05-10 | Minnesota Mining & Mfg | Process for the preparation of acrylic acid, methacrylic acid or their alkyl esters by splitting off hydrogen halide from ª ‡ -chloropropionic acid and their esters |
| DE1118193B (en) * | 1957-09-17 | 1961-11-30 | Knapsack Ag | Process for the production of methacrylic acid esters by catalytic elimination of water from ª ‡ -oxyisobutyric acid esters |
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