US3676489A - Process for producing organic acids - Google Patents
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- US3676489A US3676489A US880890A US3676489DA US3676489A US 3676489 A US3676489 A US 3676489A US 880890 A US880890 A US 880890A US 3676489D A US3676489D A US 3676489DA US 3676489 A US3676489 A US 3676489A
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- 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
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- ABSTRACT An improvement in a process for converting an unsaturated, acyclic hydrocarbon to an acid in which the unsaturated, acyclic hydrocarbon is reacted with oxygen containing a small amount of ozone at a low temperature to obtain an intermediate product in a first stage and the intermediate product is oxidized in a second stage with molecular oxygen at a higher temperature to obtain the desired carboxylic acid, which involves heating the intermediate product in the absence of additional oxygen prior to the second stage oxidation, whereby explosive hazards in the second stage are minimized.
- This invention relates to a process for converting an unsaturated, acyclic hydrocarbon to an organic carboxylic acid by using ozone and oxygen while minimizing explosive hazards associated therewith. More specifically, this invention relates to an improvement in the process wherein an unsaturated, acyclic hydrocarbon is subjected to ozonolysis in a first stage and the product resulting therefrom is subjected to oxidation in a second stage with molecular oxygen to obtain organic carboxylic acids corresponding to said unsaturated, acyclic hydrocarbon.
- Unsaturated, acyclic hydrocarbons which can be used herein can be straight or branched chain olefins, terminal as well as internal, having from four to 40 carbon atoms, preferably from six to 30 carbon atoms.
- Specific examples of olefins that can be used are butene-l, octene-l, undecene-l, eicosene-l octene-2,dodecene-3, tetradecene-7 nonadecene-8, 3-methylpentene-l, 4-ethyldecene-2, 3- methyl-4-ethyl-nonene-l etc.
- the ozonolysis procedure used in the first step can follow any conventional outline.
- a stream of gas containing molecular oxygen, such as oxygen itself, and from about 0.5 to about 6, or even higher, but preferably about 2 to about 3 percent, by weight of ozone relative to oxygen is passed continuously through the olefin charge dissolved in a suitable solvent, for example, a carboxylic acid having from two to ten carbon atoms, such as acetic acid, propionic acid, heptanoic acid and decanoic acid, or an alcohol having from one to six carbon atoms, such as methanol, propanol-I, hexanol-l etc., at such a rate so that the exit stream will be substantially free of ozone, continuing until some ozone is found in the exit gas, at which time the ozonolysis reaction will have terminated.
- a suitable solvent for example, a carboxylic acid having from two to ten carbon atoms, such as acetic acid, propionic acid
- ozonolysis is substantially instantaneous, the time of contact depends upon obtaining suitable contact between ozone and unreacted olefin.
- the temperature can be from about 20 to about 35 C., preferably about to about C., and while pressures as high as about 50 pounds per square inch gauge can be employed, atmospheric pressure is preferred.
- pressures as high as about 50 pounds per square inch gauge can be employed, atmospheric pressure is preferred.
- the olefin for example, R and R" being alkyl substituents is believed to be converted to wherein R' represents an alkyl group, in the case of an alcohol solvent, and an acyl group, in the case of an acid solvent.
- the hydroperoxide is believed to result from the addition reaction of the intermediate Zwitterion with the solvent therein.
- the aldehydes and hydroperoxides so produced are then subjected to oxidation in a second stage with a gas containing molecular oxygen, preferably air.
- a gas containing molecular oxygen preferably air.
- Any effective method which insures contact between the aldehyde and the hydroperoxide and oxygen can be used.
- air is continuously passed through the ozonolysis product and this is preferably continued until there is no noticeable reduction in oxygen content of the exit stream.
- the amount of oxygen stoichiometrically needed, relative to the ozonolysis product, defined as consisting essentially of aldehydes and hydroperoxides, on a molar basis must be at least about 1:1, but in general from about 5:1 to about 100:], is used.
- the hydroperoxide content of the ozonolysis product charged to the second stage can be substantially reduced, thereby minimizing the amount thereof that can find its way into the vapor space above the product being treated in the second stage and reducing the explosive character thereof, by heating the ozonolysis product obtained in the first stage in the absence of added oxygen prior to oxidation in the second stage.
- heating converts the hydroperoxide to the corresponding aldehydes and acids.
- the latter are the desired acids and the aldehydes so produced, together with the aldehydes obtained in the first stage, are then oxidized to the corresponding acids in the second stage in the manner hereinabove defined.
- the yield of desired acids is not adversely affected by the heating step.
- the ozonolysis product from the first stage consisting essentially of the defined aldehydes and hydroperoxides, is heated at a temperature of about to about 140 C., preferably about l00 to about C., a pressure of about atmospheric to about 200 pounds per square inch gauge, preferably about atmospheric to about 50 pounds per square gauge, for about 1 minute to about 30 minutes, preferably for about 10 minutes to about 20 minutes.
- any oxygen which may be present, which does not adversely affect the operation is that small amount that may be present as a result of entrainment in the first stage, that which may be in the air in the reaction zone or that which may be released in the decomposition of the hydroperoxide. It is critical that the above temperature and time limitations be strictly observed. At lower temperatures, the reaction time necessary for the decomposition of the hydroperoxides becomes too long, whereby the formation of polymers and other by-products is favored. At higher temperatures the decomposition reaction proceeds too violently, thus presenting a potentially hazardous situation in addition to a tendency for formation of undesired byproducts.
- EXAMPLE I 20 grams of octene-l were dissolved in 80 grams of propionic acid and the resulting mixture was cooled to a temperature of 4 C. An oxygen stream containing from three to 4 percent by weight of ozone was passed through the mixture over a period of about 3 hours at a rate of about I liter per minute while maintaining the temperature of the reaction mixture at 5 to 8 C. The reaction product was found to have a peroxide number of 2180. By peroxide number we mean milliequivalent active oxygen per 1,000 grams of product when determined by an iodometric method. By active oxygen” we mean the oxygen in the ozonolysis product associated with the hydroxyl group forming the hydroperoxide. The reaction product was then maintained at a temperature of 100 to 108 C.
- EXAMPLE 11 The run of EXAMPLE 1 was repeated except that the ozonolysis product at the end of the first stage was heated at a temperature of 100 to 109 C. and atmospheric pressure, in the absence of additional oxygen, over a period of minutes, prior to treatment in the second stage. The peroxide number of the heated mixture was 355. The final product was found to contain 94.3 percent by weight of heptanoic acid, with the remainder being substantially hexanoic acid and neutral compounds.
- the improvement which comprises heating said intermediate product in the absence of added oxygen prior to said oxidation in said second stage at a temperature of about to about 140 C.
Abstract
An improvement in a process for converting an unsaturated, acyclic hydrocarbon to an acid in which the unsaturated, acyclic hydrocarbon is reacted with oxygen containing a small amount of ozone at a low temperature to obtain an intermediate product in a first stage and the intermediate product is oxidized in a second stage with molecular oxygen at a higher temperature to obtain the desired carboxylic acid, which involves heating the intermediate product in the absence of additional oxygen prior to the second stage oxidation, whereby explosive hazards in the second stage are minimized.
Description
United States Patent Ellis et al.
[72] Inventorsi Alan F. Ellis, Murrysville; Alfred N. Kresge, Verona; Richard Seekircher, Cheswick, all of Pa.
[73] Assignee: Gulf Research & Development Company, Pittsburgh, Pa.
[22] Filed: Nov. 28, 1969 [21] Appl. No.: 880,890
[52] US. Cl. ..260/533 R, 260/413 [5 l Int. Cl ..C07c 51/32 [58] Field oiSearch ..260/533 R, 533 C,4l3
[56] References Cited UNITED STATES PATENTS 3,557,166 l/l97l Lachowicz ..260/533 R 3,219,675 11/1965 Seekircher ..260/533 C 3,238,250 3/1966 Bailey ..260/533 R 3,441,604 4/1969 Baylis et al. ..260/533 C PROCESS FOR PRODUCING ORGANIC ACIDS 51 July 11,1972
OTHER PUBLICATIONS Noller Chemistry of Organic Compounds, 3rd ed. Saunders (l965)pg. 101.
Primary ExaminerLorraine A. Weinberger Assistant ExaminerRichard D. Kelly Attorney-Meyer Neishloss, Deane E. Keith and Joseph J. Carducci [5 7] ABSTRACT An improvement in a process for converting an unsaturated, acyclic hydrocarbon to an acid in which the unsaturated, acyclic hydrocarbon is reacted with oxygen containing a small amount of ozone at a low temperature to obtain an intermediate product in a first stage and the intermediate product is oxidized in a second stage with molecular oxygen at a higher temperature to obtain the desired carboxylic acid, which involves heating the intermediate product in the absence of additional oxygen prior to the second stage oxidation, whereby explosive hazards in the second stage are minimized.
9 Claims, No Drawings PROCESS FOR PRODUCING ORGANIC ACIDS This invention relates to a process for converting an unsaturated, acyclic hydrocarbon to an organic carboxylic acid by using ozone and oxygen while minimizing explosive hazards associated therewith. More specifically, this invention relates to an improvement in the process wherein an unsaturated, acyclic hydrocarbon is subjected to ozonolysis in a first stage and the product resulting therefrom is subjected to oxidation in a second stage with molecular oxygen to obtain organic carboxylic acids corresponding to said unsaturated, acyclic hydrocarbon.
Unsaturated, acyclic hydrocarbons which can be used herein can be straight or branched chain olefins, terminal as well as internal, having from four to 40 carbon atoms, preferably from six to 30 carbon atoms. Specific examples of olefins that can be used are butene-l, octene-l, undecene-l, eicosene-l octene-2,dodecene-3, tetradecene-7 nonadecene-8, 3-methylpentene-l, 4-ethyldecene-2, 3- methyl-4-ethyl-nonene-l etc.
The ozonolysis procedure used in the first step can follow any conventional outline. Thus, for example, a stream of gas containing molecular oxygen, such as oxygen itself, and from about 0.5 to about 6, or even higher, but preferably about 2 to about 3 percent, by weight of ozone relative to oxygen is passed continuously through the olefin charge dissolved in a suitable solvent, for example, a carboxylic acid having from two to ten carbon atoms, such as acetic acid, propionic acid, heptanoic acid and decanoic acid, or an alcohol having from one to six carbon atoms, such as methanol, propanol-I, hexanol-l etc., at such a rate so that the exit stream will be substantially free of ozone, continuing until some ozone is found in the exit gas, at which time the ozonolysis reaction will have terminated. Since ozonolysis is substantially instantaneous, the time of contact depends upon obtaining suitable contact between ozone and unreacted olefin. The temperature can be from about 20 to about 35 C., preferably about to about C., and while pressures as high as about 50 pounds per square inch gauge can be employed, atmospheric pressure is preferred. As a result of ozonolysis, cleavage of the olefinic double bond occurs and the individual fragments so produced react with ozone and are believed to form aldehydes and hydroperoxides. Thus, the olefin for example, R and R" being alkyl substituents, is believed to be converted to wherein R' represents an alkyl group, in the case of an alcohol solvent, and an acyl group, in the case of an acid solvent. The hydroperoxide is believed to result from the addition reaction of the intermediate Zwitterion with the solvent therein.
The aldehydes and hydroperoxides so produced are then subjected to oxidation in a second stage with a gas containing molecular oxygen, preferably air. Any effective method which insures contact between the aldehyde and the hydroperoxide and oxygen can be used. In a preferred embodiment air is continuously passed through the ozonolysis product and this is preferably continued until there is no noticeable reduction in oxygen content of the exit stream. The amount of oxygen stoichiometrically needed, relative to the ozonolysis product, defined as consisting essentially of aldehydes and hydroperoxides, on a molar basis must be at least about 1:1, but in general from about 5:1 to about 100:], is used. Temperatures ofabout 70 to about 150 C., preferably about 80 to about I 10 C., can be used. Pressures as high as about 100 pounds per square inch gauge can be employed, but in general atmospheric pressure is preferred. A reaction time of about 0.5 to about 2 hours will generally suffice. As a result of the oxidation step it is believed the aldehydes are oxidized and the hydroperoxides are rearranged to the corresponding organic carboxylic acids. Recovery of the organic carboxylic acids from the reaction mixture can be effected in any desired manner, but in general fractional distillation is preferred.
Unfortunately, we have found in our studies that during the oxidation in the second stage the vapor phase above the ozonolysis product through which molecular oxygen is being passed has potentially an explosively violent nature. We believe this occurs because the passage of molecular oxygen through the ozonolysis product removes therefrom some of the hydroperoxide therein and the latter forms a mixture with unreacted molecular oxygen that has passed therethrough and it is this mixture that can explode.
We have found that the hydroperoxide content of the ozonolysis product charged to the second stage can be substantially reduced, thereby minimizing the amount thereof that can find its way into the vapor space above the product being treated in the second stage and reducing the explosive character thereof, by heating the ozonolysis product obtained in the first stage in the absence of added oxygen prior to oxidation in the second stage. We believe that such heating converts the hydroperoxide to the corresponding aldehydes and acids. The latter are the desired acids and the aldehydes so produced, together with the aldehydes obtained in the first stage, are then oxidized to the corresponding acids in the second stage in the manner hereinabove defined. Fortuitously,
the yield of desired acids is not adversely affected by the heating step.
In conducting the intermediate heating step the ozonolysis product from the first stage, consisting essentially of the defined aldehydes and hydroperoxides, is heated at a temperature of about to about 140 C., preferably about l00 to about C., a pressure of about atmospheric to about 200 pounds per square inch gauge, preferably about atmospheric to about 50 pounds per square gauge, for about 1 minute to about 30 minutes, preferably for about 10 minutes to about 20 minutes. As noted, no oxygen is added to the ozonolysis product during such intermediate heating, and any oxygen which may be present, which does not adversely affect the operation, is that small amount that may be present as a result of entrainment in the first stage, that which may be in the air in the reaction zone or that which may be released in the decomposition of the hydroperoxide. It is critical that the above temperature and time limitations be strictly observed. At lower temperatures, the reaction time necessary for the decomposition of the hydroperoxides becomes too long, whereby the formation of polymers and other by-products is favored. At higher temperatures the decomposition reaction proceeds too violently, thus presenting a potentially hazardous situation in addition to a tendency for formation of undesired byproducts.
The process of this invention can further be illustrated by the following.
EXAMPLE I 20 grams of octene-l were dissolved in 80 grams of propionic acid and the resulting mixture was cooled to a temperature of 4 C. An oxygen stream containing from three to 4 percent by weight of ozone was passed through the mixture over a period of about 3 hours at a rate of about I liter per minute while maintaining the temperature of the reaction mixture at 5 to 8 C. The reaction product was found to have a peroxide number of 2180. By peroxide number we mean milliequivalent active oxygen per 1,000 grams of product when determined by an iodometric method. By active oxygen" we mean the oxygen in the ozonolysis product associated with the hydroxyl group forming the hydroperoxide. The reaction product was then maintained at a temperature of 100 to 108 C. for 60 minutes while air was passed therethrough at a rate of 1 liter per minute. The resulting product was subjected to distillation sufficient to remove propionic acid therefrom. It was found that 94.3 percent by weight of the remainder was heptanoic acid, with substantially the rest being hexanoic acid and neutral compounds.
EXAMPLE 11 The run of EXAMPLE 1 was repeated except that the ozonolysis product at the end of the first stage was heated at a temperature of 100 to 109 C. and atmospheric pressure, in the absence of additional oxygen, over a period of minutes, prior to treatment in the second stage. The peroxide number of the heated mixture was 355. The final product was found to contain 94.3 percent by weight of heptanoic acid, with the remainder being substantially hexanoic acid and neutral compounds.
EXAMPLE Ill grams of tetradecene-7 were dissolved in 80 grams of propionic acid and the resulting mixture was cooled to a temperature of 4 C. An oxygen containing from three to 4 percent by weight of ozone was passed through the mixture over a period of 100 minutes at a rate of about 1 liter per minute while maintaining the temperature of the reaction mixture at 7 to 9 C. The reaction product was found to have a peroxide number of 2120. The reaction product was then maintained at a temperature of 100 to 108 C. for 60 minutes while air was passed therethrough at a rate of 1 liter per minute. The resulting product was subjected to distillation sufficient to remove propionic acid therefrom. lt was found that 92.2 percent of the remainder was heptanoic acid, with acids of lower and higher molecular weight and some neutral compounds as byproducts.
EXAMPLE IV The run of EXAMPLE I" was repeated except that the ozonolysis product at the end of the first stage was heated at a temperature of 100 to 108 C. and atmospheric pressure, in the absence of additional oxygen, over a period of 15 minutes, prior to treatment in the second stage. The peroxide number of the heated mixture was 575. The final product was found to contain 91.9 percent by weight of heptanoic acid. The byproducts consisted of acids of lower and higher molecular weight and some neutral compounds.
A comparison of the runs in which an intermediate thermal treatment without oxygen was applied with those in which the oxidation step followed the o'zonization step immediately shows that the thermal treatment reduces the peroxide content of the mixture to a level which can be considered essentially safe in terms of formation of an explosive mixture in the vapor phase.
Obviously, many modifications and variations of the invention, as hereinabove set forth, can be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.
We claim:
1. In a process for converting an unsaturated, acyclic hydrocarbon having from four to 40 carbon atoms to an acid wherein the unsaturated, acyclic hydrocarbon is reacted with ozone at a lower temperature of about 20 to about 35 C. to obtain an intermediate product in a first stage and the intermediate product is oxidized in a second stage with molecular oxygen at a higher temperature of about 70 to about 150 C.
to obtain the desiredcarboxylic acid, the improvement which comprises heating said intermediate product in the absence of added oxygen prior to said oxidation in said second stage at a temperature of about to about 140 C.
2. The process of claim 1 wherein said heating of said inter mediate product prior to said second stage is in the temperature range of about to about C.
3. The process of claim 1 wherein said heating of said intermediate product prior to said second stage is within a period of about 1 to about 30 minutes.
4. The process ofclaim 1 wherein said heating of said intermediate product prior to said second stage is within a period of about 10 to about 20 minutes.
5. The process of claim 1 wherein the temperature in said first stage is within the range of about 10 to about 20 C.
6. The process of claim 1 wherein the temperature in said second stage is within the range of about 80 to about 1 10 C.
7. The process of claim 1 wherein said unsaturated, acyclic hydrocarbon has from six to 30 carbon atoms.
8. The process of claim 1 wherein said unsaturated, acyclic hydrocarbon is octene-I.
9. The process of claim 1 wherein said unsaturated, acyclic hydrocarbon is tetradecene-7.
Claims (8)
- 2. The process of claim 1 wherein said heating of said intermediate product prior to said second stage is in the temperature range of about 100* to about 120* C.
- 3. The process of claim 1 wherein said heating of said intermediate product prior to said second stage is within a period of about 1 to about 30 minutes.
- 4. The process of claim 1 wherein said heating of said intermediate product prior to said second stage is within a period of about 10 to about 20 minutes.
- 5. The process of claim 1 wherein the temperature in said first stage is within the range of about 10* to about 20* C.
- 6. The process of claim 1 wherein the temperature in said second stage is within the range of about 80* to about 110* C.
- 7. The process of claim 1 wherein said unsaturated, acyclic hydrocarbon has from six to 30 carbon atoms.
- 8. The process of claim 1 wherein said unsaturated, acyclic hydrocarbon is octene-1.
- 9. The process of claim 1 wherein said unsaturated, acyclic hydrocarbon is tetradecene-7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88089069A | 1969-11-28 | 1969-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3676489A true US3676489A (en) | 1972-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US880890A Expired - Lifetime US3676489A (en) | 1969-11-28 | 1969-11-28 | Process for producing organic acids |
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| Country | Link |
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| US (1) | US3676489A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4038297A (en) * | 1973-05-17 | 1977-07-26 | Emery Industries, Inc. | High molecular weight monocarboxylic acids and ozonization process for their preparation |
| US4138417A (en) * | 1975-12-17 | 1979-02-06 | Asahi Glass Company, Ltd. | Process for producing perfluorocarboxylic acid |
| WO2020035528A1 (en) * | 2018-08-16 | 2020-02-20 | Rise Research Institutes of Sweden AB | Concept for the production of food with reduced environmental impact |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3219675A (en) * | 1961-11-02 | 1965-11-23 | Columbian Carbon | Preparation of alpha,omega-alkandioic acids and omega-formylalkanoic acids |
| US3238250A (en) * | 1961-03-31 | 1966-03-01 | Exxon Research Engineering Co | Selective oxidation of ozonolysis inter-condensation products to carboxylic acids with ozone catalyzed oxygen in the presence of at least two mols of formic acid per mol equivalent of peroxide groups |
| US3441604A (en) * | 1964-09-01 | 1969-04-29 | Geigy Chem Corp | Process for producing dicarboxylic acids |
| US3557166A (en) * | 1965-06-24 | 1971-01-19 | Texaco Inc | Process for producing carboxylic acids and nitrogen containing intermediates from olefins |
-
1969
- 1969-11-28 US US880890A patent/US3676489A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238250A (en) * | 1961-03-31 | 1966-03-01 | Exxon Research Engineering Co | Selective oxidation of ozonolysis inter-condensation products to carboxylic acids with ozone catalyzed oxygen in the presence of at least two mols of formic acid per mol equivalent of peroxide groups |
| US3219675A (en) * | 1961-11-02 | 1965-11-23 | Columbian Carbon | Preparation of alpha,omega-alkandioic acids and omega-formylalkanoic acids |
| US3441604A (en) * | 1964-09-01 | 1969-04-29 | Geigy Chem Corp | Process for producing dicarboxylic acids |
| US3557166A (en) * | 1965-06-24 | 1971-01-19 | Texaco Inc | Process for producing carboxylic acids and nitrogen containing intermediates from olefins |
Non-Patent Citations (1)
| Title |
|---|
| Noller Chemistry of Organic Compounds, 3rd ed. Saunders (1965) pg. 101. * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4038297A (en) * | 1973-05-17 | 1977-07-26 | Emery Industries, Inc. | High molecular weight monocarboxylic acids and ozonization process for their preparation |
| US4138417A (en) * | 1975-12-17 | 1979-02-06 | Asahi Glass Company, Ltd. | Process for producing perfluorocarboxylic acid |
| WO2020035528A1 (en) * | 2018-08-16 | 2020-02-20 | Rise Research Institutes of Sweden AB | Concept for the production of food with reduced environmental impact |
| CN112638858A (en) * | 2018-08-16 | 2021-04-09 | 瑞典赖斯研究院有限责任公司 | Concept for producing food with reduced environmental impact |
| US11959044B2 (en) | 2018-08-16 | 2024-04-16 | Green-On Ab | Concept for the production of food with reduced environmental impact |
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| Date | Code | Title | Description |
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| AS | Assignment |
Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A COR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE.;REEL/FRAME:004610/0801 Effective date: 19860423 Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A COR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE.;REEL/FRAME:004610/0801 Effective date: 19860423 |