Process for preparing acrylic acid

Abstract: This invention relates to a process for preparing acrylic acid which utilizes an aqueous stream which includes recycled wastewater, at least part of which is stripped of undesirable components in a stripping column prior to being recycled to an acrylic acid absorber.

Description: This invention relates to a process for preparing (meth)acrylic acid. In particular, the invention relates to a process for preparing (meth)acrylic acid which utilizes an aqueous stream which includes recycled wastewater in the process to separate product (meth)acrylic acid from a mixed product gas. Acrylic acid is generally prepared by the catalytic oxidation of at least one hydrocarbon material. For instance, acrylic acid may be prepared from propylene and/or acrolein in a one or two step process. In a first step propylene is oxidized in the presence of oxygen, diluent inert gases, water vapor, and appropriate catalysts to produce acrolein according to equation (I): C 3 H 6 + O 2 ⇒ C 2 H 3 CHO + H 2 O + heat The acrolein is then oxidized, in a second step, in the presence of oxygen, diluent inert gases, water vapor, and appropriate catalysts to form acrylic acid according to equation (II): C 2 H 3 CHO + ½ O 2 ⇒ C 2 H 3 COOH + heat The acrolein may be provided as starting material in a one step reaction (II) to produce acrylic acid. Alternatively, propane may be used as a starting material. The propane is oxidized using appropriate catalysts, for instance, as described in U.S. Patent 5,380,933 to form product acrylic acid. Methacrylic acid is similarly prepared by catalytic oxidation of isobutylene and/or isobutane. The acrylic acid prepared using such catalytic oxidation reactions is present in a mixed product gas exiting the reactor. Generally, the mixed product gas is cooled and is contacted with an aqueous stream in an absorption tower, thereby providing an aqueous acrylic acid solution which is then dehydrated in a distillation step to provide a crude acrylic acid solution. The crude acrylic acid solution can be used to produce various acrylic esters or be further purified to provide various grades of purified acrylic acid which can then be further utilized, for instance in the production of super absorbent polymer products. Typically in chemical manufacturing processes, including such processes for the production of acrylic acid, a large waste load is generated. Such waste load usually takes the form of waste product gases and waste water streams. Waste product gases may be generated at several points in the acrylic acid manufacturing process. Of particular interest is the remainder of the mixed product gas emerging from the absorber which has had product acrylic acid absorbed from it upon contact with the aqueous stream in the absorber. This remainder of the mixed product gas, known as the absorber waste gas or absorber off-gas, typically undergoes some sort of waste treatment such as thermal oxidation, incineration, or catalytic oxidation before being released to the air so as to comply with applicable environmental requirements. Wastewater is also generated in the acrylic acid production process as well as in other manufacturing processes. A typical acrylic acid production facility may generate up to two pounds of wastewater per pound of acrylic acid produced, depending on the particular process used. Of particular interest is the wastewater recovered in dehydration processes, such as in the dehydration of acrylic acid. Generally such wastewater also must be treated in some manner to comply with applicable environmental standards before being released into the environment. Consequently, since treatment and disposal of waste gases and wastewater constitutes a significant expense for the acrylic acid manufacturer alternative uses and treatments which add value to the manufacturing process and/or reduce expenses is a constant goal to such manufacturers. Several methods have been developed in the art to meet this goal. It is known in the art to recycle at least a portion of the absorber off-gas back to the reactor(s). This recycle serves several purposes including providing inert diluent gas and steam to the reactant composition, and reducing wastewater generated by the process by reducing the amount of steam that is fed to the process. Furthermore, small amounts of unreacted propylene and acrolein contained in the off-gas are given another chance to react and thereby improve the overall acrylic acid yield by increasing conversions of propylene and acrolein. Recycle of certain generated wastes in an acrylic acid process for reuse in the process absorbing step has been taught in the art. For instance, Japanese Patent Application Kokai (Laid Open) No. 246941/1993 teaches recycle of a recovered acetic acid solution for reuse as an absorbent in an acrylic acid absorption tower. However, the application states that acrylic acid recovery is inefficient in the absorber because no solvent and substantially no acrylic acid is present. U.S. Patent No. 5,785,821 discloses wastewater recycle to the absorber of an acrylic acid process wherein the recycled wastewater stream has a specific composition of acetic acid (3-10 wt %), acrylic acid (0.5-5.0 wt%), and distillation solvent (0.01-0.5 wt%). Such a recycle stream, containing these specific amounts of acetic acid, acrylic acid and distillation solvent is said to enable collection of acrylic acid in the absorber at a high efficiency. GB-A-2146636 discloses a process for the production of acrylic acid which comprises catalytically oxidizing propylene and/or acrolein in the vapor phase with a gas containing molecular oxygen, wherein: the reaction product gas obtained by the oxidation is rapidly cooled to collect a condensate; uncollected substances are collected by causing them to be absorbed by water; the resulting aqueous solution composed mainly of acrylic acid, acetic acid and water is fed into a distillation column having at least 10 theoretical trays in its recovery section and distilled in the presence of an azeotropic agent; an azeotropic composition consisting substantially of the azeotropic agent and water and being free from acrylic acid and acetic acid is distilled off from the top of the column; water is separated from the distillate and recycled to the collecting device; and a mixture composed mainly of acrylic acid and acetic acid, and free from water and the azeotropic agent, is obtained from the bottom of the column. However, one problem envisioned with recycle of wastewater is that the recycled wastewater may contain an unacceptable concentration of undesirable components such as volatile organic compounds (VOC). Such high concentrations of undesirable components in the recycled wastewater stream can lead to a higher waste concentration, e.g., acetic acid and organic distillation solvent, in the absorber off-gas. Consequently, when some or all of an absorber off-gas is recycled to the reactor it will contain a higher level of undesirable components. Such materials may be detrimental to the catalytic oxidation reactions which form acrolein and/or acrylic acid in the reactor. In particular, it is believed that activity of the oxidation catalysts may be reduced by the presence of the higher level of volatile organic components. Furthermore, certain organic, such as toluene, may actually compete with starting materials so that less starting materials are reacted and more by-products show up in the acrylic acid product. The preparation and isolation of methacrylic acid proceeds by similar steps. Consequently, methacrylic acid manufacturers suffer from similar problems. The present inventors have now discovered that by stripping the wastewater of undesirable components using a stripping gas including process waste gas overcomes the problem of unsuitable levels of undesirable components being recycled to the absorber. Furthermore, the invention enables obtaining additional value from process wastewater and waste gas streams. This is done while maintaining a suitable acrylic acid collection efficiency in the absorber. Accordingly, a novel process for preparing (meth) acrylic acid is set out in the accompanying claims. The process of the invention provides the following advantages: (1) a decreased amount of undesirable components in the absorber off-gas leading to a decreased amount of potentially harmful components recycled back to the reactor; (2) additional value is obtained from process waste gas streams by using them to strip process wastewater streams; (3) stripped wastewater having a lower level of components potentially harmful to the catalytic reactions in the reactor are recycled to the absorber for acrylic acid absorption thereby reducing the wastewater load in the facility; (4) stripping gas streams sent to thermal oxidizers for treatment have a higher concentration of organic material from the stripping process, thereby reducing the fuel requirement of the thermal oxidizer. Figure 1 depicts a flow chart showing one embodiment of the process of the present invention. Throughout this specification and claims, unless otherwise indicated, references to percentages are by weight percent and all temperatures are in degree centigrade. It is also to be understood that for purposes of this specification and claims that the range and ratio limits, recited herein, are combinable. For example, if ranges of 1-20 and 5-15 are recited for a particular parameter, it is understood that ranges of 1-15 or 5-20 are also contemplated. Also, the term "major amount" is understood to mean greater than 50 percent by weight of the total composition. The term "minor amount" is understood to mean less than 50 percent by weight of the total composition. The term "wastewater" is understood to mean any water stream having impurities and/or additives contained therein. In a like manner, the term "waste gas" is understood to mean a gas or mixture of gases having impurities and/or additives contained therein. The term "(meth)acrylic acid" is understood to encompass both acrylic acid and methacrylic acid. The process of the present invention will be initially described with reference to Figure 1. Also, although the present invention is described following in terms of a process for preparing acrylic acid, it is to be understood that the invention encompasses preparation of methacrylic acid also. As recited above, the process of the present invention for preparing (meth)acrylic acid includes feeding a mixed product gas 1 from the vapor phase catalytic oxidation of at least one hydrocarbon material selected from (isobutylene and isobutane) propylene and propane with a molecular oxygen containing gas to an absorption tower 2 . The mixed product gas is generally obtained by the vapor phase catalytic oxidation of a hydrocarbon material with a molecular oxygen containing gas in the presence of a suitable oxidation catalyst. The vapor phase catalytic oxidation of a hydrocarbon material to acrolein and/or acrylic acid as well as reactors, catalysts, and processes for performing the same are generally known in the art and are described, for instance in U.S. Patents 4,203,906; 4,256,783; 4,365,087; 4,873,368; 5,161,605; 5,177,260; 5,198,578; 5,739,391; 5,821,390, and co-pending U. S. patent application 09/244182. Depending on the reactants fed to the reactor, the mixed product gas generally includes inert gas(es), including but not limited to, nitrogen, helium, argon, etc.; acrylic acid; unreacted hydrocarbon reactants, including but not limited to, propylene, acrolein, and propane; steam, and molecular oxygen containing reactants, including but not limited to, air, and oxygen; reaction by-products, including but not limited to, acetic acid, formaldehyde, maleic acid, and other organics; as well as CO 2 ,, CO and H 2 O. Generally, the composition of the mixed product gas feed 1 includes from 5 to 30 percent by weight acrylic acid, from 0.1 to 3.0 percent by weight acetic acid, from 0.02 to 0.2 percent by weight acrolein, from 30 to 95 percent by weight inert gas, and from 1 to 30 percent by weight steam. The process of the present invention for preparing acrylic acid also includes feeding an aqueous stream 3 which includes recycled wastewater derived from a (meth) acrylic acid process stream to the absorber 2 . It is not necessary that the wastewater be derived from the same acrylic acid process stream into which it is recycled. Rather, the wastewater may be derived from one acrylic acid process stream and recycled into another. Suitable examples of wastewater derived from a (meth) acrylic acid process stream include, but are not limited to, wastewater derived from dehydration of acrylic acid, other aqueous distillates, and raffinates. The aqueous stream 3 may include any suitable amount of recycled waste water up to 100 weight percent recycled wastewater. Typically, the aqueous stream 3 will be a mixture of a wastewater stream 22 from an acrylic acid manufacturing process and an essentially pure water stream 5 , e.g., deionized water. In one embodiment, the aqueous stream 3 includes a major amount of wastewater. In another embodiment, the aqueous stream 3 includes from 0.1 percent by weight to 100 percent by weight of wastewater. Preferably, the aqueous stream 3 contains 100 percent by weight wastewater. Regardless of how much recycled wastewater is utilized, the aqueous stream will contain a major amount of water and minor amounts of at least one of acrylic acid, acetic acid, or distillation solvent(s). Generally, the aqueous stream contains less than 3.0, preferably less than 2.0, more preferably less than 1.5 percent by weight acetic acid. In another embodiment, the aqueous stream is substantially free of distillation solvent(s) and/or acrylic acid. As indicated in Figure 1, all or a portion of wastewater stream 4 may be stripped of undesirable components before being introduced into aqueous stream 3. Wastewater stream 4 is stripped of undesirable components in a stripping column 6 using a stripping gas stream 7, which includes waste gas, to produce a stripped wastewater stream 29. Wastewater stream 29 is then fed to aqueous stream 3 as wastewater stream 22 . Alternatively, a portion of wastewater stream 4 is stripped to form stripped wastewater stream 29 with the unstripped portion of wastewater stream 4 being combined with stripped wastewater stream 29 to form wastewater stream 22 which is then fed to aqueous stream 3 . The amount of wastewater stream 4 which is stripped or unstripped will vary according to the amount of undesirable components in wastewater stream 4 . The stripping gas stream 7 may include, but not be limited to, combustion air and fresh air as well as waste gases. The waste gas stream is an absorber off-gas stream. Such an embodiment of the present invention is illustrated in Figure 1 wherein the absorber off-gas stream 8 from the absorber 2 is fed to the stripping column 6 as stripping gas stream 7 to remove undesirable components from the wastewater stream 4 in the stripping column 6 . The absorber off-gas stream 8 is typically split so that a portion, stream 30 , is recycled to an oxidation reactor with the remainder used as a stripping gas 7 . The waste gas stream 31 from the stripper 6 is generally sent to waste treatment for incineration and/or oxidation and then released to the atmosphere. Generally, the stripping waste gas has a water content of from 0 to 100, preferably 5 to 30, more preferably 8 to 20 weight percent and a temperature from 20 to 250, preferably 45 to 125, more preferably from 50 to 90 degrees Centigrade. The use of a portion of the absorber off gas stream 8 as a stripping gas 7 is advantageous because the absorber off gas emerges from the absorber with a sufficient heat and water content for adequately stripping undesirable components from the wastewater. Accordingly, treatment of a potential waste gas stripping stream, i.e., heating and adding or removing water, is avoided. However, at times it may be desirable to either use other stripping gas streams such as air, combustion air, etc., in combination with an absorber off-gas stream. This may require additional heating of the stripping gas to obtain a proper operating temperature range. Also, additional heat may be required to increase the removal of organics from the wastewater stream. Consequently, a live steam sparge, external or internal reboilers, stripping gas feed pre-heater, or other methods known in the art of supplying additional heat to a stripping column may be utilized. In addition, there may be instances wherein additional momentum transfer within the stripping column is required. For example, where there is an increased pressure drop within the column and absorber pressure is insufficient to provide adequate momentum transfer. Consequently, devices such as a blower may be utilized to increase such momentum transfer. The stripping column 6 may be any column suitable for stripping undesirable components from wastewater. Such columns are known in the art and include packed columns and tray containing columns. In a further embodiment, the aqueous stream 3 includes a polymerization inhibitor introduced at the polymerization inhibitor feed 12 . The polymerization inhibitor may include a water soluble or alcohol soluble polymerization inhibitor. Suitable examples include but are not limited to, hydroquinone; 4-methoxy phenol; 4-ethoxyphenol; 1,2-dihydroxybenzene; catechol monobutyl ether; pyrogallol; 4-aminophenol; 2-mercaptophenol; 4-mercaptophenol; 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy, free radical; 4-oxo-2,2,6,6-tetramethylpiperidinyloxy, free radical; 4-amino-2,2,6,6-tetramethylpiperidinyloxy, free radical; isomers thereof; derivatives thereof; mixtures of two or more thereof; or mixtures of one or more of the above with molecular oxygen. In the absorber the mixed product gas 1 is contacted with the aqueous stream 3 to form an aqueous acrylic acid stream 9 . The aqueous acrylic acid stream 9 formed generally includes from 20 to 95, preferably 35 to 90, and more preferably 50 to 80 percent by weight acrylic acid; from 80 to 5, preferably from 65 to 10, more preferably from 50 to 20 percent by weight water; and up to 8, preferably up to 6, more preferably up to 5 percent by weight acetic acid. Generally, the mixed product gas 1 is fed to the absorber at a temperature from 165 to 400, preferably 200 to 350, more preferably 250 to 325 degrees. The aqueous stream 3 is fed to the absorber at a rate of 0.045 to 0.45 Kg (0.1 to 1.0 pounds) of aqueous per 0.45 Kg (one pound) of hydrocarbon material fed to the reactor depending on the desired concentration of acrylic acid to be recovered from the bottoms of the absorber 2 . The absorber 2 may be any suitable absorber design known in the art. The aqueous acrylic acid stream 9 is then fed to a distillation column 10 wherein it is subjected to azeotropic distillation in the presence of at least one distillation solvent to form an acrylic acid stream 11 . The distillation column may be any suitable distillation column known in the art. For instance, a sieve tray, a dual flow tray design, or a packed column may be used. The distillation solvent or solvents may be any solvent(s) suitable for the azeotropic distillation of an acrylic acid stream. In one embodiment, the solvent is substantially water insoluble, generally having a solubility in water at room temperature of 0.5 weight percent or less, preferably 0.2 weight percent or less. Suitable examples of such a water insoluble solvent include, but are not limited to heptane; heptene; cycloheptane; cycloheptene; cycloheptatriene; methylcyclohexane; ethylcyclopentane; 1,2-dimethylcyclohexane; ethylcyclohexane; toluene; ethylbenzene; ortho-, meta-, or para- xylene; trichloroethylene; trichloropropene; 2,3-dichlorobutane; 1-chloropentane; 1-chlorohexane; and 1-chlorobenzene. In another embodiment, the solvent is selected from ethyl acetate, butyl acetate, dibutyl ether, hexane, heptane, ethyl methacrylate, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, and methyl tert-butyl ketone. In a further embodiment, the distillation solvent is a mixed solvent which includes at least two solvents. Suitable examples of solvents useful in such mixed solvent include, but is not limited to, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, isopropyl acetate, n-propyl acetate, toluene, heptane and methylcyclohexane. The preferred distillation solvent is toluene. In one embodiment, the aqueous acrylic acid stream 9 is fed to a light ends stripper column before being fed to the distillation column 10 . The light ends column strips light ends, including but not limited to, acrolein, formaldehyde, acetaldehyde, propionaldehyde, methyl ether, and methyl vinyl ketone, from the aqueous acrylic acid stream 9 . Generally, the stripping gas used is steam. Emerging from the bottom of the light ends column is an acrylic acid stream which is substantially free of light ends. The acrylic acid stream is then introduced into the distillation column 10 . The stream emerging from the top of the light ends column is recycled back to the absorber 2 wherein some of the stripped acrolein is recovered in the absorber off gas and recycled back to the oxidation reactor thereby improving the yield of acrylic acid. In a further embodiment, the aqueous stream 9 includes a polymerization inhibitor introduced at polymerization inhibitor feeds 20 and 21 . Suitable inhibitors are as described above. In one embodiment, the polymerization inhibitor is 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy, free radical; derivatives thereof or mixtures of 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy, free radical with molecular oxygen. In an alternative embodiment, the polymerization inhibitor is a mixture of 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy, free radical; derivatives thereof or mixtures of 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy, free radical with at least one other inhibitor and molecular oxygen. Certain distillation column designs, such as a sieve tray column, require use of a vapor phase polymerization inhibitor. Examples of suitable vapor phase inhibitors useful in the present invention include, but are not limited to, N-nitrosophenylhydroxylamine and salts thereof, nitric oxide, nitrosobenzene, and p-benzoquinone. Emanating from the bottoms of the distillation column 10 is an acrylic acid stream 11 which is substantially free of water. Generally, the acrylic acid stream 11 has less than 1000, preferably less than 800, more preferably less than 500 ppm of water. The acrylic acid stream may also contain insubstantial amounts of at least one of the following: acetic acid, propionic acid, β-acryloxypropionic acid (AOPA), acrolein, furfural, benzaldehyde, maleic acid, maleic anhydride, protoanemonin, and acetaldehyde. The acrylic acid stream 11 is generally sent to be used as a raw material in acrylic ester or acrylate polymer production. The acrylic acid may be used as is or be further processed, including but not limited, additional distillation to remove specific impurities and further processing to form various grades of acrylic acid. The overhead distillate stream 23 emanating from the top of the distillation column 10 generally includes, but is not limited to, azeotropes of water, acetic acid, and/or acrylic acid with the distillation solvent. For instance, should tol uene be utilized as a distillation solvent toluene/water, toluene/acetic acid, and toluene/acrylic acid azeotropes would be taken overhead in a two liquid phase system. The overhead distillate stream 23 is phase separated into organic and aqueous phases. The phase separation may be done by any means known in the art. In one embodiment, the overhead distillate stream 23 is introduced into a tank 24 and allowed to phase separate into an organic phase 25 and an aqueous phase 26 . The organic phase 25 predominantly includes the distillation solvent. The aqueous phase 26 includes, but is not limited to, acrylic acid, acetic acid, the distillation solvent and water. In one embodiment, the organic phase 25 is recycled back to the distillation column by way of the solvent feed line 27 so that the distillation solvent may be reused. Also, at least a portion of the aqueous phase 26 may be recycled 28 as wastewater directly to aqueous stream 3. Alternatively, at least a portion of the aqueous phase 26 may be recycled 28 as wastewater directly to stripper 6 and then on to aqueous stream 3 after stripping. In another embodiment, at least a portion of the aqueous phase 26 may be recycled 28 as wastewater directly to aqueous stream 3 and at least a portion of the aqueous phase 26 may be recycled 28 as wastewater directly to stripper 6 and then on to aqueous stream 3 after stripping. In this embodiment the stripped wastewater stream 29 and unstripped wastewater stream 4 are combined as wastewater stream 22 and introduced into aqueous stream 3 . It is to be understood that the aqueous phase 26 may be recycled, in part or completely, to another wastewater stream in another acrylic acid manufacturing process. Alternatively, part or all of the organic and aqueous phases may be diverted or treated and released to the environment.

Claims: A process for preparing (meth)acrylic acid involving the catalytic oxidation of at least one hydrocarbon material selected from (isobutylene and isobutane) propylene, acrolein and propane with a molecular oxygen containing gas, comprising the steps of: (A) feeding to an absorption tower (i) a mixed product gas from said catalytic oxidation of said at least one hydrocarbon material with a molecular oxygen containing gas, and (ii) an aqueous stream comprising recycled wastewater derived from a (meth) acrylic acid process stream and less than 3.0 percent by weight acetic acid; (B) contacting the mixed product gas with the aqueous stream in the absorption tower to form an aqueous (meth)acrylic acid stream; and (C) feeding the aqueous (meth)acrylic acid stream to a distillation column, wherein it is subjected to azeotropic distillation in the presence of at least one distillation solvent to form an (meth)acrylic acid solution substantially free of wastewater characterised in that at least a portion of the recycled wastewater is stripped of undesirable components in a stripping column using an absorber off gas stream as the stripping gas, said absorber off gas stream being derived from a (meth) acrylic acid process stream. The process of claim 1, wherein the aqueous (meth)acrylic acid stream is stripped in a light ends stripper before being fed to the distillation column. The process of claim 1, wherein the aqueous stream is 100 percent by weight wastewater. The process of claim 1, wherein the at least one distillation solvent is toluene. The process of claim 1, further comprising: (i) phase separating overheads from the distillation column; (ii) recycling the organic phase back to the distillation column; and (iii) recycling at least a portion of the aqueous phase as wastewater to the stripping column and then as wastewater to the aqueous stream. The process of claim 1, wherein at least one polymerization inhibitor selected from the group hydroquinone; 4-methoxyphenol; 4-ethoxyphenol; 1,2-dihydroxybenzene; catechol monobutyl ether; pyrogallol; 4-aminophenol; 2-mercaptophenol; 4-mercaptophenol; 4-hydroxy-2,2,6,6-tetramethyl piperidinyloxy, free radical; 4-oxo-2,2,6,6-tetramethylpiperidinyloxy, free radical; 4-amino-2,2,6,6-tetramethylpiperidinyloxy, free radical; isomers thereof; derivatives thereof, mixtures of two or more thereof; or mixtures of one or more of the above with molecular oxygen is added to the absorber. The process of claim 1, wherein at least one polymerization inhibitor selected from the group hydroquinone; 4-methoxyphenol; 4-ethoxyphenol; 1,2-dihydroxybenzene; 2-methoxyphenol; p-benzoquinone; phenothiazine; pyrogallol; t-butyl catechol; 4-aminophenol; 2-aminophenol; di-t-butyl nitroxide; 2,2,6,6-tetramethylpiperidinyloxy, free radical; 4-hydroxy-2,2,6,6-tetramethyl piperidinyloxy, free radical; 4-oxo-2,2,6,6-tetramethylpiperidinyloxy, free radical; 4-amino-2,2,6,6-tetramethylpiperidinyloxy, free radical; 4-ethanoyl-2,2,6,6-tetramethylpiperidinyloxy, free radical; 2,2,5,5-tetramethylpyrrolidinyloxy, free radical; isomers thereof; derivatives thereof; mixtures of two or more thereof; or mixtures of one or more of the above with molecular oxygen is added to the distillation column.

Inventors: CHAPMAN JOSEFINA TSENG, DAY JAMES CLARENCE, EBERT DONALD ALAN, KAMINSKI THOMAS ALBERT, MASON ROBERT MICHAEL, TSAY CHORNG-SHYUAN, CHAPMAN, JOSEFINA TSENG, DAY, JAMES CLARENCE, EBERT, DONALD ALAN, KAMINSKI, THOMAS ALBERT, MASON, ROBERT MICHAEL, TSAY, CHORNG-SHYUAN, Day, James Clarence, English Village Apts, Bldg. 5
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 2000
Main classification: C07C57
IPC codes: C07C57, C07C51