Material for chromatography

(54) MATERIAL FOR CHROMATOGRAPHY

(75) Inventors: Gregory T. Gaudet, Acton, MA (US);

Agathagelos Kyrlidis, Maiden, MA
(US)

(73) Assignee: Cabot Corporation, Boston, MA (US)

( * ) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days.

(21) Appl. No.: 11/348,538

(22) Filed: Feb. 6, 2006

(65) Prior Publication Data

US 2006/0186047 Al Aug. 24, 2006

Related U.S. Application Data

(62) Division of application No. 10/884,090, filed on Jul. 2, 2004, now Pat. No. 7,008,534, which is a division of application No. 09/944,064, filedonAug. 31, 2001, now Pat. No. 6,787,029.

(51) Int. CI.

B01D 15/08 (2006.01)

(52) U.S. CI 210/635; 210/656; 210/198.2;

210/502.1

(58) Field of Classification Search 210/635,

210/656, 198.2, 502.1; 502/416, 417, 418, 502/437; 264/29.5; 428/707 See application file for complete search history.

(56) References Cited

U.S. PATENT DOCUMENTS

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4,060,592 A 11/1977 Luhleich et al 423/448

(Continued)

FOREIGN PATENT DOCUMENTS

DE 3837724 6/1989 210/198.2

(Continued)

OTHER PUBLICATIONS

Mikes, Laboratory Handbook of Chromatographic and Allied Methods, Ellis Horwood Limited, New York, 1979, pp. 218-224 and 385-391.

(Continued) Primary Examiner—Ernest G. Therkorn

(57) ABSTRACT

Granulated products are provided and include carbonaceous particles and a carbonized agent or binder. The agent or binder is preferably a synthetic resin, pitch component, or mixture thereof. Packing materials for packing columns used in chromatographic separations are also provided as are methods of chromatographic separation using the materials. In addition, methods are provided to provide a variety of different types of carbonaceous products. A variety of chemical groups can be, prior to heat-treatment and/or thereafter, attached to the granules to form modified granules.

14 Claims, 1 Drawing Sheet

U.S. PATENT DOCUMENTS

4,081,370 A 3/1978 Schmitt, Jr. et al 210/39

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FOREIGN PATENT DOCUMENTS

JP 54041296 4/1979 210/198.2

JP 54046247 4/1979 210/198.2

JP 60195012 10/1985 210/198.2

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OTHER PUBLICATIONS International Search Report for PCT/US02/27296. * cited by examiner

1

MATERIAL FOR CHROMATOGRAPHY

This application is a divisional of U.S. patent application Ser. No. 10/884,090, filed Jul. 2, 2004 now U.S. Pat. No. 7,008,534, which in turn is a divisional of U.S. patent 5 application Ser. No. 09/944,064, filed Aug. 31, 2001, now U.S. Pat. No. 6,787,029 B2.

BACKGROUND OF THE INVENTION

10

The present invention relates to a packing material for chromatographic separations and to a method of manufacturing the same. More particularly, the present invention relates to a packing material for liquid chromatography produced by mixing a carbon product, such as carbon black 15 with a synthetic resin and/or a pitch component, granulating the mixture, and heat treating the resultant granules. The present invention also relates to methods of chromatographic separation that employ the granules.

Conventionally, packing materials for liquid chromatog- 20 raphy have included silica gel materials and synthetic resinbased materials. However, problems such as chemical stability, including solubility, have resulted in silica gel-based materials exhibiting poor durability as a packing material.

In chromatography and other separation methods, there is 25 a certain amount of selectivity that is necessary in order for the stationary phase to separate the various components in a mixture. For this reason, carbon products, such as carbon black, have not been used as a standard stationary phase in separation systems because carbon is a strong non-specific 30 adsorbent. This has been disappointing in the past, because carbon products, otherwise, would have many advantages over commercially available adsorbents. For instance, there are no corrosion problems with carbon products nor are there any swelling problems with carbon products. In addi- 35 tion, carbon products can be subjected to large temperature ranges and/or extreme pressures which would be beneficial for certain types of adsorptions, such as temperature swings used in some types of chromatography. In addition, with certain separation processes used in the production of biop- 40 harmaceuticals for clinical applications, the sterilization requirements or recommendations provide for the use of hot sodium hydroxide. With such sterilization procedures, the current separation devices such as silica columns, cannot be used. Further, the polymeric columns such as cellulose 45 polymers, are chemically but not physically stable to such sterilization treatments.

U.S. Pat. No. 5,270,280 relates to the use of carbon black packing materials for liquid chromatography, wherein the carbon blacks have specific dimensional ratios, specific 50 particle diameters and surface areas, and specific micropore volumes. The patent is incorporated herein in its entirety by reference. The methods of making the packing material according to U.S. Pat. No. 5,270,280 include granulating a carbon black-containing mixture and heat-treating the gran- 55 ules at a high temperature in the range of from 800° C. to about 3000° C, in an inert atmosphere. The high temperature heat-treatment is most likely necessary to carbonize and graphitize the binder material in order to form a graphitic layer. According to the patent, if the temperature is below 60 800° C, the graphitization of the binder is not sufficient, resulting in the packing material having insufficient strength. While the patent describes the packing material as providing improved mechanical durability and separating characteristics, a need still exists for an improved liquid chromatog- 65 raphy packing material that has improved mechanical durability and improved separating properties.

2

It is desired to provide an improved liquid chromatographic packing material and a method of producing such a material which does not require a high temperature heattreatment or graphitization step.

In addition, it is desired to provide a method of chromatographic separation that provides improved separation of sample components.

SUMMARY OF THE INVENTION

The present invention relates to an improved chromatographic packing material made of carbonaceous particlecontaining granules preferably having at least one organic group attached thereto. The granules include carbonaceous particles and the carbonized product of a carbonizable synthetic resin, pitch component, or both. Preferred granules include carbon black particles having attached organic groups and a carbonized synthetic resin, pitch component, or both.

The present invention further relates to a process for making the packing material of the present invention and includes: mixing carbonaceous particles with at least one synthetic resin, pitch component, or both, and with at least one organic or aqueous solvent, to form a mixture; granulating the mixture to form granules; heating the granules at a relatively low temperature of from about 400° C. to less than 800° C. to carbonize the synthetic resin, pitch component, or both, and to evaporate the solvent. Once formed, the packing material can be further customized for specific uses by attaching an organic group or groups to the carbon surface.

The carbonized synthetic resin, pitch component, or both, preferably acts to strongly bind the carbonaceous particles into a strong granule, very differently than the temporary binding action of pelletizing or binding agents designed to facilitate ready dispersal of carbon black particles from a pelletized carbon black.

The packing materials of the present invention preferably exhibit excellent mechanical durability and preferably provide improved separating abilities in chromatographic separation applications. The surface-modified granular packing materials of the present invention are particularly useful in liquid chromatographic separation applications.

Additional features and advantages of the present invention will be set forth in part in the description that follows, and in part will be apparent from the description, or may be learned by practice of the present invention. The objectives and other advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the description and appended claims.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a microphotograph (at 5,000x magnification) of chromatographic packing materials of the present invention.

DETAILED DESCRIPTION OF THE PRESENT
INVENTION

The present invention relates to a chromatographic packing material. The carbonaceous particles are preferably