Catalysts are key to direct methanation - C&EN Global Enterprise

Sep 16, 1974 - 168TH ACS NATIONAL MEETING. Among the growing number of coal gasification processes, the upgrading of low-B.t.u. product gas to ...
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tion. In old reactors the necessary con­ trol was achieved by using extreme dilutions of carrier solvents to control heat transfer in the reactors. Better re­ sults are obtained, says Dr. Callihan, with "third generation" reactors, which use no carrier solvents or integral rib­ bon mixers. Though the newer reactors may be more costly in themselves, they compensate economically by permitting use of cheaper ancillary equipment. It is time to reverse the trend of phasing out research on cellulose deriv­ atives, says Dr. Callihan. Cellulose is a quickly renewable resource, he stresses, whose chemistry isn't nearly as formi­ dable as it was once thought to be.

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C&EN Sept. 16, 1974

168TfMG iwioNN. meaiNG Among the growing number of coal

FOOD · COSMETICS PHARMACEUTICALS INDUSTRIAL USES G-V PROCESS

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Catalysts are key to direct methanation

gasification processes, the upgrading of 168TH Λ3 low-B.t.u. product gas to pipeline qual­ ItJIOMM. N\eaiNG ity is of major importance. So far the

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Paulis and his coworker, Dr. Joseph S. Wall. Glutelin appears to further re­ duce the already low lysine content of corns high in zein. Thus, to get a bet­ ter total protein-lysine correlation, βmercaptoethanol is added to the basic alcohol solvent (0.1M) to yield glutelin as well as zein. β-Mercaptoethanol cleaves the disulfide bonds linking polypeptide chains (due to the amino acid cystine), Dr. Paulis explains. The result is a greater turbidity.

An aid to development of high-protein cereal grains comes from the U.S. De­ partment of Agriculture's Northern Re­ gional Research Laboratory in the form of a simpler and quicker method to screen cereals for protein quality. Basi­ cally, the method involves extraction of zein (a protein low in lysine) and sub­ sequent precipitation and measure­ ment of zein by turbidity. Lysine in cereals is important to pro­ tein quality because it is a nutritionlimiting amino acid in cereals. Thus, the proportion of lysine-deficient pro­ tein to total protein provides an index of a cereal's nutritional value. Lysine content varies among the dif­ ferent solubility classes of cereal pro­ teins. In normal and high-lysine corns, an inverse ratio (-0.87) between total lysine content and the amount of zein has been established, USDA's Jerrold W. Paulis told a symposium on chemi­ cal and biological methods for protein quality determination sponsored by the Division of Agricultural and Food Chemistry. Other methods for deter­ mining lysine content in cereals— amino acid analysis, gas chromatogra­ phy, colorimetry, and enzymic and mi­ crobiological methods—have been de­ veloped. But high cost and the necessi­ ty for special technical skills are drawbacks. In the USDA method, ground corn is shaken with a 70% solution of ethanol containing 0.5% sodium acetate. A por­ tion of the supernatant liquor is sepa­ rated and a 1.0% solution of sodium chloride added to precipitate the zein. Turbidity is measured in a colorimeter at590nm. Some corn genotypes exhibit varia­ tions in the amino acid composition of the protein glutelin, as well as in the amounts of glutelin and zein, thereby causing accuracy of the lysine estima­ tion to be reduced, according to Dr.

chief processes have employed multistep gasification procedures in which the methanation (upgrading) of the low-B.t.u. product gas is accomplished separately from primary gasification. The ideal process would accomplish pri­ mary gasification and upgrading in a single step. Technical problems have frustrated a single-step design, but Babcock & Wilcox Co. hasn't given up. B&W's Gordon D. Woolbert told the Division of Fuel Chemistry that the company has been looking into direct production of methane for some time because of the economic advantages in single-step conversion. The attractive­ ness of single-step conversion centers on higher efficiency, which can ap­ proach 90%, compared to a 69% limit for multistep processes. B&W is using a single-step process first conceived at the University of Wyoming several years ago. Though the single-step process is preferable on economic grounds, problems of catalyst maintenance have yet to be overcome. Mr. Woolbert says that most methana­ tion catalysts are forms of nickel and sell for about $3.00 per pound. Unless the catalysts can be maintained for pe­ riods exceeding 15 months, they are too expensive to justify a one-step process. So far all the tests that B&W has run with 55 catalysts indicate that the ac­ tive lifetime of the catalysts is much less than 15 months. The environment around the nickel catalysts is very harsh. In addition to temperatures of 1200° F, there is the presence of many contaminants, the worst ones being sulfur and sulfur com­ pounds. There also are problems with coking of the catalyst and high-temper­ ature sintering. Despite discouraging results with the tests so far, B&W still believes that the one-step methanation process is a good idea and it is continu­ ing the search for a catalyst rugged enough for the process environment.