CHROMIUM, FERROCHROMIUM, AND FERROCHROMIUM-SILICON A.

Commodity Summary

Chromite ore, the sta rting material for chrom ium metal, alloys, and other chromium produ cts, is not produced in the United States. 1 The metallurgical and chemical industry consumed 93 percent of the imported chromite ore used domestically in 1994; the refractory industry consumed the remainder. The major end uses of chromium metal and ferroalloys were stainless and heat-resisting steel (78 percent), full-alloy steel (8 percent), superalloys (2 percent) and other miscellaneous uses (12 percent).2 Exhibit 1 summa rizes the produc ers of chromium p roducts in 1992. O nly a small amount of the chromite is processed to produce ductile chromium; the rest is used in an intermediate form.3 EXHIBIT 1 SU M M A R Y
OF

PRODUCERS

OF

C H R O M IU M P RODUCTS ( I N 1992) a Location Corpus Christi, TX Marietta, OH Alloy, WV Lehi, UT Industry Chemical Metallurgical Metallurgical Refractory Refractory Metallurgical Refractory Refractory Refractory Chemical Metallurgical

Facility Name American Chrome & Chemicals Inc. Elkem AS, Elke m Metals Co. Elkem AS, Elke m Metals Co. General R efractories Co. Harbison-Walker Refractories Macalloy Corp. National Refractories and Mining Corp. National Refractories and Mining Corp. North American Refractories Co. Ltd. Occidental Chemicals Corp. Satra Concentrates Inc.
a b

Hammond, IN Charleston, SC Moss Landing, CA Columbiana, OH Womelsdorf, PA Castle Hayne, NC Steubenville, OH

- Papp, John. "Chromium," Minerals Yearbook Volume 1. Metals and Minerals 1992. United States Bureau of Mines. 1992. p. 355. - a division of Dresser Industries Inc.

Ferrochromium , an alloy of iron and chrom ium, is used as an a dditive in steel making. Th ere are three major grades of ferrochromium: low carbon, high carbon, and charge grade. In the past, low carbon ferrochromium was required by steel makers to keep the carbon content of steel low. However, improved ladle refining techniques such as argon oxygen decarburization, have allowed the steel industry to use high carbon ferrochromium, which is less expensive.4

John Papp, "Chromium," from Mineral Commodity Summaries, U.S. Bureau of Mines, 1995, p. 43.
2

Ibid, p. 42.

"Chromium and Chromium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. VI, 1993, p. 230. John Papp, "Chromium," Minerals Yearbook Volume 1. Metals and Minerals 1992, U.S. Bureau of Mines, 1992, p. 325.
4

Ferrochromium-silicon is used in the metallurgical industry to produce stainless, alloy, and tool steels and cast irons.5 Ferrochromium-silicon is a smelted produc t of chromite ore; silicon is add ed during the sme lting process. Although a high silicon f errochromium is som etimes produce d as an interme diate in the produc tion of low carbon ferrochromium, no ferrochromium-silicon has been produced in the United States since 1982, and it is unlikely to be produced domestically again.6,7 Ferrochromium-silicon typically contains 34 to 42 percent chromium, 38 to 45 percent silicon and 0.05 to 0.06 percent carbon.8 B. Generalized Process Description 1. Discussion of Typical Production Processes Chromite ore is prepared for processing using several methods, depending on the ore source and the end use requirements. Course clean ore is hand sorted, while fine clean ore is gravity separated. Lumpy ore mixed with host rock may require hea vy-media separation. If the chromite minera l occurs in fine grains intermixed with host roc k, crushing, gravity separation and magnetic separation may be used.9 Chromite ore is typically beneficiated before it is sold, hence many of these operations may not be conducted in the United States. 10 Exhibit 2 is a conceptual diagram of chromite ore processing. Either ferrochromium or sodium chromate is produced, and may be sold or further processed to manufacture other chromium c ompounds, as we ll as chromium meta l. 2. Generalized Process Flow Diagram Ferrochromium Ferrochromium is made by smelting chromite ore in an electric arc furnace with flux materials (quartz, dolomite, limestone, and aluminosilicates) and a carbonaceous reductant (wood chips, coke, or charcoal.) Lumpy ore may be fed direc tly to the furnace, while fin er ore must be agglom erated before it is added to the furna ce. In efficiently operated smelters, furnace dust is collected and resmelted, and slag is crushed and processed to recover chromium. The chromium conte nt of the ferrochrom ium is determined by the chromite ore's chr omium to iron ratio. 11 The production of low carbon ferrochromium requires

John Papp, "Chromium," Mineral Facts and Problems, U.S. Bureau of Mines, 1985, p. 141.

Personal Communication between ICF Incorporated and John Papp, U.S. Bureau of Mines, March 1994.
7

"Chromium and Chromium Alloys," 1993, Op. Cit., p. 232. Ibid, p. 234. John Papp, 1992, Op. Cit., p. 327.

John Papp, "Chromite," Industrial Minerals and Rocks, 6th Ed., Society for Mining, Metallurgy, and Exploration, 1994, p. 210.
11

10

John Papp, 1992, Op. Cit., p. 328.

EXHIBIT 2 C ONCEPTUAL D I A G R A M
OF

C HROMITE O RE P R O C E S S IN G

Graphic Not Available.

Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology, 1993, p. 233.

top blowing with oxygen. Alu minum, or more fre quently, silicon is used as the reducing agen t. Extremely low carb on ferrochromium is made by the simplex process, in which high carbon ferrochromium and oxidized ferrochromium are heated unde r high vacuum. Th e carbon and oxygen form carbon monoxide, leaving a p ure ferrochrom ium with a carbon content of about 0.01 weight percen t.12 Sodium Chroma te and Dichromate Sodium chromate and dichromate are produced at two facilities by a hydrometallurgical process during which ground chrome ore and soda ash are mixed (lime and/or leached calcine are sometimes added as well), roasted in an oxidizing atmosphere, and leached with weak chromate liquor or water, as shown in Exhibit 3.13 The resulting leach liquor is separated from the remaining leach residue. At the American Chrome and Chemicals facility, the roasting/leaching sequence is repeated, that is, two complete chromium extraction cycles are performed prior to removal of the residue. Th e leach residu e is then treated, a s discussed below . The treatmen t residue from this ope ration is classified as a RCRA special waste; it is disposed on-site at both facilities.14 The leach solution contains unrefined sodium chromate; this liquor is neutralized and then filtered (not shown) to remove metal precipitates (primarily alumina hydrate).15 The alumina-fr ee sodium chrom ate may be marke ted, but the predom inant practice is to con vert the chromate to the dichromate form. Occidental Chemicals Corp. uses a continuous process that involves treatment with sulfuric acid, evaporation of sodium dichromate, and precipitation of sodium sulfate (see left output stream from leaching and precipitation operation in Exhibit 3.) Sodium sulfate may be sold as a byproduct or disposed. American Chrome and Chemicals uses carbon dioxide (CO2) to convert the chromate to dichromate (see right output stream from leaching and precipitation opera tion in Exhibit 3.) This pr ocess confers the advantage of not gen erating a sludge. Th e dichromate liquor may be sold as 69 percent sodium dichromate solution or returned to the evaporators, crystallized, and sold as a solid.16 Chromium Oxide Sodium dichromate can be converted into both anhydrous chromic oxide and hydrated chromic oxide.17 To produce anhydrous chromic oxide (not shown), sodium dichromate, sulfur and wheat flour are blended with water, and the resultant slurry is heated in a kiln. The material recovered from the kiln is slurried with water, filtered, washed, dried, ground to size, screened and packaged. To produce hydrated chromic oxide (not shown), sodium dichromate solution and boric acid are blended and heated in a kiln. The reacted material is slurried with water and washed. Most of the washwater from the process is treated with sulfuric acid to recover boric acid. A waste stream containing boric acid and sodium sulfate leave the boric acid recovery unit. The product with some of the final washwater is filtered, rewashed, dried, ground, screened and packaged.18 Chromium Metal

12

"Chromium and Chromium Alloys," 1993, Op. Cit., p. 232. Ibid., p. 275.

13

American Chrome and Chemicals and Occidental Chemical, 1989. Company Responses to the "National Survey of Solid Wastes from Mineral Processing Facilities", U.S. EPA, 1989. Marks, et al., editors, Encyclopedia of Chemical Technology, Wiley Interscience, New York, NY, 1978, pp. 93-94. U.S. Environmental Protection Agency, Report to Congress on Special Wastes from Mineral Processing, Volume II, Office of Solid Waste, July 1990, p. 4-2. Processing of either form of chromic oxide, as well as chromium metal are not primary mineral processing, and are therefore outside the scope of this report. Brief descriptions of these processes have been included for completeness. Versar, Inc., Multi-Media Assessment of the Inorganic Chemicals Industry, Vol. II, Prepared for U.S. Environmental Protection Agency, Industrial Environmental Research Laboratory, August 1980, pp. 3-13 - 3-16.
Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology, 1993, p. 233.
18 17 16 15

14

Chromium meta l can be made either pyrometallurgica lly or electrolytically. In the pyrometallurgical m ethod (not shown), chromium oxide (Cr2O 3) reacts with alum inum powder in a refractory lined vesse l after being ignited with barium peroxid e and magne sium powder. Ch romium metal may also b e made from the oxide by reduction w ith silicon in an electric arc furnace. The chromium from this process is similar to that obtained by the aluminothermic process, except the aluminum content is lower and the silicon content may approach 0.8 percent. Chromium may also be made by reducing chromium oxide briquets with carbon at low pressure and temperatures of 1,275 to 1,400C.19 Exhibit 4 shows the production of electrolytic chromium by the chrome alum process conducted at the Elkem Metals Company's Marietta Plant. High carbon ferrochromium is ground and leached with a hot solution of reduced anolyte, chrome alum mother liquor, and m akeup sulfuric a cid. Cold mother liquor is a dded, and the slurry is filtered to remove the undissolved solids, which are mostly silica. The filtrate is conditioned at elevated temperature for several hours to convert the chromium to the non-alum form. The filtrate is then cooled to 5C, allowing a crude ammonium sulfate to crystallize. This iron salt is further treated to form technical ferrous ammonium sulfate, which can be sold as fertilizer and other purposes. The filtrate is clarified and aged, allowing ammonium chrome alum to precipitate. The slurry is filtered, and the chrome alum is dissolved in hot water. The chrome alum solution is clarified and fed to the electrolysis cell. After the electrolysis is complete, the c athodes are re moved, washed , and the metal is rem oved by air hammers. The metal is crushed, washed, and dehydrogenated.20 3. Identification/Discu ssion of Nov el (or otherw ise distinct) Process(es) Research is being conducted to investigate the feasibility of using plasma smelting both worldwide, as a more efficient way of processing ferrochromium, and in the United States, to utilize low quality chromium bearing ores.21 4. Beneficiation/Processing Boundaries EPA established the criteria for determining which wastes arising from the various mineral production sectors come from miner al processing opera tions and which a re from benef iciation activities in the Sep tember 1989 final rule (see 54 Fed. R eg. 36592, 3661 6 codified at 261.4 (b)(7)). In essenc e, beneficiation op erations typically serve to sepa rate and concen trate the mineral va lues from waste m aterial, remove impu rities, or prepare the ore for further ref inement. Beneficiation a ctivities generally do not cha nge the mineral va lues themselves othe r than by reducing ( e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate processing. A chemical change in the mineral value does not typically occur in beneficiation. Mineral processing operations, in contrast, generally follow beneficiation and serve to change the concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or chemical reactions (e.g., acid digestion, chlorin ation) to change the chemical comp osition of the mineral. In contra st to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming ore or mineral feedstock such that the materials lea ving the operation do not close ly resemble those that e ntered the oper ation. Typically, beneficiation wastes are ea rthen in chara cter, wherea s mineral proces sing wastes are de rived from melting or chemical changes. EPA approached the problem of determining which operations are beneficiation and which (if any) are processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more detailed examination of un it operations, as nece ssary. To locate the be neficiation/proces sing "line" at a given fa cility within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on ore type(s), the functional importance of each step in the production sequence, and waste generation points and quantities presented above in Section B. Ferrochromium EPA determined that for ferrochromium, mineral processing first occurs when the chromite ore undergoes smelting in an electric arc furnace and the physical/ch emical structure of the chromite ore is signific antly altered. Therefore, b ecause EP A has determ ined that all operations following the initial "process ing" step in the produ ction

19

"Chromium and Chromium Alloys," 1993, Op. Cit., pp. 232-234. Ibid., pp. 234-236.

20

J.E. Goodwill, "Developing Plasma Applications for Metal Production in the USA," Iron and Steelmaking, 17, No. 5, 1990, p. 352.
Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology, 1993, p. 233.

21

sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise defined as be neficiation, all solid waste s arising from any such operation(s) after th e initial mineral proce ssing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams ge nerated after the beneficiation/p rocessing line, along with a ssociated informa tion on waste genera tion rates, characteristics, and management practices for each of these wa ste streams. Sodium Chroma te/Dichromate EPA dete rmined that for sodium chromate/dichr omate, mineral pr ocessing occurs a t the "leaching" se quence of the process because the ore is vigorously attacked (digested) with a concentrated acid to significantly change the physical structure of the ore . Therefore, be cause EPA has determine d that all operations followin g the initial "processing" step in the production sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams genera ted after the ben eficiation/processin g line, along with associate d information on was te generation rates, characteristics, and management practices for each of these wa ste streams. Chromium Oxide Since chromium oxide is produced from sodium dichromate, all of the wastes generated during chromium oxide production are m ineral processing w astes. For a descrip tion of where the be neficiation/proces sing boundary occu rs for this mineral commodity, please see the sodium chromate/dichromate section above. Chromium Metal Since chromium metal is produced from either ferrochromium or chromium oxide, all of the wastes generated during chromium oxide production are mineral processing wastes. For a description of where the beneficiation/processing boundary occurs for this mineral commodity, please see the ferrochromium and chromium oxide sections above.

Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology, 1993, p. 233.

EXHIBIT 4 C. Process Waste Streams 1. Extraction and Beneficiation Wastes Wastes from the e xtraction and be neficiation of chrom ite may include gangu e, and tailings. No inform ation on waste chara cteris tics, wa ste gen eration , or was te man ageme nt was a vailab le in the source s listed in the b ibliogra phy. 2. Mineral Processing Wastes The following waste streams have been associated with the production of sodium dichromate, ferrochromium, and ferrochr omium-silicon. Sodium Dichrom ate Production Treated roast/leach residue is classified as a RC RA special w aste. We note, howe ver, that prior to treatmen t, the roast/leach residue is not a RCRA special waste. Treatment of the leach residue consists of treating the residue slurry with either a fer rous or sulfide ion to redu ce hexavale nt chromium followed by treatment with sulfu ric acid to lower the pH leve l. American C hrome and Ch emicals pumps the leach residu e directly to a dedicate d treatment unit, in which sulfuric acid and sodium sulfide are used to induce the desired chemical changes in the residue, while at Occidental Chemicals Corp., the untreated residue is pumped to a wastewater treatment plant which receives, and apparently comb ines, several other inf luent streams prior to tre atment with severa l different chem ical agents. At both plants, the treated residue is pumped in slurry form to disposal surface impoundments. 22 The treated residue from roasting/leaching of chrome ore, is a solid material, though it typically is generated as a slurry containing particle s between 2 mm and about 0.08 m eters (3 inches) in diameter. The treated roast/leac h residue is composed primarily of metallic oxides, such as those of iron, aluminum, silicon, magnesium, and chromium, as well as sulfates.23 Using the available data on the composition of treated roast/leach residue, EPA evaluated whether the residue exhibited any of the four characteristics of hazardous waste: corrosivity, reactivity, ignitability, and extraction procedure (EP) toxicity. The limited available data ind icated that the wa ste did not exhibit any of the four hazardou s waste characteristics. According to the Newly Identified Mineral Processing Waste Characterization Data Set, approximately 102,000 metric tons of treated leach residue are produced annually in the United States. 24 Ferrochromium Dust or Sludge was a listed haza rdous waste that ha s been reman ded, therefore , the agency did not eva luate this material further. Data from the Newly Identified Mineral Processing Waste Characterization Data Set indicate the ollowing constituents above detection limits for untrea ted and treated K091 (baghou se dust): aluminum , antimony, arium, chromium, magnesium, manganese, molybdenum, nickel, selenium, thallium, vanadium, and zinc. Other EP oxicity leachate ana lyses indicated man y of the same constituen ts, as well as lead an d silver. In addition, the data set ndicated that organics were found in the dust or sludge, but did not list them by name or concentration.25 The data set lso indicated that approximately 3,000 metric tons of dust or sludge are produced annually in the United States.26 Additional data is provided in Attachment 1.

22

U.S. Environmental Protection Agency, 1990, Op. Cit., p. 4-2.

Occidental Chemical Corp., Company Responses to the "National Survey of Solid Wastes from Mineral Processing Facilities", U.S. EPA, 1989. U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set, Vol. I, Office of Solid Waste, August 1992, p. I-3.
25 24

23

Ibid, pp. 15-1 - 15-10. Ibid, p. I-4.

26

E L E C T R O L Y TI C C H R O M IU M M ETAL P R O D U C T I O N

Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology, 1993, p. 235.

Slag and Residues - According to the N ewly Identified Min eral Processin g Waste Chara cterization Data Set, approximately 47,0 00 metric tons of slag an d residue are p roduced ann ually in the United Sta tes, and the availab le data do not indicate that the waste is hazardous.27 Ferrochromium -silicon Dust or Sludge was a listed haza rdous waste that ha s been reman ded, therefore , the Agency did not e valuate this material further.28 According to the N ewly Identified Min eral Processin g Waste Chara cterization Data Set, there is no domestic production of ferrochromium-silicon currently. Additional data is provided in Attachment 1. D. Ancillary Hazardous Wastes

Ancillary haza rdous wastes ma y be generated a t on-site laboratories, and m ay include used c hemicals and liq uid samples. Other hazardous wa stes may include spe nt solvents, tank cleanin g wastes, and polychlorin ated biphenyls from electr ical tra nsform ers an d capa citors. N on-haz ardou s waste s may inc lude tir es from trucks and la rge ma chine ry, sanitary sewage, an d waste oil and other lubricants.

27

Ibid. Ibid.

28

BIBLIOGRAPHY Brown, R.E., and G.F. Murphy. "Ferroalloys." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 265-275. "Chromium and Chromium Alloys." From Kirk-Othmer E ncyclopedia of Ch emical Tech nology. 4th ed. Vol VI. 1993 . pp. 228-263. Goodwill, J.E. "Developing Plasma Applications for Metal Production in the USA." Iron and Steelmaking, 17, No. 5. 1990. pp. 350-354. Katayama, H. "Smelting Reduction Process with a Thick Layer of Slag for Producing Ferroalloys and Iron." Materials Transactions, JIM, 33, No. 6. June 1992. pp. 531-542. Papp, John. "Chromite." From Industrial Miner als and Rocks . 6th ed. Society for Mining, M etallurgy, and Explora tion. 1994. p. 210. Papp, John. "Chromium." From Mineral Commodity Summaries. U.S. Bureau of Mines. 1995. pp. 42-43. Papp, John. "Chromium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 139-155. Papp, John. "Chromium." From Minerals Yearbook Volume 1. Metals and Minerals 1992. U.S. Bureau of M ines. 1992. pp. 325-378. Personal Communication between ICF Incorporated and John Papp, U.S. Bureau of Mines. March, 1994. U.S. Environme ntal Protection Age ncy. Newly Identified Mineral Processing Waste Characterization Data Set. Office of Solid Waste. August 1992. U.S. Environmental Protection Agency. "Sodium Dichromate Production." From Report to Congress on Special Wastes from Mineral Processing. Volume 2. Office of Solid Waste. July 1990. pp. 4-1 - 4-12. Vazarlis, H.G., and A. Lekatou. "Pelletising-Sintering, Prereduction, and Smelting of Greek Chromite Ores and Concentrates." Ironmaking and Steelmaking, 20, No. 1. 1993. pp. 42-53. Versar, Inc. Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. II. Prepared for U.S. Environmental Protection Agency, Industrial Environmental Research Laboratory. August 1980.