PROCESSES FOR CONVERTING CHLORINATED BYPRODUCTS AND WASTE PRODUCTS TO USEFUL

MATERIALS

The present invention relates generally to processes for converting chlorinated hydrocarbons to less chlorinated products and to the catalysts used in such processes

European Patent Application EP 0496446A, published on July 29, 1992, describes the preparation of chlorotπfluoroethylene and tnfluoroethylene from 1 , 1 ,2-trιchloro- 1 ,2,2- tπ fluoroethane via a catalyst comprised of copper and a Group VIII metal (palladium and platinum being preferred) on a carbon support Several prior publications address the same conversion and describe the same or different catalysts, see, for example EP 025341 OB, EP 0355907B and EP 0459463A None of these publications describes or suggests, however, that other halogenated feedstocks might be suitably catalytically converted to less halogenated and more useful or more salable materials, and in particular none of these references suggest that the catalysts described therein might be useful outside of the fluorocarbon art A seemingly separate course of development has occurred with respect to the class of chlorinated hydrocarbon feedstocks which are exclusive of the chlorofluorocarbon feedstocks (and which will henceforth and for simplicity be referred to geneπcally as the chlorinated hydrocarbon feedstocks)

A number of references relate to the conversion of a chlorinated alkene feedstock to a less chlorinated alkene product German Patent Publication DE 3804265A is exemplary of the known art relating to such processes and catalysts, and describes a method for preparing trichloroethylene from hydrogen and perchloroethyiene over a carrier catalyst of an activated charcoal carrier, copper in an elemental or chemically-bonded (compound) form, rhodium in an elemental or chemically-bonded form, and an organic phosphine or phosphite promoter A provisional specification is referenced in this publication which purportedly describes a method for preparing trichloroethylene from hydrogen and perchloroethyiene, in which the catalyst uses an activated charcoal carrier, copper metal or a copper compound, and elemental palladium, ruthenium or rhodium or a compound thereof

Canadian Patent No 1 ,119,203 is similar to the DE 3804265A reference in describing the conversion of perchloroethyiene to trichloroethylene via a catalyst including an activated carbon carrier, copper metal or a copper compound, one or more of the palladium, ruthenium or rhodium metals or compounds thereof, and optionally, an alkali metal compound as a promoter Earlier processes for converting perchloroethyiene to trichloroethylene in the presence of copper salts on alumina, and including activation by alkali metal salts are also described

The art further describes the catalytic conversion of still other chlorinated hydrocarbon feedstocks to less chlorinated, less saturated products For example, EP 015665 describes the conversion of 1 , 1 ,2-trιchloroethane to ethylene and vinyl chloride via a catalyst

including a noble metal chloride, an alkali metal chloride, iron chloride and optionally copper chloride Other known references relate particularly to the conversion of 1 ,2-dιchloropropane (hereafter, PDC) to the less saturated, less chlorinated propylene

In German Patent Publication No 235,630 A1 (DE '630), for example, PDC is

5 converted to propylene in a catalytic gas phase reaction at temperatures ranging from 170 degrees Celsiu. to 450 degrees Celsius The catalyst is described as an activated carbon which has been treated with a suspension of iron oxides and/or iron oxide hydrates, and then dried at temperatures in the range of 80 degrees to 200 degrees Celsius

Other methods described in DE '630 include the conversion (preferably at 180-250

T O degrees Celsius) in the presence of hydrogen and of a rhodium catalyst of PDC to propylene, the dechloπnation at normal temperatures of PDC to a mixture (9 1 ) of propylene and chloropropylene in the presence of a pure titanium catalyst, and the reductive dehalogenation with sodium sulfide and a phase transfer catalyst of chlorinated hydrocarbons to alkylenes The production of alkylenes from halogenated phosphonate esters under the influence of sulfur

! 5 and olefmating agents containing phosphorus is also described

Still other known references involve the conversion of a chlorinated alkane feedstock such as the aforementioned 1 ,2-dιchloropropane to a corresponding less chlorinated alkane United States Patent No 3,892,818 to Scharfe et al (Scharfe) is illustrative in describing processes for converting hydrocarbon chlorides including 1 ,2-dιchloropropane to hydrogen

2 chloride and hydrocarbons such as propane The processes are conducted in the gas phase in the presence of rhodium-containing catalysts, with the rhodium being present in the catalysts in an elemental state or as a compound and preferably being utilized as part of a carrier catalyst While rhodium can be the sole catalytically active component of the carrier catalysts, it is said that other metals or metal compounds can be included such as, for example, palladium,

25 platinum, ruthenium, indium, iron, cobalt, nickel, copper, gold, vanadium, chromium, molybdenum and tungsten Suitable carriers can be aluminum oxide, silicic acid, aluminum silicate, spinel, active charcoal and titanium dioxide

United States Patents No 4,818,368 to Kalnes et al , 4,899,001 to Kalnes et al , and 5,013,424 to James, Jr et al are similar to Scharfe in describing processes for the hydrogenation

30 of halogenated hydrocarbons in the presence of metal or mixed metal catalysts involving a combination of Group VIB and Group VIII metals "Hydrogenation" in these patents is contemplated as including dehalogenation and olefin saturation in addition to other processes, such as desulfuπzation, denitnfication, oxygenate conversion and hydrocracking A common objective in each of these various references is the conversion of a

35 chlorinated hydrocarbon feedstock which may be formed as a byproduct or waste material of another useful process into a more directly useful or more salable product or products A prime example is the conversion of 1 ,2-dιchloropropane or PDC (as a significant byproduct of the chlorohydπn process for producing propylene oxide) to propylene for recycle to a chlorohydπn

process for producing propylene oxide, for use in the preparation of allyl chloride or for other uses and benefits

Applicants' inventive processes are similarly focused, and provide for the catalytic conversion of various less-desired chlorinated hydrocarbon feedstocks to corresponding, less- chlorinated products in commercially substantial proportions (that is, at yields (defined as the product of the conversion and the selectivity to a corresponding, less chlorinated product, on a hydrogen chloride- and hydrogen-free basis) of at least 10 percent of a given product, but preferably at least 20 percent, and more preferably at least 30 percent), in which a chlorinated hydrocarbon feedstock is reacted with hydrogen in the presence of a supported catalyst

1 o including a selected Group IB metal or metals in an elemental or compound form with a selected Group VIII metal or metals, also in an elemental or compound form The desired product(s) are then conventionally separated from those which are not desired, and may be further processed in a conventional, known manner to be placed in condition for an appropriate use or for sale

! 5 Briefly speaking, four classes of reactions are contemplated with these catalysts

(a) a chlorinated alkane to reaction products including a corresponding less chlorinated alkane in a commercially substantial proportion, as an example, 1 ,2- dichloropropane (or PDC) to propane,

(b) a chlorinated alkene to a corresponding less chlorinated alkane, for example, 2u trichloroethylene to ethane;

(c) a chlorinated alkane to reaction products including a corresponding less chlorinated alkene, for example, PDC to propylene, and

(d) a chlorinated alkene to a corresponding less chlorinated alkene, for example, perchloroethyiene to trichloroethylene

25 " Less chlorinated", as should be clear from the examples given above of reaction classes (a) through (d), embraces still-chlor mated hydrocarbons as well as hydrocarbons having no remaining chlorine atoms associated therewith

The present invention thus embraces the catalytic conversion of a wide array of possible chlorinated hydrocarbon starting materials to corresponding less chlorinated reaction

30 products, including less chlorinated reaction products of the same or different degrees of saturation Preferred chlorinated hydrocarbon feedstocks and their corresponding preferred, less chlorinated hydrocarbon products include, for example PDC and propylene, 2- chloropropene and propylene, 1 ,3-dιchloropropene and allyl chloride, propylene, 2- chloropropane and propylene, 1 ,2,3-trιchloropropane and allyl chloride, propylene, 1 , 1 , 1 ,2-

35 tetrachloroethane to viny dene chloride and ethylene, perchloroethyiene and trichloroethylene, and, 1 ,1 ,2-tπchloroethane and vinyl chloride

The catalysts employed for the various processes in classes (a) through (d) above fundamentally comprise a selected Group IB metal or selected Group IB metals in elemental or

compound form and a selected Group VIII metal or selected Group VIII metals in elemental or compound form on a support Preferred catalysts for processes in classes (a) through (c) will consist essentially of a combination of one or more Group IB metals in elemental or compound form with one or more Group VIII metals in elemental or compound form on a support, however, while for class (d) a combination of Group IB and Group VIII metals with a promoter material from Groups IVB, VA or IVA, or from the organic phosphme, phosphite or phosphonium salt or alkali metal compounds will be preferred More preferably, the catalysts employed in the processes of classes (a) through (c) of the present invention will consist of one or more Group IB metals with one or more Group VIII metals on a support, and for class (d) will 0 consist of one or more Group IB metals with one or more Group VIII metals and a promoter material from Groups IVB, VA or IVA, or from the organic phosphme, phosphite or phosphonium salt or alkali metal compounds

The Group VIII and Group IB metal combinations which are generally favored include platinum (in elemental or compound form) and copper or silver (in elemental or compound form, with copper being preferred to silver) for classes (c) and (d) (in class (d) a promoter material is again preferably included), and platinum/gold or platinum/silver (platinum/gold being more preferred) for classes (a) and (b) Other Group VIII and Group IB metals can be included, but more preferably, the Group IB and Group VIII metals in a given catalyst will consist substantially entirely of platinum and copper in their elemental or o compound forms on the one hand or platinum and gold on the other A most preferred catalyst will employ only platinum and copper or platinum and gold in their elemental or compound forms as the Group IB and Group VIII metals

The proportions and amounts of platinum or other selected Group VIII metal and copper or other selected Group IB metal in these catalysts will of course vary depending on the 5 other circumstances of the catalyst's intended use, but in general terms the selected Group IB metal can be from 0 01 to 20 percent by weight (on an elemental basis) of the catalyst, with platinum or another selected Group VIII metal comprising from 0 01 to 5 0 percent by weight (also on an elemental basis) of the catalyst

More preferably, for classes (a) through (c) the Group IB metal will be from 0 05 to 0 15 percent by weight of the catalyst (on an elemental basis) and the Group VIII metal will be from 0 03 to 3 0 percent by weight of the catalyst, while for class (d) the Group IB metal will be from 0 5 to 18 percent by weight and the Group VIII metal will be from 0 02 to 3 0 percent by weight of the catalyst Most preferably, for classes (a) through (c) the Group IB metal can be from 0 1 to 10 percent by weight of the catalyst (on an elemental basis) and the Group VIII 5 metal will be from 0 05 to 1 0 percent by weight of the catalyst, while for class (d) the selected Group IB metal will be from 1 O to 15 0 percent by weight and the Group VIII metal will be from 0 04 to 1 0 percent by weight of the catalyst

The support in each of these various catalysts can be any of the known conventional supports, but is preferably silica or carbon, with carbon being most preferred The carbon is preferably a high surface area carbon, for example, a carbon having a specific surface area in an unimpregnated condition of 200 m ² / g or more, especially 400 m ² / g or more, and most especially 600 m ² /g or more

An example of a commercially-available carbon which has been found to be well- suited for use in various of the contemplated processes is a coal-based carbon produced by Calgon Carbon Corporation under the designation "BPLF3", and may generally be characterized as having a specific surface area of 1100 m ² /g to 1300 m ² /g, a pore volume of 0 7

T O to O 85 cm ³ /g, and an average pore radius of 12 3 to 14 angstroms Based on an X-ray fluorescence analysis of this carbon, a typical bulk composition of the BPLF3 carbon has been determined to be as follows (by weight percent): silicon, 1 5 percent; aluminum, 1 4 percent, sulfur, 0 75 percent, iron, 0 48 percent; calcium, 0 17 percent; potassium, 0 086 percent, titanium, 0 059 percent, magnesium, 0 051 percent; chlorine, 0 028 percent, phosphorus, 0 026

1-5 percent, vanadium, 0 010 percent, nickel, 0 0036 percent; copper, 0 0035 percent, chromium, 0 0028 percent, and manganese, 0 0018 percent (the remainder being carbon)

Other carbons may be preferable for specific processes within the classes (a) through (d) above For example, either a coconut-based carbon such as produced by Calgon Carbon Corporation under the designation PCB (having a published specific surface area of

20 from 1 150 to 1250 m ² /g and a pore volume of 0 72 cm ³ / g ) or a wood-based carbon such as produced by Calgon Carbon Corp as WSIV Special carbon (having a published or reported specific surface area of 1400 m ² / g, and a pore volume of 1 25 cm ³ /g) is preferred for the conversion of 1 ,2,3-trιchloropropane to propylene because of the lower rate of catalyst deactivation observed with the use of these catalyst supports in this process application as

25 compared to the aforementioned BPLF3 carbon

The reaction conditions preferred for the various processes of the present invention will again vary, depending for example on the particular catalyst and the particular chlorinated hydrocarbon feedstock involved, or whether the process is to be conducted in the gas phase or liquid phase In general, however, in the gas phase processes reaction pressures

30 can range from atmospheric up to 1500 psιg (10 3 Pa (gauge)), with temperatures of from 100 deg C to 350 deg C , residence times of from 0 25 seconds to 180 seconds, and hydrogen/chlorinated alkane or alkene feed ratios ranging on a molar basis from 0 1 . 1 to 100.1 More preferably, reaction pressures will range from 5 psig (0 03 Pa (gauge)) to 500 psig (3 4 Pa (gauge)) with temperatures of from 180 deg C to 300 deg C , residence times of from

35 0 5 seconds to 120 seconds, and hydrogen/chlorinated alkane or alkene feed ratios of from 0 5.1 to 20 1 Most preferably, reaction pressures in the gas phase processes will range from 40 psig (0 28 Pa (gauge)) to 300 psig (2 1 Pa (gauge)), with temperatures of from 200 deg C to 260 deg C , residence times of from 1 second to 90 seconds, and hydrogen/chlorinated alkane or

alkene molar feed ratios of from 0 75.1 to 6 1 In the liquid phase processes (which can be conducted in a batchwise or continuous manner, as desired), it is anticipated that the reaction pressures will generally range from atmospheric up to 3000 psig (20 6 Pa (gauge)), at temperatures of from 25 degrees Celsius to 350 degrees Celsius, residence times of from 1 to 30

5 minutes and hydrogen to chlorinated alkane or alkene molar feed ratios of from 0 1 1 to 100 1 Of the classes of processes described above, the conversion of a chlorinated alkane feedstock to reaction products including (in a commercially substantial proportion, that is, at a yield (defined as the selectivity to a gi en product multiplied by the conversion from a corresponding, more highly chlorinated material, on an hydrogen chloride- and hydrogen-free

10 basis) of a given product of at least 10 percent, but more preferably at least 20 percent and most preferably at least 30 percent) a corresponding less chlorinated alkene is particularly of interest A preferred example from this class of processes is the gaseous-phase reaction of 1 ,2- dichloropropane or PDC with hydrogen to form reaction products including propylene For this particular process, the catalyst is preferably a supported bimetallic

15 platinum/copper catalyst of from 0 01 to 5 0 percent by weight of platinum (calculated on an elemental basis) and from 0 01 to 15 percent by weight of copper (also calculated on an elemental basis) on a carbon support having a specific surface area of at least 200 m ² /g More preferably, the catalyst includes from 0 10 to 3 0 percent by weight of platinum and from 0 05 to 5 percent by weight of copper, and the carbon support has a specific surface area of at least

20 500 m /g Most preferably, the catalyst includes from 0 20 to 1 0 percent by weight of platinum and from 0 1 to 2 0 percent by weight of copper, and the carbon support has a specific surface area of at least 800 m ² / g A particularly preferred carbon is the above-described BPLF3 carbon

Preferably the catalyst for this process (and for other contemplated processes which desirably produce propylene over propane) will have been pretreated by exposure to a

25 chloride source, for example, hydrogen chloride, to improve initial selectivity to propylene over propane and to make the product stream immediately useful in an allyl chloride process (wherein impurity propane in the feed can react with chlorine to produce 1-chloropropane, which because of a similarity in boiling points to allyl chloride is difficult to separate therefrom), for example, or to minimize venting in a propylene oxide process of any propane in

30 the product stream fed or recycled to the propylene oxide process In this regard, catalysts of the present invention which have been impregnated, dried and reduced under hydrogen have been observed to produce propane with decreasing selectivity and propylene with increasing selectivity over time The initial chloride source pretreatment substantially reduces, however, the amounts of venting or downstream processing involved in making use of the product

35 stream in a propylene oxide process or allyl chloride process, respectively

Catalysts that have been pretreated by exposure to a chloride source and not reduced, or which have been merely dried and started up (and which have been in essence treated with hydrogen chloride in situ on start up), have been observed to produce the least

amount of propane initially, albeit with a substantial penalty in conversion For this reason, it is considered that it will generally be preferable to both reduce and pretreat (by exposure to a chloride source) a given catalyst, as opposed to reducing the catalyst solely, or not reducing the catalyst at all in favor of chloride-source pretreatment or treatment with HCI in situ on startup It will also be preferred in the context of this process (and further, in each of the various processes contemplated herein) to employ hydrogen chloride in the feed to reduce coking and catalyst deactivation rates, as exemplified below Preferably the rate of conversion loss is no more than about 0 03 percent per hour, and especially no more than about 0 01 percent per hour The pressure under which the PDC to propylene reaction is conducted preferably ranges from atmospheric pressure to 1500 psig (10 3 Pa (gauge)), more preferably from 5 psig (0 03 Pa (gauge)) to 500 psig (3 4 Pa (gauge)), and most preferably from 50 psig (0 34 Pa (gauge)) to 300 psig (2 1 Pa (gauge)) The temperature will preferably be from 100 deg C to 350 deg C , more preferably will be from 180 deg C to 300 deg C , and most preferably will be from 200 deg C to 260 deg C Preferred residence times will be from 0 25 second ^' s to 180 seconds, more preferably will be from 1.0 seconds to 20 seconds, and most preferably will be from 5 to 15 seconds Hydrogen to 1 ,2-dιchloropropane feed ratios will preferably be (again, on a molar basis) from 0 1.1 to 100.1 More preferably, the hydrogen to PDC feed ratios will be from 0 3 1 to 10 1 , and most preferably from 0 5: 1 to 3 1 Preferably this process will on a commercial-scale further include a recycle stream comprised of any unreacted PDC and 2- chloropropane (as a by-product of the reaction), although as suggested above the amount of 2- chloropropane that is produced is preferably minimized by reduction and chloride source pretreatment of the Pt/Cu bimetallic catalyst

The conversion of a chlorinated alkene feedstock to a corresponding less chlorinated alkene is also of some interest, and a preferred example from this class of processes is the conversion in the gas phase of perchloroethyiene to reaction products including trichloroethylene in a commercially substantial proportion

For this particular process, the catalyst preferably comprises from 0 01 to 5 0 percent by weight of platinum (calculated on an elemental basis), from 0 5 to 20 percent by weight of copper (also calculated on an elemental basis) and from 0 01 to lO percent by weight of a promoter, which is preferably tin or a compound thereof, on a carbon support having a specific surface area of at least 200 m ² /g More preferably, the catalyst includes from 0 02 to 3 0 percent by weight of platinum, from 1 to 15 percent by weight of copper and from 0 02 to 0 75 percent by weight on an elemental basis of tin, and the carbon support has a specific surface area of at least 500 m ² /g Most preferably, the catalyst includes from 0 04 to 1 0 percent by weight of platinum, from 4 to 12 percent by weight of copper and from 0 1 to O 6 percent by weight of tin, and the carbon support has a specific surface area of at least 800 m ² /g A

presently preferred carbon is the wood-based WSIV Special activated carbon (Calgon Carbon Corporation) having a published specific surface area of 1400 m ² /g.

The pressure under which this reaction is conducted preferably ranges from atmospheric pressure to 1500 psig ( 10.3 Pa (gauge)), more preferably from 15 psig (0.10 Pa (gauge)) to 500 psig (3.4 Pa (gauge)), and most preferably from 30 psig (0.21 Pa (gauge)) to 300 psig (2.1 Pa (gauge)). The temperature will preferably be from 100 deg. C. to 350 deg. C, more preferably will be from 160 deg. C. to 280 deg. C., and most preferably will be from 180 deg. C. to 250 deg C Preferred residence times will be from 0.25 seconds to 180 seconds, more preferably will be from 30 seconds to 120 seconds, and most preferably will be from 50 seconds to 100 seconds. Hydrogen to perchloroethyiene molar feed ratios will preferably be from 0.1 : 1 to 100: 1. More preferably, the hydrogen to perchloroethyiene feed ratios will be from 0.3: 1 to 10: 1 , and most preferably from 0.5: 1 to 3.0: 1. Illustrative Examples

The present invention is more particularly illustrated by the examples which follow hereafter. In Examples 1-10, a number of catalyst preparations were evaluated for converting 1 ,2-dichloroρropane to selected reaction products, for example propylene. Several parameters were measured and/or calculated for purposes of comparison, including PDC conversion (100 minus the mol percent of PDC in the test reactor effluent, excluding unreacted hydrogen and the hydrochloric acid produced by the reaction), selectivity to a given component (mols of component divided by mols PDC converted, multiplied by 100), liquid hourly space velocity (in hr ¹ , the volume of liquid PDC fed per hour to the reactor divided by the packed bed volume of catalyst in the reactor), and catalyst productivity (on a basis of kilograms of propylene produced per hour per cubic meter of catalyst used).

For each example in Examples 1-10, PDC was converted to the selected reaction products by flowing hydrogen and PDC in the gas phase over a given catalyst to be evaluated. Liquid PDC was pumped via a piston pump through 1/16th inch (1.6 mm) (O.D.) nickel tubing to a Monel " alloy (Huntington Alloys, Inco Alloys International, Inc.) gas sample cylinder packed with glass beads (unless specifically noted, all fittings and tubing were of Monel '" alloy). The 1/ 16th inch tubing extended to the center of the sample cylinder, with the sample cylinder being heated to a vaporization temperature of 1 10 degrees Celsius by electrical heat tracing. A thermocouple was used to monitor the skin temperature of the sample cylinder.

The flow of the hydrogen feed stream was controlled by a pre-calibrated mass flow controller. The desired flow of hydrogen was passed through the heated sample cylinder, where mixing of the gaseous PDC and hydrogen occurred. The mixed gases were then passed into a charged Monel " tubular reactor (.0.75 in. ^" ( 1.9 cm) O.D., 18 inches (45.7 cm.) in length) heated by ceramic lined electric elements to a desired reaction temperature.

The catalyst (1.2 cubic centimeters) was in each case charged into the reactor between 3 mm glass beads, and placed in the middle of the reactor. The catalyst was thereafter

dried under a flow of nitrogen for one hour at 130 degrees Celsius, and then reduced the catalyst under a 5 1 molar ratio of flowing nitrogen and hydrogen In reducing the catalyst, the temperature was ramped up from 130 to 220 degrees Celsius at 3 degrees per minute, and then held at 220 degrees for a total reducing cycle time of about 2 hours Upon reaction of the mixed hydrogen and PDC in the reactor at a prescribed reaction temperature, the effluent from the reactor passed to a gas sampling valve, which provided gaseous aliquots for online gas chromatographic analysis in a Hewlett-Packard Model 5890 Series II gas chromatograph (Hewlett-Packard Company) The gas chromatograph was equipped with a flame lonization detector, and used 30 meter by 0 53 millimeter (I D ) 100 o percent methyl si 11 cone/fused silica and 30 meter by 0 53 millimeter (I D ) porous polymer-lined fused silica columns to separate the various reaction products Response factors were conventionally determined by injections of gravimetncally-prepared standards of the individual reaction products These response factors were applied in conjunction with individual peak areas and the total mols of all reaction products to determine the mol percents 5 of individual components in the reactor effluent, and the selectivity to individual reaction products as described above Example 1

For this example a bimetallic platinum-copper catalyst was prepared on a carbon support for comparison to platinum on a carbon support alone, to copper on a carbon support 0 alone, and to the carbon support alone

For the platinum-copper catalyst, an aqueous H ₂ P Cl6 stock solution was prepared by dissolving 3 179 grams of H ₂ F»tCl66H ₂ 0 (J T Baker, Inc ; Baker Analyzed Grade, 37 6 percent Pt) in 100 00 mL of deionized and distilled water 0 381 grams of CuCI ₂ (Aldrιch Chemical Company, Inc , 99 999 percent purity) were placed in a 250 mL Erlenmeyer flask, and 8 305 5 grams of the HafHCIe stock solution were added with swirling to dissolve the CuCI The solution was then diluted with 42 64 grams of deionized, distilled water and swirled 40 04 grams of Calgon BPLF3 activated carbon (6 x 16 mesh, Calgon Carbon Corp , Pittsburgh, Pa ) were added to the flask, and the flask was agitated rapidly so that the carbon carrier was evenly coated with the aqueous Pt/Cu solution The catalyst preparation was dried in an 0 evaporating dish in air at ambient temperatures for 18 hours, and then further dried in an oven in air at 120 degrees Celsius for 2 hours before being charged to the reactor and reduced The resulting catalyst was comprised of 0 25 percent by weight of platinum (on an elemental basis) and 0 45 percent by weight of copper (also on an elemental basis)

Similar methods of preparation were used to make catalysts of 0 48 percent by weight of copper on the Calgon BPL F3 activated carbon support (omitting the chloroplatmic acid solution), and of 0 25 percent by weight of platinum on the same activated carbon (omitting the CuCI ₂ from the process)

Reactions were run at various reaction temperatures on the apparatus described above with separate charges of each of these catalysts, as well as running reactions at various temperatures with an unimpregnated Calgon BPLF3 activated carbon support as a test for reactivity of the support Each of the catalysts was loaded into the 18 inch (45 7 cm ) long tubular reactor described above, using about 1 2 cubic centimeters of catalyst The liquid hourly space velocity (LHSV) was 1 25, and the hydrogen and PDC were fed to the reactor at a molar ratio of 6 0 1 Reactor temperatures, PDC conversions, productivities, and individual product selectivities for the runs with these catalysts are shown in Table 1 below Propylene yields for the two runs o with the bimetallic platinum/copper catalyst were thus 30 1 percent (for the 220 degree Celsius reaction temperature, or (30 64 x 98 16)/100), and 67 4 percent (for the 250 degree Celsius reaction temperature, or (70 53 x 95 5)/100)

5

0

5

0

5

TABLE 1

a) 1-CPE = 1-Chloropropene d) 2-CPA = 2-Chloropropane b) C3H6 = Propylene e) 1-CPA = 1-Chloropropane c) C3H8 = Propane

Examples 2-6

In Examples 2-6, platinum-copper catalysts were prepared which used the same activated carbon support as in Example 1. The catalysts were each prepared and reduced as in Example 1 , except that the catalysts for these examples used different amounts of platinum and copper (both on an elemental basis)

In the runs with each of these catalysts, 1.2 cubic centimeter charges of a gi en catalyst were employed in the 18 inch (45.7 cm.) Monel'" reactor, and the hydrogen to PDC feed ratio on a molar basis was set at 5: 1 (rather than the 6: 1 ratio seen in Example 1). Liquid hourly o space velocities and reaction temperatures were varied The results of these runs are shown in

Table 2

5

0

5

0

5

TABLE 2

Example 7

The catalyst prepared for this Example included palladium instead of platinum, along with the copper of previous examples

5 In making the bimetallic palladium-copper catalyst of this example, 0 393 grams of PdCI ₂ (Aldπch Chemical Company, Inc , 99 999% purity) was dissolved in 2 mL of 12M hydrochloric acid (HCI) and diluted to 25 00 mL in a volumetric flask with distilled, deionized water 0 097 grams of CuCI ₂ (Aldrich Chemical Company, Inc , 99 999% purity) was placed in a 50 mL Erlenmeyer flask, and 1 435 grams of the prepared H ₂ PdCI ₄ stock solution was added

10 with swirling to the flask containing the CuCI When the CuCI had dissolved, the resulting solution was diluted with 1 1 00 grams of deionized, distilled water and swirled

10 00 grams of Calgon BPLF3 activated carbon (6 x 16 mesh, Calgon Carbon Corp ) were then added with agitation to coat the carbon evenly with solution, and the catalyst thus prepared was dried in air at ambient temperatures for 18 hours The catalyst, which comprised

15 0 13 percent by weight of palladium on an elemental basis and 0 45 percent by weight of copper on an elemental basis on the activated carbon support, was then further air-dried in an oven at 120 degrees Celsius for 2 hours and reduced as described previously

Three runs were conducted sequentially with this catalyst in the apparatus and according to the general procedure set forth just prior to Example 1 above, using a single 1 2

20 cubic centimeter charge of catalyst in the tubular reactor The results from these runs are shown in Table 3 below, and suggest or show that a palladium/copper catalyst is considerably less active than the previous platinum/copper catalyst (0 25 Pt/0 45 Cu//C) of equimolar proportions for the conversion of PDC to propylene

25

30

35

TABLE 3

TABLE 4

TABLE 5

a) LHSV = Liquid Hourly Space Velocity b) C3H6 = Propylene c) C ₃ H ₈ = Propane d) 2-CPA = 2-Chloropropane e) 1-CPE = 1-Chloropropene

TABLE 6

a) LHSV = Liquid Hourly Space Velocity b) ₃ Hβ = Propylene c) C ₃ H ₈ = Propane d) 2-CPA = 2-Chloropropane e) 1-CPE = 1-Chloropropene oo

Example 8

The catalyst for the sample runs in this example was comprised of 0.25 percent by weight of iridium (on an elemental basis) and 0.45 percent by weight of copper (again, on an

5 elemental basis) on the same activated carbon support used in previous examples.

The iridium-copper catalyst was prepared via a stock solution of lrCI ₄ , by dissolving 0.91 1 grams of lrCI xH 0 (53.4 percent iridium) in 4.988 grams of 0.1 M HCI solution in a 50.00 mL volumetric flask, and diluting this solution to 50.00 mL with deionized, distilled water.

-, 0 0.095 grams of CuCI (Aldrich Chemical Company, Inc., 99.999% purity) were placed in a 50 mL Erlenmeyer flask, and 2.553 grams of the lrCI stock solution were added with swirling to dissolve the CuCI . This solution was diluted with 10.00 grams of deionized, distilled water. 10.00 grams of Calgon BPLF3 activated carbon (6x 16 mesh) were added to the flask, and the flask agitated thoroughly to ensure that the activated carbon was evenly coated with the

15 aqueous solution of lrCI ₄ and CuCI ₂ . The catalyst made in this fashion, with 0.25 percent by weight of iridium (elemental basis) and 0.45 percent by weight of copper (elemental basis) on activated carbon, was air-dried as in previous examples, that is, at ambient temperature for 18 hours and then in an oven at 120 degrees Celsius for another 2 hours, and then reduced.

Three runs were conducted with the catalyst in the apparatus and according to

20 the procedures described previously, with 1.2 cubic centimeter charges of catalyst being charged to the reactor for each set of reaction conditions. The remaining reaction parameters and the results of the runs are as indicated in Table 4 above.

These results suggest or show that the iridium/copper catalyst is generally less selective for converting PDC to propylene than a like-proportioned platinum/copper catalyst.

25 Example 9

The catalyst tested in this example comprised 0.29 percent by weight on an elemental basis of platinum and 0.75 percent by weight of silver on the Calgon activated carbon, and was prepared first by making an aqueous stock solution from 0.048 grams of Pt(NH3) ( θ3)2, 0.1 16 grams of silver nitrate, and 12.43 grams of distilled, deionized water in a

30 50 mL Erlenmeyer flask. The same activated carbon as used in previous examples was then added (at 9.68 grams) to the flask containing the stock solution, and the flask agitated and the catalyst dried as in previous examples. A single 1.2 cubic centimeter charge (weighing 500.1 milligrams) of the catalyst was placed in the reactor dried and reduced, then tests were conducted sequentially with this catalyst at several hydrogen to PDC molar feed ratios.

35 The results from the testing are shown in Table 5 above.

Example 10

For this example, an aqueous F^F'tCle 6H2O stock solution was prepared by dissolving 3.179 grams of H ₂ PtCI ₆ 6H ₂ 0 (J. T. Baker, Inc., Baker Analyzed Grade, 37.6 percent Pt)

in 100.00 mL of distilled, deionized water. A portion (0.995 grams) of this stock solution was added with swirling to a 50 mL Erlenmeyer flask containing 0.134 grams of HAuCI 3H ₂ 0 (Aldrich Chemical Co., Inc., ACS purity) until the HAuCI 3H 0 was dissolved. The solution was diluted with 5.42 grams of distilled, deionized water, and then 4.79 grams of the same acti ated carbon used in previous examples were added to the flask with sufficient agitation to coat the carbon fully with the solution.

The catalyst was air-dried, again as in previous examples, at ambient temperatures for 18 hours and in an oven at 120 degrees Celsius for 2 hours. The catalyst thus prepared comprised 0.24 percent by weight of platinum (on an elemental basis) and 1 .37 o percent by weight of gold (on an elemental basis) on the activated carbon support. These loadings correspond in terms of molar ratio to the 0.25 Pt 0.45 Cu catalyst of Example 1 , and permit a direct comparison of the effectiveness of gold and copper in these catalyst combinations. The same proportions were observed in the other catalysts exemplified herein, that is, palladium and iridium were used in the same molar ratios as platinum in any of the 5 platinum catalysts, and silver, gold and copper were used in the same molar ratios in the various catalysts as well.

A 1.2 cubic centimeter charge (again, about 500 mg in weight) of the catalyst was placed in the test reactor for drying, reduction and evaluation. The results of the single run conducted with this platinum/gold catalyst are summarized above in Table 6, and indicate that 0 although some propylene is produced with this platinum/gold catalyst the dominant product is propane. Examples 1 1-14

Examples 1 1 -14 below focus on the dechlorination of various feedstocks over a supported platinum/copper catalyst of the present invention, with the catalyst having been 5 prepared according to the method of Example 1 above.

In each instance, the particular feedstock to be dechlorinated was pumped via a high pressure syringe pump through 1.6 mm (O.D.) (1/16 inch) Monel'" nickel alloy tubing (unless specifically noted below all of the components, tubing and fittings of the test reactor apparatus were also made of Monel '" nickel alloy (Huntington Alloys, Inco Alloys International, 0 Inc.)) into a packed sample cylinder serving as a feed evaporator.

The 1/16th inch tubing extended almost to the center of the packed cylinder, which was heated to a vaporizing temperature of 180 degrees Celsius using electrical heat tracing. Vaporization of the feedstock was accomplished in the feed line, so that the feedstock was superheated when combined with the hydrogen feed stream. Thermocouples were used 5 to monitor the skin temperature of the feed evaporator and the temperature of the gas exiting the feed evaporator, and the temperature of the feed evaporator was controlled by computer. The hydrogen feed stream was metered to a preheater using a Model 8249 linear mass flow controller from Matheson Gas Products, Inc. Secaucus, N.J., with the preheater

consisting of a packed sample cylinder wrapped with electrical heat tracing Thermocouples were used to monitor both the skin temperature of the preheater and the temperature of the gas exiting the preheater The preheater temperature was set and maintained at 140 degrees Celsius Vaporized feedstock exiting the evaporator was mixed with the hydrogen gas from the preheater in a 2 foot (0 61 meter) long section of 1/4 inch (0 64 cm) tubing maintained at a temperature of 140 degrees Celsius The mixed gases then were passed into and reacted within a tubular reactor ( 1/2 inch (1 27 cm) O D , 12 inches (30 5 cm) in length) located within an aluminum block heated by a cartridge heater and regulated via a computer The catalyst charge (0 6 grams in each of Examples 1 1-14) was generally placed in the tubular reactor over a glass wool support contained in the center of the reactor tubing The catalyst was then covered with a plug of glass wool

The catalyst was dried for from 8 to 24 hours at 150 degrees Celsius under a nitrogen purge The catalyst was thereafter reduced by passing hydrogen through the reactor at a flow rate of 34 mL/minute for 24 hours, and the reactor temperature was lowered to the temperature setpoint of the particular catalyst run The reactor temperature and hydrogen gas flow were allowed to equilibrate for about 1 hour before the liquid feedstock flow was started into the apparatus

After reacting the feedstock and hydrogen in the vapor phase in the tubular reactor thus prepared, the products from the reaction were passed to a gas sampling valve, which provided gaseous aliquots for online gas chromatographic analysis in a Hewlett-Packard Model 5890 Series II gas chromatograph (Hewlett-Packard Company) The gas chromatograph was equipped with a flame lonization detector, and used 30 meter by 0 53 millimeter (I D ) 100 percent methyl si 11 cone/fused silica and 30 meter by 0 53 millimeter (I D ) porous polymer-lined fused silica columns to separate the various reaction products Response factors were conventionally determined by injections of gravimetπcally-prepared standards of the individual reaction products These response factors were applied in conjunction with individual peak areas and the total mols of all reaction products to determine the mol percents of individual components in the reactor effluent, and the selectivity to individual reaction products

The feedstocks, conditions and results of Examples 1 1-14 are reported in Table 7 below.

TABLE 7

Products & Selectivities (%)q

78% C ₃ H ₆ , 10% C ₃ H ₈

62% allyl chloride, 20% C ₃ H ₆

80% C ₃ H ₆ , 20% C ₃ H ₈

44% C ₂ H4, 40% vinyl chloride, 15% C ₂ H ₆

49% C ₃ H ₆ , 49% C ₃ H ₈ 30% C ₃ H ₆ , 20% Peh, 5% allyl chloride

a = 1,2,3TCPa = 1,2,3-trichloropropane b = 2CPa = 2-chloropropane

- = 1,1,2TCEta = 1,1,2-trichloroethane d = Mixture of 30% 2-chloropropene (molar basis), 30% trans-1-chloropropene, 30% cis-1-chloropropene, 10% 1,2-dichloropropane = Individual Component Conversions: 2-chloropropene - 98% t-1-chloropropene - 93% c-1-chloropropene - 98% 1,2-dichloropropane - 100% f - 1,3DCPe = 1,3-dichloropropene g = Balance to 100% are miscellaneous hydrocarbons h = 1CPe = 1-chloropropene

Examples 15-20 Experimental Apparatus and Procedure

Examples 15-20 focus on the gaseous phase reaction, over several catalysts, of hydrogen and perchloroethyiene to produce reaction products including trichloroethylene The experimental apparatus and procedure for these examples are fundamentally like those for Examples 1 - 10 above, except that the reactor used was 1/2 inch (1 27 cm) in outside diameter and was 21 inches (53 3 cm) long instead of 18 inches (45 7 cm), as in the earlier examples Catalysts were charged to the reactor in 20 0 cubic centimeter charges, with a liquid hourly space velocity (LHSV) of 0 075 (LHSV = volume liquid perchloroethyiene fed per

1 hour per packed bed volume of catalyst), a residence time of 47 7 seconds and a hydrogen to perchloroethyiene molar feed ratio of 1 5 1 Analysis of the reaction products was accomplished in a Hewlett-Packard Model 5790 gas chromatograph (Hewlett-Packard Company) The gas chromatograph was equipped with a thermal conductivity detector Indi idual components of the reactor effluent/product stream were separated by a 30 meter by

-15 0 53 millimeter (I D ), 5 percent phenyl, 95 percent methyl silicone/fused silica column

Selectivity to the individual reaction products was determined by dividing the number of moles of an individual reaction product by the number of moles of perchloroethyiene converted, and multiplying by 100 Perchloroethyiene conversion and thus individual component selectivities were calculated on a hydrogen- and hydrogen chloride-free

2o L asι Catalyst productivity was calculated by dividing the number of kilograms of trichloroethylene produced per hour by the cubic meters of catalyst used to produce the trichloroethylene (kg/m3 hr) Example 15

For this example, a catalyst was prepared and evaluated which consisted of 0 1

25 percent by weight on an elemental basis of platinum and 10 percent by weight of copper on a carbon support This catalyst was compared to a catalyst consisting of 0 1 percent by weight of tin and 10 percent by weight of copper

The platinum/copper catalyst was prepared by first dissolving 12 732 grams of CuCI ₂ (Aldrich Chemical Co , Inc , Catalog No 22-201-1 , 97 percent purity, containing

30 approximately 0 46 percent of sodium, 0 13 percent of zinc, 380 parts per million of iron, 120 parts per million of sulfur, 120 parts per million of phosphorus and 500 parts per million of calcium as impurities) in 80 00 mL of distilled and deionized water 60 15 grams of Calgon's WSIV Special activated carbon having a published specific surface area of 1400 m /g were added to the CuCI ₂ solution, and the flask was agitated rapidly to evenly coat the carbon carrier

35 with the CuCI ₂ solution The impregnated carrier was then dried in an evaporating dish in air at ambient temperatures for 18 hours Thereafter, the carbon carrier was further air-dried in an oven at 120 degrees Celsius for 2 hours

An aqueous H ₂ PtCl6 stock solution was then prepared by dissolving 1.342 grams of H ₂ tCl6 XH ₂ 0 (J. T. Baker, Inc., Baker Analyzed Grade, 37.5 percent platinum) in 50.00 mL of distilled, deionized water. 1.000 grams of this solution were placed in a 50 mL Erlenmeyer flask and diluted with 7.00 grams of distilled, deionized water. 9.98 grams of the dried, copper- impregnated carbon carrier were then added to the flask, and the flask agitated to evenly coat the carbon with the aqueous H ₂ F>tCl6 stock solution. The resulting catalyst was then dried in an evaporating dish in air at ambient temperatures for 18 hours, and further dried in an oven in air at 120 degrees Celsius for 2 hours.

The tin/copper catalyst was prepared for comparison by dissolving 0.0329 grams o of Sn(C ₆ H ₅ ) ₄ (Aldrich Chemical Co , Inc.) in 20.00 grams of perchloroethyiene in a 50 mL Erlenmeyer flask. 9.14 grams of the previously-dried, copper-impregnated carbon material were then added to the flask with swirling to evenly coat the carbon with the Sn(CbHs), ₎ solution The catalyst was air-dried, again, in an evaporating dish for 18 hours at ambient temperatures, and then dried for 2 hours at 120 degrees Celsius. 5 After charging, drying and reduction, evaluations were conducted of single charges of the platinum/copper and tin/copper catalysts at several temperatures. The results of these evaluations are provided below in Table 8:

0

5

0

5

TABLE 8

Selectivity (%) trans- CIS- Productivity C?H?Cb 2H _? CI _? (kq/m3_-hr)

22.4

1.2 30.4 2.2 1.8 46.4

3.4 3.9 70.4

4.8 8.0

^a = TCE = trichloroethylene

Example 16

For this example a supported platinum/ tin/copper catalyst was prepared, having 0 l O percent by weight on an elemental basis of platinum, 0 37 percent by weight of tin, and 10 0 percent by weight of copper deposited on the same carbon carrier employed in Example 15

0 122 grams of Sn(C ₆ Hs) was dissolved in 48 69 grams of perchloroethyiene in a 125 mL Erlenmeyer flask 17 23 grams of the previously-dried platinum/copper catalyst were added to the flask with swirling to coat the solution onto the carbon support, and the resulting X Q catalyst was air-dried at ambient temperatures for 18 hours, then at 120 degrees Celsius for 2 hours

A single charge of this catalyst was dried, reduced and evaluated at several reaction temperatures but otherwise under the same overall conditions as in Example 15, with the results shown in Table 9.

15

0

25

30

35

TABLE 9

Productivity

Catalyst Other (kq/m3^hr) 0.1 Pt/0.37Sn/10Cu//C 30.4 65.6 76.8 0.7b 78.4

a = TCE = trichloroethylene

NJ "» b = Vinyl Chloride

Tables 8 and 9 taken together demonstrate a higher perchloroethyiene conversion for the tin-promoted platinum/copper catalyst, as compared to a like platinum/copper catalyst which does not include a promoter material Example 17

A supported platinum/copper catalyst containing 0 044 percent by weight (on an elemental basis) of platinum and 10 O percent by weight of copper was prepared and evaluated in this example The preparation of this catalyst was according to the procedure and materials employed in Example 15, with accommodations for the diminished platinum level The results of the evaluation of a single charge of this catalyst at several temperatures are as shown in Table 10 below

NJ KΩ a = TOE = trichloroethylene b = Vinyl Chloride

Example 18

A supported platinum/copper catalyst was prepared and evaluated for this example which was identical to that prepared in Example 17, but for the use in the present example of a starting CuCI ₂ salt which was 99.999 percent pure as opposed to the 97 percent purity salt of Example 17.

The results from the evaluation of a charge of this catalyst at several temperatures are shown in Table 1 1 as follows:

a = TCE = trichloroethylene

Tables 10 and 1 1 together show that a platinum/copper catalyst made from the particular 97 percent purity copper salt from Aldrich Chemical Co , Inc , yields a higher conversion of perchloroethyiene than does a 99 999 percent pure salt The precise reasons for this difference are not presently known, although it is suspected that several or perhaps all of the various trace metals in the 97 percent purity grade may act synergistically with the prevailing copper and platinum metals Example 19

A platinum/tin/copper catalyst was prepared, charged, reduced and tested in this example which contained 0 044 percent by weight of platinum, 0 023 percent by weight of tin, and 10 0 percent by weight of copper

An aqueous H ₂ PtCl6 stock solution was prepared by dissolving 2 684 grams of H ₂ PtCI ₆ H _ι! 0 (37 5% Pt, J T Baker, Inc , Baker Analyzed Grade) in 100 00 mL of distilled, deionized water 2 122 grams of the stock solution and 10 138 grams of the 97% purity CuCI ₂ Aldrich salt were placed in a 250 mL Erlenmeyer flask, and diluted with swirling with 52 00 grams of distilled water 38 27 grams of Calgon's WSIV Special activated carbon were added to the flask with rapid agitation The catalyst was dried in an evaporating dish in air at ambient temperatures for 18 hours, after which the catalyst was further air-dried m an oven at 120 degrees Celsius for 2 hours A solution of Sn(CeHs) dissolved in C ₂ CI was prepared by dissolving 0 0352 grams of this salt in 40 00 grams of C ₂ CI ₄ in a 250 mL Erlenmeyer flask 42 69 grams of the previously dried catalyst was added to this flask with rapid agitation The catalyst was again air-dried at ambient temperatures for 18 hours, and then m an oven at 120 degrees Celsius for 2 additional hours

The results of the evaluation are as shown below in Table 12.

TABLE 12

^a = TCE = trichloroethylene

Example 20

A platinum/tin/copper catalyst was also prepared in this example, but a CuCI ₂ salt of 99.999 percent purity was used to start rather than a 97 percent purity salt as in Example 19. In addition, the relative amount of tin was increased substantially, from 0.023 percent by weight in the previous example, to 0.15 percent by weight on an elemental basis

The results of testing on a charge of this catalyst at various temperatures are provided in Table 13, all other circumstances and conditions being the same as in the immediately preceding examples:

Catalyst 0.044Pt/0.15Sn/10Cu//C

a = TCE = trichloroethylene

Comparing Tables 12 and 13, the catalyst prepared from the 97 percent purity copper salt again converted more of the perchloroethyiene than the 99 999 percent pure copper salt Examples 21 -25

The experimental method and apparatus of Examples 1 1-14 above were employed (except as indicated below) in these Examples for determining the effects on the rate of catalyst deactivation in converting 1 ,2,3-trιchloropropane to propylene of adding hydrogen chloride (HCI) to a 1 ,2,3-trιchloropropane feed, and of omitting HCI from the feed but using a different wood- or coconut-based carbon support

Bimetallic platinum/copper alloy catalysts were prepared for these examples in the ratios indicated in Table 14, by dissolving H PtCle 6H ₂ 0 (J T Baker, Inc , Baker Analyzed Grade, 37 6 percent Pt) in deionized and distilled water An amount of CuCI ₂ (Aldrich Chemical Company, Inc , 99 999 percent purity) was placed in a 250 mL Erlenmeyer flask, and the H ₂ PtCl _b stock solution was added with swirling to dissolve the CuCI ₂ The solution was then diluted with deionized, distilled water and swirled An activated carbon (Calgon BPLF3 carbon, 6 x 16 mesh, Calgon Carbon Corp , Pittsburgh, Pa for the runs with HCI in the feed, Calgon PCB brand coconut-based activated carbon or Calgon WSIV Special wood-based activated carbon) was added to the flask, and the flask was agitated rapidly so that the carbon carrier was evenly coated with the aqueous Pt. Cu solution

The various catalysts were charged to the reactor and dried under flowing nitrogen at 90 cubic centimeters per minute, at temperatures increasing from 25 degrees Celsius to 120 degrees Celsius at a rate of 3 degrees Celsius per minute with the 120 degree temperature being held for an hour These catalysts were then reduced with flowing hydrogen at 90 cubic centimeters per minute, with the temperature being raised from 120 degrees Celsius to 220 degrees Celsius at 3 degrees per minute and the 220 degree temperature being held for 2 hours

The reaction temperature was set at the same 220 degrees Celsius, with a reaction pressure of 20 pounds per square inch, gauge (0 14 Pa (gauge)), a residence time of 3 5 seconds, a liquid hourly space velocity of 0 91 hr ¹ and a hydrogen to 1 ,2,3-trιchloropropane (TCP) molar feed ratio of 6 0 to 1 Hydrogen chloride when added was metered in as a gas in a 3 0 to 1 molar ratio with respect to the 1 ,2,3-trιchloropropane

Selectivities to allyl chloride and to propylene, as well as percent conversion of the 1 ,2,3-trιchloropropane, were assessed initially for all of the catalysts, and at a later period in time when the percent conversion reached 20 percent for the standard BPLF3 carbon-based catalyst as well as for the runs of the BPLF3 carbon-based catalyst involving HCI in the feed The results are as indicated in Table 14.

TABLE 14

Initial (Pet.) 20 Percent Conversion

Deactivatio

Propylene Allyl Hrs. Propylene Allyl Rate TCP Conversion Selectivity Selectivity Online Selectivity Selectivity (Pct.Conv/

85 85 23 20 80 2.8

55 70 26 136 13 85 0.26

75 85 0.33

25 85 0.4

30 65 0.4

Examples 26-29

These examples compare the effects on conversion and the selectivities to propylene and propane in a PDC to propylene process of pretreating a bimetallic

5 platinum/copper catalyst by exposure to a chloride source (hydrogen chloride) without any reduction of the catalyst under hydrogen, of combining reduction under hydrogen with chloride source pretreatment, of using reduction without any chloride source pretreatment, and of starting up the dried catalyst without prior exposure to a chloride source or reduction A quantity of catalyst was prepared according to the methods described in Examples 21 -25

1 o above, including 0 5 percent by weight of platinum and 0 9 percent by weight of copper on the Calgon BPLF3 carbon support

Using the apparatus and basic procedures of Examples 1 1- 14 and 21 -25, a first catalyst sample was charged to the reactor and dried under flowing nitrogen at 90 cubic centimeters per minute, at temperatures increasing from 25 degrees Celsius to 120 degrees

! 5 Celsius at a rate of 3 degrees Celsius per minute and with the 120 degree temperature being held for an hour The catalyst was then reduced with flowing hydrogen at 90 cubic centimeters per minute, with the temperature being raised from 120 degrees Celsius to 235 degrees Celsius (instead of 220 degrees Celsius, as in Examples 21-25) at 3 degrees per minute and the 235 degree temperature being held for 2 hours The catalyst prepared and treated in this fashion is

20 catalyst "A" in Table 15 below

A second sample was charged and dried from 25 degrees Celsius to 120 degrees Celsius under flowing nitrogen, as with the first sample After holding at 120 degrees for one hour, however, a 50 cubic centimeter per minute flow of hydrogen chloride was introduced and maintained for one half hour The temperature was then raised from 120 degrees to 235

25 degrees Celsius at 3 degrees per minute, under a reducing and chloride-source pretreating flow of 140 cc/min of a 2 1 mixture of hydrogen and hydrogen chloride The resulting catalyst was held at 235 degrees for two hours, and is designated as catalyst "B" in Table 15 below

A third catalyst sample was dried from 25 degrees Celsius to 235 degrees Celsius at a rise of 3 degrees Celsius per minute, under flowing nitrogen at 90 cc/min After holding for 4

30 hours at 235 degrees Celsius, a flow of 50 cc/min of pure HCI was begun and maintained over an additional 4 hours The catalyst "C" in Table 15 corresponds to this third catalyst sample

Finally, a fourth catalyst sample was held under flowing nitrogen (at 90 cc/min ) as the temperature was raised from 25 degrees Celsius to 235 degrees Celsius at 3 degrees per minute, and then maintained at 235 degrees for 3 hours This catalyst is catalyst "D" in Table

35 ¹ 5

Reaction conditions for catalysts "A" and "B" were 235 degrees Celsius, 75 psig (0 52 Pa (gauge)), a liquid hourly space velocity of 0 44 hr ¹ , a residence time of 5 seconds and a hydrogen to PDC molar feed ratio of 3 0 Reaction conditions for catalysts "C" and " D" were

somewhat different, in that the residence time was 10 seconds instead of 5 seconds and the hydrogen to PDC ratio was 1 : 1 instead of 3: 1.

The selectivities to propylene, 2-chloropropane (2-CPa) and propane, as well as the percent of PDC converted, are as summarized in Table 15 for each of the catalysts A-D.

Table 15

Example 30

The feedstock for this run was 1,1,2-trichloroethane. A 0.5 percent by weight of platinum, 0.9 percent by weight of copper on BPLF3 carbon catalyst was prepared, charged, dried, and reduced for use in this Example as in previous Examples. Using the apparatus of Examples 1 1-14, 1 , 1 ,2-trichloroethane was fed with hydrogen to the reactor in a 1 : 1 molar feed ratio and with a 5.0 second residence time, at 76 psig (0.52 Pa (gauge)) and 235 degrees Celsius. Eighty (80) percent of the 1 , 1 ,2-trichloroethane was observed to be converted initially to reaction products including vinyl chloride at 76 percent selectivity, ethylene at 14 percent selectivity, and ethane at 8 percent selectivity.

A second run was then conducted at a 3: 1 molar feed ratio of hydrogen to 1 , 1 ,2- trichloroethane (other conditions being the same), with an initial conversion rate of 84 percent. Products were vinyl chloride at 86 percent selectivity, ethylene at 8 percent selectivity and ethane at 5.5 percent selectivity. Example 31

The apparatus and procedures of Example 30 were used with a feedstock of 1 , 1 , 1 ,2-tetrachloroethane, except that the molar feed ratio of hydrogen to 1 ,1 ,1,2- tetrachloroethane was set at 1.6: 1 and the residence time was 4.0 seconds instead of 5.0. Virtually all of the 1 , 1 ,1 ,2-tetrachloroethane (99.95 percent) was initially converted to reaction products including vinylidene chloride at 93 percent selectivity, vinyl chloride at 1 percent selectivity, trichloroethylene at 3 percent, and ethane and ethylene at 3 percent combined. Catalytic activity declined fairly rapidly thereafter due (it is believed) to polymerization of the vinylidene chloride on the catalyst.

Examples 32-41

The feedstock for these Examples was 2-chloropropane, with propylene the desired product A bimetallic platinum/copper on carbon catalyst was prepared by initially dissolving H ₂ PtCl6 6H ₂ 0 (J T Baker, Inc , Baker Analyzed Grade, 37 6 percent Pt) in distilled, deionized water A portion of this stock solution was added with swirling to a 50 mL

Erlenmeyer flask containing a corresponding amount of CuCI (Aldrich Chemical Co , Inc , 99 999 percent purity) until the CuCI was dissolved The solution was diluted with additional distilled, deionized water, and then Calgon's BPLF3 activated carbon was added to the flask with sufficient agitation to coat the carbon fully with the solution, and to form a catalyst which o after drying and being reduced comprised 0 9 percent by weight of copper and 0 5 percent by weight of platinum

The catalyst was air-dried, reduced and charged as in previous examples The apparatus and procedures of Examples 1 1-14 were again employed to carry out a series of runs with 2-chloroρropane at a constant pressure of 76 psig (0 52 Pa (gauge)), but at varying 5 residence times (see Table 16 below), varying hydrogen to 2-chloropropane molar feed ratios (Table 17) or varying temperatures (Table 18)

Analyses of the reaction products from these runs were carried out as in Examples 1 1 - 14, with reaction conditions and results shown in Tables 16- 18, where "RT" is the residence time, " PE Sel " is the selectivity to propylene, and "PA Sel " is the selectivity to propane. 0

Table 16

Table 17

Table 18

Examples 42-47

The procedures and apparatus described in Examples 1 1-14 were employed with a catalyst (prepared generally as described in previous examples) which was 0.5 percent by weight of platinum, and 0.45 percent by weight of copper on the BPLF3 carbon. The results of these runs (at residence times in the range of 4.6 to 5.6 seconds, at a pressure of 76 psig (0.52 Pa (gauge)), and at various temperature and hydrogen to 2-chloropropane molar feed ratios) are as shown in Table 19.

Table 19

Example 48

For this Example, a bimetallic platinum/copper on carbon catalyst was prepared which contained 0.5 percent by weight on an elemental basis of platinum and 0.9 percent by weight of copper on Calgon BPLF3 activated carbon (6 x 16 mesh, Calgon Carbon Corp., Pittsburgh, Pa.). In making this catalyst, an aqueous H PtCle stock solution was prepared by dissolving H PtCI ₆ 6H ₂ 0 (J. T. Baker, Inc.; Baker Analyzed Grade, 37.6 percent Pt) in deionized and distilled water. An amount of CuCI ₂ (Aldrich Chemical Company, Inc., 99.999 percent purity) was placed in a 250 mL Erlenmeyer flask, and an appropriate amount of the H ₂ t l6 stock solution added with swirling to dissolve the CuCI ₂ . The solution was then diluted with

deionized, distilled water and swirled Calgon BPLF3 activated carbon was added to the flask, and the flask agitated rapidly so that the carbon carrier was evenly coated with the aqueous Pt/Cu solution The catalyst preparation was dried in an evaporating dish in air at ambient temperatures for 18 hours, and then further dried in an oven in air at 120 degrees Celsius for 2

5 hours

Liquid 1 ,3-dιchloropropene was pumped via a piston pump through 1/16th inch ( 1 6 mm) (O D ) nickel tubing to a Monel'" alloy (Huntmgton Alloys, Inco Alloys International, Inc ) gas sample cylinder packed with glass beads (unless specifically noted, all fittings and tubing were of Monel '" alloy) The 1/16th inch tubing extended to the center of the sample

1 o cylinder, with the sample cylinder being heated to a vaporization temperature of 1 10 degrees Celsius by electrical heat tracing A thermocouple was used to monitor the skin temperature of the sample cylinder

The flow of the hydrogen feed stream was controlled by a pre-calibrated mass flow controller The desired flow of hydrogen was passed through the heated sample cylinder,

15 where mixing of the gaseous 1 ,3-dιchloropropene and hydrogen occurred The mixed gases were then passed into a charged Monel'" tubular reactor (0 75 in (1 9 cm ) 0 D , 18 inches (45 7 cm ) in length) heated by ceramic lined electric elements to a desired reaction temperature

The catalyst charge (1 2 cubic centimeters) was placed in the middle of the reactor between 3 mm glass beads The catalyst was thereafter pretreated by drying under a flow of

20 nitrogen for one hour at 130 degrees Celsius, and then by being reduced under a 5 1 molar ratio of flowing nitrogen and hydrogen In reducing the catalyst, the temperature was ramped up from 130 to 220 degrees Celsius at 3 degrees per minute, and then held at 220 degrees for a total reducing cycle time of about 2 hours

Upon reaction of the mixed hydrogen and organic feed (at 220 degrees Celsius,

25 73 5 psig (0 51 Pa, gauge), a residence time of 5 0 seconds and a hydrogen to mixed organic molar feed ratio of 6.1), the effluent from the reactor was passed to a gas sampling valve, which provided gaseous aliquots for online gas chromatographic analysis in a Hewlett-Packard Model 5890 Series II gas chromatograph (Hewlett-Packard Company) The gas chromatograph was equipped with a flame lonization detector, and used 30 meter by 0 53 millimeter (I D ) 100

30 percent methyl si 11 cone/fused silica and 30 meter by 0 53 millimeter (I D ) porous polymer-lined fused silica columns to separate the various reaction products

Response factors were conventionally determined by injections of gravimetπcally- prepared standards of the individual reaction products These response factors were applied in conjunction with individual peak areas and the total mols of all reaction products to determine

3 the mol percents of individual components in the reactor effluent, and the selectivity to individual reaction products on a hydrogen- and hydrogen chloride-free basis The percent of the 1 ,3-dιchloropropene which was converted to these reaction products was also determined on a hydrogen- and hydrogen chloride-free basis

Results of this analysis showed an initial conversion of 100 percent of the 1 ,3- dichloropropene fed, with 2-chloropropane being produced at a selectivity of 7 9 percent, cis- 1 -chloropropene being produced at 38 9 percent, trans- 1 -chloropropene at 7 1 percent, propylene being produced at 42 percent selectivity, 1 -chloropropane at 1 3 percent, 1 ,2- dichloropropane at 2 6 percent, and propane at 0 4 percent The catalyst deactivated quickly thereafter Example 49

The methods and apparatus of Examples 1 1- 14 were employed for converting trichloroethylene to reaction products including ethane over a catalyst of 0 24 percent by weight of platinum and 1 37 percent by weight of gold on the BPLF3 carbon support The catalyst was prepared from a solution of H ₂ PtCl6 H 0 and HAuCI ₄ H ₂ 0 in water, and to which the BPLF3 carbon had been added The catalyst was then dried, charged and reduced under flowing hydrogen as in Examples 1 1-14

At a reaction temperature of 235 degrees Celsius, a pressure of 76 psig (0 52 Pa (gauge)), a 4 9 second residence time, and a molar feed ratio of hydrogen to vaporized trichloroethylene of 2 75, there was a 75 percent conversion of trichloroethylene to reaction products including ethane at 80 percent selectivity, ethylene (16 percent selectivity), cιs-1 ,2- dichloroethylene (2 percent) and vinyl chloride, ethyl chloride, vinylidene chloride, trans-1 ,2- dichloroethylene and 1 ,2-dιchloroethane (or EDC) at less than 1 percent total Example 50

The same catalyst, procedures and apparatus were used as in Example 49, but at a reaction temperature of 235 degrees Celsius, a pressure of 76 psig (0 52 Pa (gauge)), a residence time of 4 9 seconds and a molar feed ratio of hydrogen to trichloroethylene of 5 5 After 23 hours on line, trichloroethylene conversion was at 93 percent, with ethane being produced therefrom at a selectivity of 96 percent, ethylene at 2 percent, cιs-1 ,2-dιchloroethylene at 0 5 percent, and vinyl chloride and the other minor products of Example 1 being produced at a sel ecti vity of less than 0 5 percent Examples 51-55

For these examples, the same apparatus and procedures were generally employed a- in Examples 1 1-14 above to evaluate and compare several different catalyst combinations for converting PDC to propylene Each of these catalysts was prepared from a solution in water of the chlorides of the metals involved, and using the Calgon BPLF3 activated carbon The catalysts were each charged, air- and oven-dried, and reduced with hydrogen in the manner of Examples 1- 10 The reaction temperature for this comparison was 220 degrees Celsius, the pressure was atmospheric, the residence time was 1 second, and the molar feed ratio of hydrogen to PDC was set at 3.1

The percent conversions and the selectivities to various products (in percent) from these runs are provided in Table 20, wherein "2-CPA" is 2-chloropropane:

Table 20

While various embodiments of the processes and catalysts of the present invention have been described and/or exemplified herein, those skilled in the art will readily appreciate that numerous changes can be made thereto which are nevertheless properly considered to be within the scope or spirit of the present invention as more particularly defined by the claims below