Method of dehalogenation using diamonds

A method for preparing olefins and halogenated olefins is provided comprising contacting halogenated compounds with diamonds for a sufficient time and at a sufficient temperature to convert the halogenated compounds to olefins and halogenated olefins via elimination reactions.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a method for producing olefins and halogenated 
olefins, and more specifically, this invention relates to a method for 
using diamonds and carbon composite materials containing diamonds to 
catalyze elimination reactions of halogenated compounds to produce olefins 
and halogenated olefins. 
2. Background of the Invention 
Dehalogenation reactions and hydrodehalogenation reactions are combined to 
produce polyvinyl chloride. Current production capacity for polyvinyl 
chloride is approximately 9.8 billion pounds annually. 
The above-mentioned elimination reaction is typically performed thermally 
at temperatures ranging from 500.degree. C. and 600.degree. C. However, 
the use of activated carbons in the reaction mixture has resulted in 
lowering the temperature requirements to between 300.degree. C. and 
400.degree. C. Catalytic cracking on pumice or charcoal impregnated with 
BaCl.sub.2 or ZnCl.sub.2 also has been utilized. However, these procedures 
have not been widely adopted due to the limited life of the resulting 
catalysts. 
Other efforts for enhancing the catalytic activity of activated carbon in 
these reactions include incorporating nitrogen materials into the lattice 
structure of the carbon. While the industrial applicability of the 
resulting carbon material is not known, it is likely that the resulting 
carbon is more expensive than typical activated carbon materials. 
A need exists in the art for a method to produce olefins and 
monohalogenated olefins from dihalogenated aliphatic compounds via 
elimination reactions that can be performed at temperatures much lower 
than those required in thermal processes. The method should be economical 
and also employ a reusable catalyst which does not require any 
preparation. 
SUMMARY OF THE INVENTION 
It is an object of the invention to provide a method for dehalogenating and 
hydrodehalogenating halogenated compounds that overcomes many of the 
disadvantages of the prior art. 
Another object of the present invention is to provide a method for 
converting alkyl halides to olefins and halogenated olefins. A feature of 
the invention is the use of diamonds as a catalyst for the elimination 
reaction. An advantage of the invention is that the reaction can proceed 
at temperatures much lower than those required for thermal reactions. 
Still, another object of the present invention is to provide an economical 
method for producing vinyl chloride. A feature of the invention is the 
dehalogenation and hydrodehalogenation of 1,2 allyl halide using diamond 
catalysts. An advantage of the invention is that the diamond catalyst can 
be utilized for elimination reactions at temperatures of between 
200.degree. C. and 350.degree. C., and preferably between 250.degree. C. 
and 290.degree. C. as compared to 500.degree. C. to 600.degree. C. 
currently used in thermal processes. 
Briefly, the invention provides for a method for preparing olefins and 
monohalogenated olefins comprising contacting halogenated compounds with 
diamonds for a sufficient time and at a sufficient temperature to convert 
the halogenated compounds to olefins. 
Also, provided is a device for producing olefins from halogenated compounds 
comprising an underlayment defining a chamber; a diamond coating on a 
surface of the underlayment; means for hermetically sealing the 
underlayment to an ingress manifold and an egress manifold so as to 
facilitate fluid flow through the chamber; and means for heating the 
chamber. 
A method for producing vinyl chloride is also provided comprising 
contacting 1,2 dichloroethane with a diamond catalyst for a sufficient 
time and at a sufficient temperature to convert the 1,2 dichloroethane to 
a product in a hydrodechlorination reaction.

DETAILED DESCRIPTION OF THE INVENTION 
Generally, the invention provides for a method for economically converting 
halogenated compounds to olefins and halogenated olefins. Surprisingly and 
unexpectedly, the inventors found that contrary to the generally held 
belief, diamonds which contain sp.sup.3 (saturated) carbons are 
catalytically active. Furthermore, the inventors have determined that 
these diamonds are the most reactive carbon-material catalysts for 
elimination reactions such as dehalogenation of halogen-alkanes and 
dehalogenation of 1,2 dihalogen-saturated compounds. 
While the following examples provide conversion data for specific 
halogenated reactants, this is not to be construed as the method being 
relegated to conversion of just those compounds. In fact, any halogenated 
alkanes, including alpha-beta dihalogen-saturated compounds, are 
conversion candidates. Specifically, conversion candidates include, but 
are not limited to, 1,2 dichloroethane, 1,2 difluoroethane, 1,2 
dichlorocylcohexane, 1-chlorohexadecane, 1-flourononane, and combinations 
thereof. Alkyl halogenated aromatics (i.e., aromatic compounds with 
halogenated substitutions on the alkyl moiety) are also suitable 
conversion candidates using the invented method. Any halogenated alkyl 
aromatic is a suitable feedstock. Exemplary aromatics for conversion 
include, but are not limited to chloro-ethyl benzene, fluoroalkyl benzene, 
and 1,2 dichloro-1-phenyl ethane. 
In the case of dehalogenation of alpha-beta dihalogen aliphatic compounds, 
various diamonds catalyze two different reactions at different extents and 
selectivities. In one reaction, hydrodehalogenation is effected with the 
elimination of HCl and the formation of chlorine-containing olefins. In 
the other reaction, dehalogenation, chlorine gas is eliminated and neat 
olefins are produced. 
The invented elimination method, and a device embodying the invented 
elimination process, is depicted in numeral 10 in FIG. 1. 
Generally, the device 10 employs an underlying substrate 12 onto which a 
fixed bed of diamonds 14 positioned. The diamond bed or coating serves to 
define a reaction chamber 15 in which the elimination reactions occur. 
The underlayment or substrate 12 is configured so as to maintain a 
controlled reaction atmosphere in the chamber 15, in that ambient air or 
fluids are excluded from the confines of the chamber formed by the 
underlying substrate. In one embodiment, the underlayment 12 mimics the 
inside surface of a tube or conduit with diamond or carbon catalyst 
material coating the surface. The tubular reaction chamber is adapted to 
be attached to a feed gas manifold 22 and a product egress manifold 24. 
Any weldments 26 or other manifold attachment means which remain intact at 
temperatures up to 400.degree. C. are suitable. Generally, the attachment 
between the substrate and manifolds 22, 24 are such so as to isolate the 
feed gas and product gas from ambient environment. Hermetic seals can 
serve as suitable attachment means 26, particularly when gaseous reactants 
and product are involved. 
In operation, the reaction chamber 15 receives reactant fluid 18 such as 
1,2 dihalogenated compounds. Viscosity of the reactant fluid, at the 
reaction temperature, will determine if the feed is neat or aided by 
carrier fluid 20, such as an inert carrier gas (e.g., nitrogen, argon, 
helium). 
Viscosity of the reactant fluid 18 is adjusted so as to maximize exposure 
of the fluid to the diamond bed. Maximum exposure is typically effected 
when the reactant/diamond weight percent ratios, discussed infra, are 
utilized. Higher reaction temperatures will obviate the need for 
protracted residence times. Required temperatures are provided either via 
external heat application 16, or by preheating the fluid 18 and/or carrier 
gas 20 upstream from the reaction chamber. 
Aside from a tubular fixed bed diamond catalyst bed described above, other 
configurations also can be utilized, as can fluidized bed designs. 
Diamond Detail 
Several types of diamonds, both natural and synthetic, are utilized as 
catalysts in the invented method. The majority of the diamonds have a 
cubic crystalline structure. 
Mono-crystalline and polycrystalline diamonds are suitable catalytic 
candidates. Exemplary mono-crystalline cubic diamonds include many natural 
diamonds, such as those available from Kay Industrial Diamond Corporation 
of Florida. 
Nanosize diamonds are produced by several methods. For example, nanosize 
diamonds are the detonation products of reactions described throughout the 
scientific literature, including "Diamonds in Detonation Soot," NatureVol. 
333, pp 440 (Jun. 2, 1988), incorporated herein by reference. Additional 
methods for producing and modifying nanosized diamonds are disclosed in 
"Influence of the Molecular Structure of Explosives on the Rate of 
Formation, Yield, and Properties of Ultradisperse Diamond," Combustion, 
Explosion, and Shock Waves, Vol. 30, No. 2, pp 235-238 (Plenum Publishing 
Corp., New York, N.Y. 1994), which is a translation of Fizika Goreniya i 
Vzryva, Vol. 30, No. 2, pp. 102-106, March-April 1994, also incorporated 
herein by reference. Nanosize diamonds of from 2-20 nanometers are 
produced in methods described in "Synthesis of Ultradispersed Diamond in 
Detonation Waves" Combustion, Explosion, and Shock Waves, Vol. 25, No. 3, 
pp 372-379, (Plenum Publishing Corp., New York, N.Y. 1994), which is a 
translation of Fizika Goreniya i Vzryva, Vol. 25, No. 3, pp 117-126, 
May-June, 1989, incorporated herein by reference. 
Other sources and methods for obtaining nanosized diamonds can be found in 
U.S. Pat. No. 5,709,577, issued on Jan. 20, 1998, and incorporated herein 
by reference. 
The inventors have found that synthetic nanosize, monocrystalline diamonds 
have a very high activity and selectivity for hydrodehalogenation of 1,2 
halogenated aliphatic compounds versus dehalogenation reactions. 
Furthermore, it was determined that selectivity for the 
hydrodehalogenation reaction is improved by low temperature and shorter 
reaction time. As such, the enhanced hydrodehalogenation catalysis 
provided by nanosized diamonds makes this catalyst particularly attractive 
for low-cost production of vinyl chloride monomer. 
Suitable nanosize diamonds for use in the invented method have particles 
with a diameter of from about 5 to 500 nm and preferably from about 10 to 
about 100 nm. Exemplary polycrystalline diamonds include several 
industrial diamonds, such as the Mypolex products available from 
DuPont.RTM., and some very rare natural diamonds (known as carbonado). 
Table 1 below lists the various diamond types utilized as catalysts in the 
present method. 
TABLE 1 
______________________________________ 
Diamond-based catalysts 
Material Crystalline Structure 
Particle Size 
______________________________________ 
Natural Diamond 
cubic, monocrystalline 
0.1 .mu.m 
Mypolex polycrystalline 0.1 .mu.m 
Nanosize carbon cubic and hexagonal &lt;0.02 .mu.m 
composite (sp.sup.3 + sp.sup.2) 
Nanosize diamonds cubic, monocrystalline &lt;0.02 .mu.m 
______________________________________ 
The catalytic activity of the diamonds was compared with that of other 
carbon materials, namely graphite (at 99+% purity, available through Alpha 
AESAR, Ward Hill, Mass.) having a surface area of 7 m.sup.2 /g; Carbon 
Black BP2000 (available through Cabot Corp., Boston, Mass.) having a 
surface area of 1475 m.sup.2 /g; and silicone carbide (99.8% pure, Alpha) 
at -325 mesh. The results of this comparison are depicted in Examples 8 
through 10, discussed infra. 
Elimination Detail 
The following bench-top, experimental protocol is provided merely to 
illustrate the feasibility of the invented method. As such, the invented 
method is not relegated to such micro test scales but rather as a 
prototype for industrial scale processes, as embodied in the schematic 
illustration of FIG. 1. 
In all laboratory-scaled experiments, reactions were performed in sealed 
Pyrex tubes. Typically, approximately 2 to 100 times more reaction 
substrate by weight is used than diamond catalyst material. Preferable 
weight ratios of substrate to diamond (Substrate weight: diamond catalyst 
weight) are from 2.5:1 to 10:1. As such, the bench-top processes utilized 
25 mg to 50 mg of substrate, and 2.5 to 20 mg of catalyst. 
Temperatures are selected so that no conversion, or less than 3 percent 
conversion, occurs without catalysts. As such, temperatures were selected 
from between 200.degree. C. and 350.degree. C. 
General Elimination Reaction 
Generally, the elimination reaction of monohalogenated compounds proceeds 
by the following reaction: 
EQU H--R.sub.1 --CHX--CH.sub.2 --R.sub.2 --H.fwdarw.HX+HR.sub.1 
--CH.dbd.CH--R.sub.2 --H 
Where: 
R.sub.1 and R.sub.2 are saturated aliphatic moieties (both linear aliphatic 
and saturated rings) having from 0 to 30 atoms of carbon or aromatic 
moieties (e.g., benzene, naphthalene, etc.); and 
X is a halogen (fluorine, chlorine, bromine, or iodine). 
The following elimination reaction removes adjacent or alpha-beta halogens 
from the dihalogenated organic compounds. Either of the two following 
elimination reactions may take place, with various selectivities: 
a: hydrodehalogenation: 
EQU H--R.sub.1 --CHX--CHX--R.sub.2 --H.fwdarw.HX+H--R.sub.1 
--CH.dbd.CX--R.sub.2 --H 
b: dehalogenation: 
EQU H--R.sub.1 --CHX--CHX--R.sub.2 --H.fwdarw.X.sub.2 +H--R.sub.1 
--CH.dbd.CX--R.sub.2 --H 
R.sub.1, R.sub.2, and X are the same as above. 
Although the halogen may be chlorine, fluorine, bromide or iodine, chlorine 
and bromine are the preferred halogens for use with the present process. 
Reaction Detail for 1,2 Dihalogen Conversion 
Trans-1,2 dichlorocyclohexane was used as a model compound for measuring 
diamond catalytic activity in some dehalogenation and hydrodehalogenation 
reactions. 
In the dehalogenation of 1,2,dichlorocyclohexane to cyclohexene (Equation 
1) and the hydrodehalogenation to chlorocyclohexene (Equation 2), the 
following reactions take place simultaneously: 
##STR1## 
Small amounts of the HCl formed in the hydrodehalogenation reaction 
(Equation 2) may react with cyclohexene formed in Equation 1 to form 
chlorocyclohexane (III) in a secondary reaction process depicted in 
Equation 3. 
##STR2## 
Some of the chlorocyclohexenes (III) formed via hydrodehalogenation 
(Equation 2) further eliminate HCl and aromatize to benzene (V). Small 
amounts of cyclohexadiene (IV) and of phenyl-cyclohexane (VI) also were 
observed in some cases. 
Reaction Detail for Halogen-alkane Conversion 
Chlorohexadecane (VII) was used as a model compound for hydrodechlorination 
conversion reactions and F-nonane (VIII) for hydrodefluorination 
reactions. Representative reaction sequences are Equations 4 and 5 below: 
##STR3## 
Examples 1 through 12 reports experimental data as follows: 
1. For trans-1,2 dichlorocyclohexane (Examples 1-8): 
a.) Percent (mole percent) conversion of trans-1,2 dichlorocyclohexane to 
products; 
b.) Percent selectivity of various products; 
c.) Selectivity of aromatization of chloro-cyclohexenes to benzene: 
moles benzene/(moles benzene+moles chlorocyclohexenes) 
d.) Selectivity of hydrodehalogenation reaction versus dehalogenation 
reaction calculated by the following expression: 
(chloro-cyclohexenes+cyclohexadiene+benzene)/(cyclohexene+Cl-cyclohexane); 
in which all quantities are expressed in moles. 
2. For 1-fluorononane and 1-chlorohexadecane conversions (Examples 9-12): 
a.) Percent (mole %) conversion of the initial halogenated paraffins to 
isomers of olefin with the same carbon number. 
Various products and intermediates were obtained with the conversion 
reactions. These products and intermediates are designated in the Examples 
as follows: 
______________________________________ 
Product/Intermediate Number 
Generic Description 
______________________________________ 
I Cyclohexene 
II Cl-cyclohexane 
III Isomers of Cl-cyclohexene 
IV Cyclohexadiene 
V Benzene 
VI Phenyl-cyclohexane 
______________________________________ 
EXAMPLE 1 
Control 
Trans-1,2 dichlorocyclohexane was heated in a sealed Pyrex tube for one 
hour at 290.degree. C. No reaction was observed. 
EXAMPLE 2 
Trans-1,2 dichlorocyclohexane was heated for one hour at 290.degree. C. in 
the presence of 40 weight percent natural diamonds. The following 
conversions and selectivities for both products and reactants were 
obtained. 
______________________________________ 
PRODUCTS 
Time Conversion Selectivity Percents 
(min) (%) I II III IV V VI 
______________________________________ 
60 56 10 39 10 2 27 12 
______________________________________ 
REACTANTS 
Time Conversion Selectivity Percents 
(min) 
(%) V/(III + V), % 
HCl removal/Cl.sub.2 Removal 
______________________________________ 
60 56 72 0.8 
______________________________________ 
EXAMPLE 3 
Trans-1,2 dichlorocyclohexane was heated for one hour at 280.degree. C. in 
the presence of 10 weight percent Mypolex. The following conversion and 
selectivities were obtained: 
______________________________________ 
PRODUCTS 
Time Conversion Selectivity Percents 
(min) (%) I II III IV V VI 
______________________________________ 
60 32 38 37 10 0 11 4 
31 36 37 10 0 14 3 
______________________________________ 
REACTANTS 
Time Conversion Selectivity Percents 
(min) 
(%) V/(III + V), % 
HCl removal/Cl.sub.2 Removal 
______________________________________ 
60 32 53 0.3 
31 58 0.3 
______________________________________ 
Example 3 illustrates the catalytic activity and selectivity of Mypolex and 
also the reproducibility of the micro tests. 
EXAMPLE 4 
Trans-1,2 dichlorocyclohexane was heated at 280.degree. C. for 20, 40, and 
60 minutes in three separate tests, in the presence of 10 weight percent 
nanosize carbon composite. These tests prove that the relative ratio of 
the hydrodehalogenation versus dehalogenation does not change with time 
for the above-mentioned catalyst. 
______________________________________ 
PRODUCTS 
Time Conversion Selectivity Percents 
(min) (%) I II III IV V VI 
______________________________________ 
20 41 26 32 14 3 20 5 
40 47 29 32 12 2 21 4 
60 77 29 37 9 0 19 6 
______________________________________ 
REACTANTS 
Time Conversion Selectivity Percents 
(min) 
(%) V/(III + V), % 
HCl removal/Cl.sub.2 Removal 
______________________________________ 
20 41 58 0.6 
40 47 63 0.6 
60 77 42 0.6 
______________________________________ 
EXAMPLE 5 
Trans-1,2 dichlorocyclohexane was heated for 20 minutes at 280.degree. C. 
and in a separate experiment for 20 minutes at 290.degree. C. In each 
case, the reaction was performed in the presence of 10 weight percent 
nanosize carbon composite. 
______________________________________ 
PRODUCTS 
Time Conversion Selectivity Percents 
(min) (%) I II III IV V VI 
______________________________________ 
280 38 32 22 16 4 21 5 
290 56 21 36 15 0 20 8 
______________________________________ 
REACTANTS 
Temp Conversion Selectivity Percents 
(.degree. C.) 
(%) V/(III + V), % 
HCl removal/Cl.sub.2 Removal 
______________________________________ 
280 38 57 0.6 
290 56 56 0.6 
______________________________________ 
EXAMPLE 6 
Trans-1,2 dichlorocyclohexane was heated at 280.degree. C. for 20, 40, and 
60 minutes in three separate tests, in the presence of 10 weight percent 
monocrystalline cubic nanosize diamonds. 
______________________________________ 
PRODUCTS 
Time Conversion Selectivity Percents 
(min) (%) I II III IV V VI 
______________________________________ 
20 23 12 3 59 4 20 2 
40 31 14 4 58 4 17 3 
60 53 12 6 59 5 13 6 
______________________________________ 
REACTANTS 
Time Conversion Selectivity Percents 
(min) 
(%) V/(III + V), % 
HCl removal/Cl.sub.2 Removal 
______________________________________ 
20 23 25 5.3 
40 31 23 4.5 
60 53 18 4.3 
______________________________________ 
EXAMPLE 7 
In three separate experiments, trans-1,2 dichlorocyclohexane was heated for 
one hour at 270.degree. C., 280.degree. C. and 290.degree. C., each in the 
presence of 10 weight percent nanosize diamonds. The data indicate a 
decrease in the selectivity toward hydrodechlorination with an increase in 
reaction temperature. 
______________________________________ 
PRODUCTS 
Time Conversion Selectivity Percents 
(min) (%) I II III IV V VI 
______________________________________ 
270 7 9 7 28 0 44 12 
280 53 12 6 59 5 13 6 
290 76 5 16 50 2 14 13 
______________________________________ 
REACTANTS 
Temp Conversion Selectivity Percents 
(.degree. C.) 
(%) V/(III + V), % 
HCl removal/Cl.sub.2 Removal 
______________________________________ 
270 7 61 4.6/5.6 
280 53 18 4.3/5.3 
290 76 22 3.1 
______________________________________ 
EXAMPLE 8 
The catalytic reactivity and selectivity of various forms of diamond 
discussed supra were compared with other products. 
Trans-1,2-dichiorocyclohexane was reacted for one hour at 290.degree. C. 
in the presence of various types of diamond materials, graphite, carbon 
black BP 2000, and silicon carbide. The following results were obtained. 
______________________________________ 
Catalyst Conversion, % 
HCl removal/Cl.sub.2 removal 
______________________________________ 
40 wt. % 56 0.8 
Natural Diamond 
10 wt. %* 32 0.3 
Mypolex (0.1 .mu.m) 
10 wt. % 82 0.4 
nanosize carbon 
composite 
10 wt. % 76 3.1 
nanosize diamond 
50 wt. % 36 0.2 
graphite 
10 wt. %** 6 3.8 
Carbon black 
BP 2000 
50 wt. % 13 1.3 
Silicon carbide 
______________________________________ 
*This data was obtained at 280.degree. C. Massive carbon formation is 
observed at higher temperatures. 
**For reactions which were performed at 310.degree. C., conversion was 14 
and the selectivity HCl removal/Cl.sub.2 removal was 1.7. 
The data in Examples 6, 7, and 8 show that nanosize diamonds have a very 
high activity and selectivity for hydrodehalogenation and that their 
selectivity for this reaction is further improved by low temperature and 
shorter reaction times. In fact, this example shows all selectivities 
greater than 4.0. Other examples provide selectivities less than one. 
EXAMPLE 9 
1-fluorononane was heated for one hour at various temperatures in the range 
of 200-310.degree. C. in the presence of various carbon materials. The 
conversion to isononenes was as follows: 
______________________________________ 
Conversion at .degree. C., % 
Catalyst 220 230 240 250 300 310 
______________________________________ 
None -- -- -- -- 1 -- 
Natural Diamond 44 91 96 -- 100 -- 
Mypolex 0 3 63 95 100 -- 
Nanosize Carbon -- -- -- 1 3 100 
Composite 
Nanosize Diamonds 2 100 -- 100 -- -- 
Graphite* 4 7 23 29 -- 
Carbon Black 1 1 91 97 -- 
BP 2000 
Silicon Carbide* -- &lt;2 -- -- -- 
______________________________________ 
*Due to the low surface area, graphite and silicon carbide were used as 5 
weight percent of fluorononane. 
EXAMPLE 10 
In two separate experiments, 1-chlorohexane and 1-chlorohexadecane were 
heated for one hour at 300.degree. C. in the presence of 10 weight percent 
of various catalysts. The conversions to iso-hexenes and iso-hexadecenes 
were as follows: 
______________________________________ 
Conversion % 
Catalyst 1-Cl-nC.sub.6 H.sub.13 
1-Cl-nC.sub.16 H.sub.33 
______________________________________ 
None 0 0 
Natural Diamond 8 7 
Mypolex 18 33 
Nanosize Carbon 57 50 (average) 
Composite 
Nanosize Diamonds 29 -- 
Graphite* 3 10 
Carbon Black 1 3 
BP 2000 
Silicon Carbide* 5 
______________________________________ 
*Due to low surface area, graphite and silicon carbide were used as 50 
weight percent of chlorohydrocarbons. 
EXAMPLE 11 
To assess the competitive reactivity of 1-fluorononane and 
1-chlorohexadecane in the presence of a diamond catalyst, a 1:1 by weight 
mixture of the two compounds was heated for one hour at 300.degree. C. in 
the presence of 10 weight percent of Mypolex (0.1 micron. The conversion 
of the two compounds was calculated as a percent of each initial quantity. 
This example illustrates unexpectedly higher catalytic activity of diamond 
for dihydrofluorination versus dihydrochlorination reactions. 
______________________________________ 
Compound Conversion, % 
______________________________________ 
1-fluorononane 90 
1-chlorohexadecane 29 
______________________________________ 
EXAMPLE 12 
To assess the thermal reactivities of 1-flurononane and 1 chlorohexadecane 
and the thermal interaction between 1-fluorononane and 1-chlorohexadecane, 
several thermal runs were performed at 390.degree. C. for one hour. 
______________________________________ 
Reaction: 
1-F-nC.sub.9 H.sub.19 /1-Cl-nC.sub.16 H.sub.33 
Conversion, % 
molar ratio 1-F-nC.sub.9 H.sub.19 
1-Cl-nC.sub.16 H.sub.33 
______________________________________ 
1:0 0 
0:1 46 (average)* 
1:0.87 75 71 
1:0.03 4 11 
______________________________________ 
*some cracking observed. 
Nonenes (C9-olefins) were a major product of the hydrodefluorination 
reaction of 1-fluorononane in Example 12. It is important to note that 
even at 390.degree. C. in the absence of diamond, no dehydrofluorination 
takes place thermally. Hydrofluorination takes place only in binary 
mixtures of alkyl fluorides and alkyl chlorides. Small amounts of 
1-chlorononane was also formed, probably from the addition of HCl (which 
was formed from hydrodechlorination of Cl-hexadecane) to the nonenes. 
While the invention has been described with reference to details of the 
illustrated embodiment, these details are not intended to limit the scope 
of the invention as defined in the appended claims. 
The embodiment of the invention in which an exclusive property or privilege 
is claimed is defined as follows.