JPS58216127A - Dechlorination in presence of zirconium- containing catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an improved method for dechlorinating organic compounds containing vicinal (vlclnal) chlorine atoms. To avoid confusion with other methods, it would be appropriate to mention dechlorination first.

A chlorine atom is removed from a chlorine-containing organic compound to create olefinic unsaturation between the carbon atoms and to form elemental chlorine or, if a chlorine acceptor is present, a chlorine-containing by-product. In such a reaction, fAJn/, /, is the production of vinyl chloride by dechlorination of 2-trichloroethane.

At this time, vinyl chloride is the dechlorination product of /, /, 2-trichloroethane.

On the other hand, in the dehydrochlorination reaction, seven hydrogen atoms
seven chlorine atoms are removed from adjacent carbon atoms to produce olefinic unsaturation between the carbon atoms and also to produce hydrogen chloride. Examples of such reactions are the various dehydrochlorinations of /, /, 2-trichloroethane, where the type of product depends on which hydrogen and which chlorine are removed.

α α HH α ct α α Therefore,
Vinylidene chloride, cls-/,-monochloroethylene,
trans -/, 2-dichloroethylene/, /
, , is the dehydrochlorination product of 2-trichloroethane.

Another example of a dehydrochlorination reaction is the dehydrochlorination of /1,2-dichloroethane.

Thus, vinyl chloride is the dehydrochlorination product of /, cozochloroethane, similar to the dechlorination product of /, /, 2-trichloroethane.

Characterization of compounds as dechlorination or dehydrochlorination products
It should be noted that these are performed with respect to the parent compound produced.

In many cases, both a chlorine-containing organic compound and seven or more organochlorine acceptors are introduced so that the dechlorination and dehydrochlorination reactions proceed simultaneously. IIJU/,
/,,2- Production of vinyl chloride from trichloroethane and ethylene. The general reaction is as follows.

CH2−CH2+CH2αCHα, →2CH2= CH
α 1 H α This overall reaction can be seen as the following three separate reactions.

Dechlorination CH2αC)lα,→CH2=CHαCH2=CH3+ CH2=CH3+ ct2−+ CH, czcH3αDehydrochlorination CH3αC1−12α→C1−12′=CHα+1−I
Ct The above does not imply that elemental chlorine is necessarily produced during the reaction, as the present invention does not wish to be bound by any theory. Nevertheless, viewing it as three simultaneous reactions helps relate the observed products to their mode of formation. As an example, the efficiency of dechlorination of /, /, -1 trichloroethane in the above combined method is determined by the amount of ethylene introduced and /, /,2
- the amount of trichloroethane and vinyl chloride and/or
/, can be ascertained from considering the amount of dehydrochlorination product of 2-trichloroethane and its consequences present in the product. vinylidene chloride in the product,
cls-/, 2-dichloroethylene and/or
A slight decrease in the above compounds without a corresponding increase in compounds derived from trans-/2-dichloroethylene
It shows an increase in dechlorination efficiency.

Dechlorination reactions are often carried out in the presence of catalysts containing alkali metal chlorides and copper chloride. In the method for dechlorinating chlorine-containing organic compounds in the presence of a catalyst containing an alkali metal chloride and a chlorinated steel, the present invention provides a method for dechlorinating chlorine-containing organic compounds in the presence of a catalyst containing an alkali metal chloride and a chlorinated steel. This is an improvement.

Conversion and selectivity are often used to ascertain the effectiveness of zirconium compounds in catalysts. "Conversion rate"
is the base of the compound that changed into the compound in the reaction. The "selectivity" of a starting compound to a particular product compound or group of product compounds is the number of moles of a particular product compound or group thereof relative to the number of moles of feedstock converted to all products of the reaction, expressed in no cents. This is the ratio of

The presence of zirconium compounds in the catalyst can accelerate the dechlorination reaction in several ways. In some cases, the conversion of chlorine-containing organic compounds is increased, but the selectivity to dechlorinated products remains approximately the same. In other cases, the conversion remains approximately the same, but the selectivity is increased.

In still other cases, both conversion and selectivity to dechlorinated products are increased.

α α Chlorine-containing organic compounds are numerous and vary widely in structure. However, the often used chlorine-containing organic compounds are represented by the following structural formula.

α α However, a), R and R are each independently hydrogen, chloro, alkyl, unsaturated aliphatic, alicyclic, or phenyl; 9, b), R and R are each independently hydrogen,
Chloro or alkyl.

The type of alkyl, unsaturated aliphatic, cycloaliphatic groups can vary widely, but usually the alkyl groups are each about 4 tirIA
carbon S atoms, unsaturated aliphatic groups each contain from a to about da carbon atoms, and alicyclic groups each contain from about S to about g carbon atoms. R and R3 each independently represent hydrogen, chloro,
Preferably, it is alkyl or phenyl, and R3 and R4 are each independently hydrogen, chloro, or methyl.

Examples of chlorine-containing organic compounds that can be dechlorinated according to the invention include /, -monodichloroethane, /, /,2-trichloroethane, sym-tetrachloroethane, unsym-tetrachloroethane, pentachloroethane, hexachloroethane, /, -monochloroethane. hmm,/,/,! -trichloropropane, /, 2. ．． 2) Dichloropropane, 2
3-dichlorobutane, 23--)chlorohexane, 3.
lI-nochloro/-pentene, +, 5-cyclo/-hexene, (/, kodichloroethyl)cyclohexane, (/, 2-dichloroethyl)benzene, /,',
2-cyclo/, ,2-/phenylethane, i,
Contains i,a-trichloro-/,λ-diphenylethane. A single organic compound or a mixture thereof containing vicinal chlorine atoms can be used if desired. Preferred chlorine-containing organic compounds are /, /, , 2'-trichloroethane, sym-tetrachloroethane, unsym-tetrachloroethane, pentachloroethane, hexachloroethane. /Q/, J-trichloroethane is particularly preferred.

The catalyst contains an alkali metal chloride, copper chloride, and at least seven dechlorination-promoting zirconium compounds.

Preferably, the catalyst is impregnated on a suitable support, ie the catalyst is in supported catalyst form. Such supports include silica, alumina, silicates, especially silicates of the aluminum and (also Fi)magnesium type. Examples include silica dal, diatomaceous earth, porous alumina, athanorite, Fuller's earth, montmorillonite, bentonite, talc, pyrophyllite, and kaolin. Activated carbon can be used, but
It has been found that the activity of catalysts whose support is essentially all activated carbon decreases rapidly during use and is not easily recovered.

One convenient way in which supported catalysts can be prepared is to dissolve the alkali metal chloride, steel chloride, zolconium compound in a solvent, apply this solution to the support, and evaporate the solvent. A single solution or multiple solutions of different compositions can be used. When desired, alkali metal chlorides, copper chloride, and (
or) Soluble precursors of zorconium compounds can be used.

Water is the solvent most often used, but other solvents or solvent systems can be used.

The copper content of the supported catalyst can vary widely, but is typically about
~about /a weight ratio. Copper amounts in the range of about 3 to about 50% by weight are preferred.

The atomic ratio of the alkali metal in the alkali metal chloride to the copper in the chlorinated steel can also vary widely, but is typically about O9ta:/ to about lI:
The range is /. Atomic ratios ranging from about /:/ to about 3:/ are preferred. An atomic ratio of about 2:/ is particularly preferred. Among the alkali metal chlorides, sodium chloride and potassium chloride are preferred. Particularly preferred is potassium chloride.

The atomic ratio of zirconium in the zorconium compound to copper in M chloride can likewise vary widely. Typically, this atomic ratio ranges from about 0.0/:/ to about 2:/. Approximately θ, /:/
Atomic ratios in the range from to about /:/ are preferred. Approximately o, s”, i
An atomic ratio of is particularly preferred. Among the soluble zirconium compounds that can be used to prepare the catalyst, zirconyl chloride and zirconium tetrachloride are preferred.

Steel(II) chloride and potassium chloride are complex KCuC-t
.

2Cuα4 can be formed in and. Zirconium tetrachloride and potassium chloride can form a complex 2Zrα6.

Although the state of zirconium under scheelite conditions is unknown, it is possible that at least some of the zirconium compounds exist as complexes such as alkali metal chlorides and/or copper chlorides. It is believed that the dechlorination-promoting zolconium compound contains chlorine.

The dechlorination reaction is carried out in the gas phase in fixed bed or fluidized bed reactors.

The temperature at which the dechlorination reaction is carried out can vary widely, but typically ranges from about -30°C to about 0°C. Approximately 300 to approximately 3
Temperatures in the range of 50°C are preferred.

Similarly, the pressure at which dechlorination is carried out can vary widely. The reaction can be carried out at reduced pressure, normal pressure, or elevated pressure.

Substantially reduced pressure and increased pressure above about 30 km/h are only rarely used. The preferred pressure is about θ
to about 700 kPa Cardazo pressure.

Dechlorination reactions can be carried out in the presence of organochlorine acceptors. Organochlorine acceptors are compounds that contain ethylene and/or acetinone unsaturation and are chlorinated by addition under the reaction conditions. Usually the organochlorine acceptor is a hydrocarbon, but substituents can be present provided they do not significantly interfere with the addition chlorination reaction. Examples of suitable chlorine acceptors are ethylene, propylene,
/- Contains butene, copten, and acetylene. Ethylene is preferred. If desired, only seven or more organochlorine acceptors can be used.

The molar ratio of organochlorine acceptor to chlorine-containing organic compound introduced into the dechlorination reaction can vary widely, but is typically about 0.2
! ;'', ranges from 7 to about tI:/.about θ1g:/~
A molar ratio in the range of about S:/ is preferred.

In many cases, when carrying out long runs or when performing a large number of experiments one after the other with the same supported catalyst, the activity of the supported catalyst is often was observed to often decrease. Without wishing to be bound by theory, it is believed that this is due to excessive carbon deposition on the supported catalyst. The supported catalyst is heated in air or steam or a mixture of air and steam at high temperature, usually from about 250°C to about 200°C.
It has been found that the supported catalyst can be reactivated by treatment within the range of . It has also been found that small amounts of oxygen, water vapor, or both oxygen and water vapor can be introduced with the organic feed to slow or substantially prevent deactivation of the supported catalyst.

If water vapor is used, it typically constitutes about 0.0/- to about 0.0/S mole fraction of the total feed material. Approx. 0, S to approx. 7
When using 7-oxygen, oxygen usually accounts for about 0,0 of the total feed material.
/ to about 6 molar fractions. About 0.5 to about damole is preferred.

The invention is further described by the following examples. The examples are intended to be illustrative rather than limiting.

In the examples, the following abbreviations are used:

TCE=/. /,2-trichloroethane, VC
= Vinyl chloride, VDC = Vinylidene chloride, /, 2-DCE =/, Cope chloroethylene (
both isomers), EDC= /,, 2-dichloroethane,
Tθtra = tetrachloroethane (both isomers).

In calculating the selectivity, total vinyl chloride Vi/, /, . 2-trichloroethane was used. /, /, 2-The vinyl chloride produced in excess of the stoichiometric amount attributable to 1-dichloroethane was attributed to ethylene. All 7,2-dichloroethane produced for reporting purposes, regardless of whether the 2-dichloroethane produced is in υ excess over the stoichiometric lid attributable to ethylene
-Dichloroethane was derived from ethylene.

The dechlorination to dehydrochlorination ratio is a measure of the degree of dechlorination to dehydrochlorination that occurs during the reaction. Numerically, this is equal to the selectivity of /, /, 2-trichloroethane to vinyl chloride divided by the sum of the selectivities of /, /, J-trichloroethane to the dehydrochlorination product7.
The productivity is Fi/hour per supported catalyst/f per mmol of both cynovinyl chloride and 9.2-dichloroethane.

Example/Ct+ct2-. in water yotst. 2H,05,/,,
2 f (0.03 mol), ZrOα, -gH,09,
A7 f (0.03 mol), α B, 7/ f (
0.09 mol) solution, Davison grade! ;7
(Davlson Grade 37) Added to Silica Dull 30, Of. Most of the water was evaporated on a hot plate. After drying at 130°C and then at 3SO°C, the weight of the supported catalyst on the produced Cu/Zr/3 was 'l-3.3
It was 9.

It has an inner diameter of 2.2 cm, a length of 10 cm, and a diameter of 0. A
A quartz tube containing a , 3 kcm glass thermowell was used as the reactor. A vessel Schig ring, a supported catalyst, and then a porcelain Raschig ring were introduced in sequence such that the resulting supported catalyst was held in place by the Raschig ring.

The quartz reactor was placed in a horizontal tube furnace with the supported catalyst bed in the center. Ethylene and TCE were mixed through separate flow needles into a 1-shaped tube, and from the 1-shaped tube a stainless steel copper tube with a diameter of θ-3/75 cm immersed in an oil bath at 7.20 to 730°C was passed.
It was then sent to a reactor.

The effluent from the reactor was passed through a fufusco cooled in a water bath, passed through a sample collection port, and then passed through a λ1 solid water bubbler.
r bubbler) and sent to a wet test meter. During each experiment, two or three gas samples were taken for gas chromatographic analysis. At the end of each experiment,
The liquid product was analyzed by gas chromatography.

The experiment was conducted at approximately normal pressure.

Table 1 shows the combined data for two experiments conducted at 0°C and seven experiments conducted at 900°C. Positive and negative numbers Fi &! indicates the standard deviation of multiple experiments at θ°C.

Table 1: Reaction Examples of TCE and Ethylene Cut2-. in Water 3S-. 2+, o! ;, /-29
(θ, 03 mol), Kα2. A solution of λ39<0.03 mol) was mixed with Davison grade S7 silica glue ao, ot
added to.

Most of the water was evaporated on a hot plate with intermittent stirring. First, after drying at 730° C. overnight and then at 3 SO° C. for 1 hour, the weight of the produced Cu/supported catalyst was 5 tons.

CuC1,·;lH3O in water 37-! ;, /, 29
(0.03 mol), ZrOα, @gH, 09, Otsu 79
(0.03 mol), Kα2.23? (0.03 mol) of Davison Grade S7 Silica Glu 30. O
Added to f. Most of the water was evaporated on a hot plate with intermittent stirring.

First, after drying at /3θ℃ overnight, then at 3Sθ℃ for 9 hours,
The weight of the produced Cu/zr/K supported catalyst is 3g, g'?
Met.

CuCl2・,2)-1,05,/,A in water go-
9 (0.03 mol), ZrOα, ・gH20q, Otsu 7
9 (0,03 mol), ni α da, '17 f (0, (M
mol) solution of Davison Grade S Cusilica Glu 30
．． Added to ot. Before mixing, mix both the upper fie solution and the silica gel with g! ;Heated to -90°C. The flask containing the above solution and silica gel was placed on a Rincon rotary evaporator (Rlnc).
Most of the water was evaporated at a water bath temperature of 5 to 99° C. and an absolute pressure of 10 kilograms. Apply pressure 7.3
The pressure decreased to kilopascals absolute and continued evaporation. 3 left O℃
After drying, the weight of the obtained Cu/Zr/2 supported catalyst was 'I/, 4L1. ? Met.

Cuα in water tIo-, @, 2H20! ;, /,2
t (0,03 mol), ZrOCl2-gH209, Otori t (0,03 mol), KCl, 911 f (0,7
, 2 mol) of Davison grade S7 silica dal 3 o, ot. Most of the water was evaporated on a hot plate with intermittent stirring.

First, after drying at 730℃ overnight, then at 330℃ for t hours,
The weight of the produced Cu/Zr/4tK supported catalyst is lS, lit
Met.

Experiments were carried out at 350° C. using the supported catalyst prepared above and the quartz reactor system of Example/using TCE and ethylene as feed materials. Experiments were conducted at approximately normal pressure.

The data are shown in Table 1. Table 2 also includes data from two experiments using the Cu/Zr/JK supported catalyst at 3 kO<0>C reported in Example/.

Plus and minus numbers indicate standard deviation of two experiments.

Example 3 Experiments were conducted at 1 Ioo<0>C using the three supported catalysts prepared in Example 1 and the quartz reactor system of Example 1, with TCE and ethylene as feed materials.

Experiments were conducted at approximately normal pressure. The data are shown in Table 3. Plus and minus numbers represent the standard deviation of two experiments.

Table 3 Examples of water 10θ-medium o CuCl2-JH20! r, /2 f
(0.03 mol), Kα+, +71<0. θ otsu mole)
A solution of Davison Grade S Xilicaglu 30. Of
added to.

Before mixing, both the above solution and silica gel are heated to 3-90℃.
heated to. Place the flask containing the above solution and silica gel in a Rincon rotary evaporator? tθ at a water bath temperature of O~qg℃
Most of the water was evaporated at an absolute pressure of kilopascals. The pressure was then reduced to 7.3 kg/IP skull absolute and evaporation continued. After drying at 730°C overnight and then at 330°C for an hour, the weight of the catalyst supported on Cu/2 produced was 37.3?
Met.

Several other types of supported catalysts were made using this general procedure. Table 4 shows the type of catalyst and the raw materials used for its production. Davison grade S7 silica was used in all cases.

Using the supported catalyst prepared above and the quartz reaction system of Example/2, experiments were carried out at 33θ°C using TCE and ethylene as feed materials. Experiments were conducted at approximately normal pressure.

The data are shown in Table 3.

Example S Inner diameter, 2. ! Cu/θ, Zr/2 and supported catalyst 3/l, which were used in Example 2, were added to a nickel mother plate having a concentration of 1 cm. The supported catalyst bed was held in place by a porcelain Raschig ring. This nickel reactor was converted into a Lindperk tube furnace.
(furnace). Ethylene and TCE were passed through separate flow meters to a mixing tube, from the tube through a preheater maintained at 130° C., and then to the reactor. The effluent from the reactor was sequentially routed to a control valve used to regulate the pressure in the reactor, an ice water cooled receiver, two water bubblers, and a wet test meter. The composition of the off-gas was determined periodically in each experiment by removing it through a rubber septum located between the entire sample receiver and the first water bubbler and immediately injecting the sample into a gas chromatograph. The composition of the liquid was also determined by chromatography. Experiments were conducted at 330°C.

The data for the /l experiments performed in sequence are shown in Table 6. 6th
Before some of the experiments shown in the table and after run number/lI, the supported catalyst was treated with air overnight at 20°C. In three cases, i.e. before run number 7 and /2 and after run number /4', the off-gas from the air treatment was bubbled through a potassium hydroxide solution and the amount of carbon on the catalyst was estimated from the amount of potassium carbonate produced. . The amount of carbon on the supported catalyst is /, t, o, qq t, o, sb, respectively.
It turned out to be t.

Example 6 Cuα, -aH2on, os t in water/20-
(0.70 mol), Zr0C1,2・gH20/Otsu,/
/t (0,0!rmol), niC1,/Hiro, qOt(
A solution of 0, Both the above solution and silica gel were heated to gS ~90°C before mixing. Place the flask containing the above solution and silica gel in a Rincon rotary evaporator, and
Most of the water was evaporated at a water bath temperature of ˜95° C. and an absolute pressure of lIO kilopascals. The supported catalyst was first heated to 730°C and then heated to 3! ; Dry at 0°C. After evaporation of water, the supported catalyst stuck to the inside of the flask. This was shaved and sifted for 9 minutes.

30% of the product was passed through a 20 mesh sieve (US sieve series) with 1 g gourd openings and was discarded.

Generated Cu10. ! ;B, E, T using nitrogen as adsorbent of supported catalyst on Zr/2, surface area is 370rr
? /l.

The quartz reactor system of Example/ was modified for the introduction of oxygen as additional feed material. When oxygen was used, ethylene and oxygen were sent to the mixing tube through separate flow meters. This ethylene-oxygen mixture was then sent to a first mixing tube into which a weighed amount of TCE was also introduced. The ternary mixture from the first mixing tube was then sent to a stainless steel tube in an oil bath as described in Example/. The rest of the equipment and general operation was as described in Examples/.

Experiments were conducted using the supported catalyst prepared above using a 7.7 t and modified quartz reactor system of Example/, using TCE and ethylene, and in some experiments also using oxygen. The experiment was conducted at approximately normal pressure.

Data from sequential /9 experiments are shown in Table 7.

Prior to Experiment No. B, the supported catalyst was treated with air at 37θ°C overnight. Experiment No./Before De
Treated overnight at °C.

Example 7 Cuα2−. in water/20−. 2H20g, see P (0,
(B mol), ZrOα2-gH3Og, OA f (0
,0,2! ; mol), a solution of C17,'Rt
Added to 9. g before mixing both the above solution and silica gel.
Heated to s-qo°C.

The flask containing the above solution and silica gel was placed in a Rincon rotary evaporator, and most of the water was evaporated at an absolute pressure of 4 tθ kg·gs with a water bath source at 90-95°C.

The supported catalyst was first dried at 130°C and then at 3SO°C. The product was sieved. One tenth of the product passed through a 20 mesh sieve (US sieve series) and was discarded. Generated Cu10. ! B, E, T using nitrogen as an adsorbent of a supported catalyst on Zr/co, the surface area is S0-/
It was 2.

The quartz reactor system of Example/ was modified to introduce water vapor as an additional feed material. When using steam,
This was introduced by bubbling ethylene through a 1/l flask containing water. This flask was located in front of the mixing tube.

Supported catalyst made above! ;b, Of and T
Experiments were performed using CE and ethylene, and in some cases oxygen or water vapor. If TCE and ethylene are the only feed materials, use the quartz reactor system of Example A; if oxygen is also introduced, use the modified quartz reactor system of Example B, and if water vapor is also introduced. used the modified quartz reactor system described in this example. In experiment numbers and experiments, the flask containing the water in which the ethylene was bubbled was kept at 7°C. For runs number 9-// and 7g-10, the flask was kept at //°C. Experiments were conducted at approximately normal pressure. The data of 20 experiments conducted sequentially are shown in Table 1. Prior to run number 15, the supported catalyst was treated with air at 3gO 0 C overnight. Before experiment number/g, the supported catalyst was blown with air.
Treated overnight at Iio<0>C.

Example g Cuα2·, 2) in water g0−120 g, e29<0
．． Qtamor), zroct2-gH2og, 0ot? (0,0,2!; -E-#), Kd7.1p(
A solution of 0.7 mol) of carbon type PCB (Cal
gon Type PCB) added to activated carbon so,ot.

Both the above solution and activated carbon were heated to 5-90°C before mixing. The flask containing the above solution and activated carbon was placed in a Rincon rotary evaporator to evaporate most of the water at a water bath temperature of g7-q left C and an absolute pressure of tO kilopascals. Then increase the pressure to 7
．． The pressure was reduced to 3 kg/4'scull absolute and evaporation continued for 2'1 minute. The supported catalyst was then dried at 730° C. and the portion passing through a 1.20 mesh sieve (US sieve series) was discarded.

Using the supported catalyst 'IO,3t' prepared above and the quartz reactor system of Example, 72 experiments were conducted successively at approximately normal pressure. The data are shown in Table 9.

Although the invention has been described with respect to specific details of certain embodiments thereof, such details are not beyond the scope of the invention.
It is not intended to be considered as imposing an ilJ limit.

Claims (1)

[Claims] A method for dechlorinating an α α -containing organic compound in the presence of a catalyst containing an alkali metal chloride and a chlorinated steel, the catalyst comprising at least seven dechlorination-promoting zirconium compounds. Featured improvement method. (2) Claims (C) in which the catalyst is in the form of a supported catalyst; Claims in which the atomic ratio of zolconium to copper of the zolconium compound is in the range of about F:/ and the atomic ratio of zolconium to copper is from about O0θ/:/ to about 2:/ (
The method described in 2. (lA) The method according to claim (21), wherein the copper content of the supported catalyst is in the range of about / to about 72% by weight. The method described in (9) Claims in which the carrier of the supported catalyst is silica del (method described in -) ('7) The chlorine-containing organic compound has the following structural formula (a), R and R2 are each independently hydrogen, chloro, alkyl, unsaturated aliphatic, alicyclic, or phenyl; b), R, and R4 are each independently hydrogen, chloro, or alkyl); (f) the alkyl contains from about 1 to about 2 carbon atoms, and the unsaturated aliphatic group contains from about 1 to about 2 carbon atoms; Claim (9) The method according to claim (9) K, wherein R and R are each independently trapped hydrogen,
7. The method according to claim 7, wherein chloro, alkyl, and phenyl; b) R3 and R4 are each independently hydrogen, chloro, or methyl. (10) The chlorine-containing organic compound is /, /, 2
-) Lichloroethane, sym-tetrachloroethane, 1Jnsyffl-tetrachloroethane, pentachloroethane, or hexachloroethane. -Trichloroethane is the method according to the claim (-). (/2) The method according to the claim @ in which water vapor is introduced into the dechlorination reaction. (/3) The water vapor is approximately 0.0/ to approximately 25 mol. (15) The oxygen is about 0.θ/~about
Claims 1ffi (/4
'). (/B) The method according to claim @, in which the dechlorination reaction is carried out in the presence of an organic chlorine acceptor. (/7) The molar ratio of the organic chlorine acceptor to the chlorine-containing organic compound introduced into the dechlorination reaction is about θ, 2/~1
I: The method described in the claims (/B) which is within the scope of /. (7g) The method according to claim (/B), wherein the organic chlorine acceptor is ethylene. (/9) The chlorine-containing organic compound is /, /,,2
- trichloroethane, sym-tetrachloroethane,
Claim 7 which is unsym-tetrachloroethane, pentachloroethane, and hexachloroethane
The method described in g). (x) The chlorine-containing organic compound is 7. /, the method according to claim (7g), which is coat trichloroethane. (2/) The method described in claim (/B) in which water vapor is introduced into the dechlorination reaction. (〃) The water vapor is about 0.07 to about 0.07 of the total feed material,
, 2S molar ratio (method described in (2)). (23) The method described in claim (/B) for introducing oxygen into the dechlorination reaction. 4. The method of claim 3, wherein the oxygen constitutes about 0.0 to about 100% of the total feed material.