# US 6,720,466 B2 · 1,1,1,3,3-pentachloropropane process purge stream concentration using a secondary refluxed evaporator and secondary product recovery

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- Number: US 6,720,466 B2
- Document ID: US6720466B2
- Status: Granted
- Kind: B2
- Application number: 10/125,141
- Filed: 2002-04-17
- Published: 2003-10-23
- Granted: 2004-04-13
- Earliest claimed: 2002-04-17
- Assignees: Vulcan Chemicals, Division of Vulcan Materials Company
- Inventors: Richard L. Wilson; John L. Dawkins; Rodney L. Klausmeyer; James J. Weller
- Web page: https://patentgrep.com/patent/US6720466B2

## CPC

- C07C 17/383: by distillation
- C07C 17/275: of hydrocarbons and halogenated hydrocarbons
- C07C 17/278: of only halogenated hydrocarbons
- C07C 17/38: Separation; Purification; Stabilisation; Use of additives
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A process for economically producing 1,1,1,3,3-pentachloropropane under conditions which preserve the activity of the catalyst. In a preferred embodiment, a two-stage distillation process is employed. In the two-stage process, the size of the equipment, temperature and vacuum are varied.

## Claims

### Claim 1

A process for preparing a desired haloalkane comprising:
(a) contacting a haloalkene feedstock and a haloalkane feedstock in the presence of effective amounts of catalyst components, ferrous chloride, ferric chloride, and a trialkylphosphate compound, under conditions effective to promote an addition reaction and to form a product stream containing said haloalkane product, higher boiling haloalkane by-products, unreacted feedstocks, and catalyst components, and
(b) separating the desired haloalkane product from the high-boiling undesired haloalkane byproducts and the catalyst components using a two-stage catalyst recovery unit (CRU), wherein
i. the bottom fraction from the first stage flows into the second stage, and the overhead fractions from the two stages are combined for further purification steps, and,
ii. the first stage of the CRU recovers, in the distillate, between 50 and 90% of the desired haloalkane product contained in the reactor effluent, leaving more than 98% of the high-boiling undesired haloalkane byproducts in the bottom fraction, and,
iii. the second stage of the CRU recovers, in the distillate, more than 70% of the remaining desired haloalkane product, leaving more than 33% of the high-boiling undesired haloalkane byproducts in the bottom fraction, together with the catalyst components, and
(c) recycling most of the bottom fraction from the second stage of the CRU to the reactor, and purging a small fraction of it from the system to control byproduct concentrations in the reactor and to avoid excessive catalyst degradation.

### Claim 2 (depends on 1)

The process of claim 1, wherein the first stage of the CRU roughly distills the desired haloalkane product and lower boiling components from the undesired high boiling haloalkane byproducts, higher boiling components, and catalyst components, producing a bottom fraction containing between 35 and 75 percent of the desired haloalkane product and wherein the second stage further separates the bottoms stream from the first stage into an overhead stream containing the desired haloalkane product and less than 2 wt. percent of the undesired high-boiling haloalkane byproducts, and produces a bottoms catalyst fraction suitable for recycle to the reactor, which contains less than 25 wt. percent of the desired haloalkane product.

### Claim 3 (depends on 1)

The process of claim 1, wherein the first stage of the CRU is operated at 10 to 50 Torr bottom pressure, and at 160-240 degrees F. bottom temperature, and the liquid residence time, defined as the ratio of the volume of liquid contained in the bottom of the tower to the volumetric liquid flow rate from the bottom of the tower, is less than five days, and the second stage of the CRU is operated at 1 to 15 Torr bottom pressure, and at 180-260 degrees F. bottom temperature, and the liquid residence time is less than 12 hours.

### Claim 4 (depends on 1)

The process of claim 1, wherein the first stage of the CRU is operated at less than 215 F. bottom temperature, and at less than five days liquid residence time, and the second stage of the CRU is operated at less than 240 F. bottom temperature, and at less than 12 hours liquid residence time.

### Claim 5 (depends on 1)

The process of claim 1, wherein the first stage of the CRU is operated at 10 to 50 Torr bottom pressure, and at 160-240 F. bottom temperature.

### Claim 6 (depends on 1)

The process of claim 1, wherein the second stage of the CRU is operated at 3 to 15 Torr bottom pressure and at 180-260 F. bottom temperature.

### Claim 7 (depends on 1)

The process of claim 1, wherein the first stage of the CRU is operated at less than 215 F. bottom temperature.

### Claim 8 (depends on 1)

The process of claim 1, wherein the second stage of the CRU is operated at less than 240 F. bottom temperature.

### Claim 9

The process of Clam 1, wherein the liquid residence time in the first stage is less than five days and the liquid residence time in the second stage is less than 12 hours.

### Claim 10 (depends on 1)

The process of claim 1, wherein the liquid residence time in the first stage is less than 24 hours and the liquid residence time in the second stage is less than 6 hours.

### Claim 11 (depends on 1)

The process of claim 1, wherein the liquid residence time in the second stage is no more than 20% of the liquid residence time of the first stage, and the temperature of the second stage bottom liquid is no more than 25 degrees F. hotter than the temperature of the first stage bottom liquid.

### Claim 12 (depends on 1)

The process of claim 1, wherein the desired haloalkane product is 1,1,1,3,3-pentachloropropane, the haloalkene feedstock is vinyl chloride, the haloalkane feed stock is tetrachloromethane, the main undesired high-boiling haloalkane byproducts are 1,1,1,3,5,5-hexachloropentane and 1,1,3,3,5,5-hexachloropentane, and the trialkylphasphate compound is tributylphosphate.

### Claim 13

A method for generating 1,1,1,3,3-pentachloropropane comprising
(a) reacting carbon tetrachloride with vinyl chloride in the presence of a catalyst comprising elemental iron, ferric chloride, and tributylphosphate, producing a reactor effluent, and
(b) distilling the reactor effluent, separating 1,1,1,3,3-pentachloropropane and lower boiling components from high boiling components at a temperature and pressure which do not substantially inactivate the catalyst, and producing a bottom fraction containing the catalyst components and less than 50% of the 1,1,1,3,3-pentachloropropane contained in the reactor affluent from step (a), and
(c) distilling the bottom fraction from step (b) to recover overhead at least 70% of the 1,1,1,3,3-pentachloropropane remaining in the bottom fraction from step (b), and producing a new bottom fraction suitable for recycle to the reactor, and
(d) combining the distillate fractions of steps (b) and (c) for further purification of the 1,1,1,3,3-pentachloropropane product.

### Claim 14 (depends on 13)

The method of claim 13, wherein the purified halohydrocarbon recovered is 1,1,1,3,3-pentachloropropane, and the olefin fed is vinyl chloride.

### Claim 15 (depends on 14)

The method of claim 14, wherein the first refluxed evaporator is operated at about 10 to 50 Torr, with a bottom temperature of about 160 to 240 F., and the second refluxed evaporator is operated at about 1 to 15 Torr, with a bottom temperature of about 180-260 F.

### Claim 16 (depends on 15)

The method of claim 15, wherein the liquid residence time in the first refluxed evaporator is less than 24 hours and the liquid residence time in the second refluxed evaporator is less than about six hours.

### Claim 17 (depends on 15)

The method of claim 15, wherein the first refluxed evaporator has a pressure of about 20 Torr and a temperature of about 187 F., and the second refluxed evaporator has a pressure of about 5 Torr, and a temperature of about 207 F.

### Claim 18

A process for preparing a desired haloalkane product comprising:
(a) contacting a haloalkene and a haloalkane feedstock in the presence of effective amounts of catalyst components ferrous chloride, ferric chloride, and a trialkylphosphate compound, under conditions effective to promote an addition reaction and to form a reactor effluent containing said haloalkane product, higher boiling haloalkane byproducts, unreacted feedstocks, and catalyst components, and
(b) separating the desired haloalkane product from the high-boiling undesired haloalkane byproducts and the catalyst components using a two-stage catalyst recovery unit, wherein
(i) the bottom fraction from the first stage flows into the second stage, and
(ii) the first stage of the CRU recovers, in the distillate, between 50 and 90% of the desired haloalkane product contained in the reactor effluent, leaving more than 98% of the high-boiling undesired haloalkane byproducts in the bottom fraction, and
(iii) the second stage of the CRU recovers, in the distillate, more than 70% of the remaining desired haloalkane product, leaving more than 33% of the high-boiling undesired haloalkane byproducts in the bottom fraction, together with the catalyst components, and
(iv) further distilling the overhead fraction from step iii. to produce a new overhead fraction containing the desired haloalkane product and less than 1 wt. % of the high-boiling undesired haloalkane products and a new bottom fraction containing the undesired haloalkane product, and
(v) disposing or otherwise using the bottom fraction of step iv., and
(c) combining the overhead fraction of step iv. with the overhead frction of step ii. for further purification, and
(d) recycling most of the bottom fraction from step iii. to the reactor, and purging a small fraction of it from the system to control byproduct concentrations in the reactor and to avoid excessive catalyst degradation.