USRE30818E - Epichlorohydrin purification process - Google Patents

Epichlorohydrin purification process Download PDF

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Publication number
USRE30818E
USRE30818E US06/152,245 US15224580A USRE30818E US RE30818 E USRE30818 E US RE30818E US 15224580 A US15224580 A US 15224580A US RE30818 E USRE30818 E US RE30818E
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United States
Prior art keywords
epichlorohydrin
resin
angstroms
surface area
iadd
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/152,245
Inventor
Leo Kim
Sunny C. Tang
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Shell USA Inc
Original Assignee
Shell Oil Co
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Filing date
Publication date
Priority claimed from US05/873,312 external-priority patent/US4127593A/en
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to US06/152,245 priority Critical patent/USRE30818E/en
Application granted granted Critical
Publication of USRE30818E publication Critical patent/USRE30818E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/32Separation; Purification

Definitions

  • This invention relates to a method of purifying epichlorohydrin by contact with a polymeric adsorbent.
  • .[.2,3-Butanedione is removed from product epichlorohydrin by contacting the epichlorohydrin with a macroreticular poly(t-butyl acrylate) adsorbent resin having a pore volume between about 0.48 and 0.57 ml/ml, an average pore diameter between about 80 and about 100 angstroms and a surface area between about 400 to about 500 square meters/gm.
  • the poly(t-butyl acrylate) resin of this invention is superior to other resins such as styrene-divinylbenzene and to resins having differing surface areas and pore diameters..].
  • .Iadd.2,3-Butanedione is removed from product epichlorohydrin by contacting the epichlorohydrin with an acrylic ester resin having a porosity of 0.55, a surface area of 450 m 2 /gm and an average pore diameter of 90 angstroms.
  • the acrylic ester resin of this invention is superior to other resins such as styrene-divinylbenzene and to resins having differing surface areas and pore diameters. .Iaddend.
  • the resins used in this invention are macroreticular poly(t-butyl acrylate) resins having a porosity (milliliter of pore/milliliter of dried resin) between about 0.48 and about 0.57 and preferably between about 0.50 to about 0.55; a surface area between about 400 to about 500 square meters per gram (of dried resin) and preferably between about 425 to about 475 square meters per gram; and an average pore diameter (of the dried resin) between about 80 to about 100 angstroms and preferably between about 85 to about 95 angstroms..].
  • the resin used in this invention is an acrylic ester resin having a porosity of 0.55, a surface area of 450 m 2 /gm and an average pore diameter of 90 angstroms. .Iaddend.
  • the resin is mixed with the epichlorohydrin and allowed to remain in contact therewith for about 0.01 to about 10 hours, preferably from about 0.1 to about 1 hours, and then separated by conventional means, e.g., filtration or centrifugation.
  • the epichlorohydrin is preferably passed through a fixed bed of resin at liquid hourly space velocities ranging from about 0.1 to about 100 hours -1 , and preferably from about 0.5 to about 2.5 hours -1 .
  • Tempertures of contact are not critical and are determined by the temperature stability of the resin and the freezing point of the epichlorohydrin. Temperatures are between about -25° C. and about 150° C.
  • the resin of this invention significantly lowers the color index, removes substantially all of the 2,3-butanedione impurity without adversely affecting the epoxide value whereas other similar resins do not do so.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

2,3-Butanedione impurity is removed from epichlorohydrin by contacting the impurity containing epichlorohydrin with .[.a macroreticular poly(t-butyl acrylate) resin .]. .Iadd.an acrylic ester resin .Iaddend.having a pore volume of about .[.0.5 .]. .Iadd.0.55 .Iaddend.ml/ml, an average pore diameter of about 90 angstroms and a surface area of about 450 m2 /gm.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of purifying epichlorohydrin by contact with a polymeric adsorbent.
2. Background of the Invention
In the commercial production of epichlorohydrin, small amounts of impurities are frequently present in the product stream that will degrade the product, causing it to be off specification. One of these impurities is 2,3-butanedione which is a color body which when present in epichlorohydrin causes it to have an undesirable greenish tint. A simple and inexpensive process for removing the impurity from the epichlorohydrin product without causing a significant loss in the epoxide value of the product would be very desirable.
SUMMARY OF THE INVENTION
.[.2,3-Butanedione is removed from product epichlorohydrin by contacting the epichlorohydrin with a macroreticular poly(t-butyl acrylate) adsorbent resin having a pore volume between about 0.48 and 0.57 ml/ml, an average pore diameter between about 80 and about 100 angstroms and a surface area between about 400 to about 500 square meters/gm. The poly(t-butyl acrylate) resin of this invention is superior to other resins such as styrene-divinylbenzene and to resins having differing surface areas and pore diameters..].
.Iadd.2,3-Butanedione is removed from product epichlorohydrin by contacting the epichlorohydrin with an acrylic ester resin having a porosity of 0.55, a surface area of 450 m2 /gm and an average pore diameter of 90 angstroms. The acrylic ester resin of this invention is superior to other resins such as styrene-divinylbenzene and to resins having differing surface areas and pore diameters. .Iaddend.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
.[.The resins used in this invention are macroreticular poly(t-butyl acrylate) resins having a porosity (milliliter of pore/milliliter of dried resin) between about 0.48 and about 0.57 and preferably between about 0.50 to about 0.55; a surface area between about 400 to about 500 square meters per gram (of dried resin) and preferably between about 425 to about 475 square meters per gram; and an average pore diameter (of the dried resin) between about 80 to about 100 angstroms and preferably between about 85 to about 95 angstroms..].
.Iadd.The resin used in this invention is an acrylic ester resin having a porosity of 0.55, a surface area of 450 m2 /gm and an average pore diameter of 90 angstroms. .Iaddend.
The .[.resins.]. .Iadd.resin .Iaddend.of the invention .[.are.]. .Iadd.is .Iaddend.contacted with the epichlorohydrin to be purified in either a batch process or a continuous or fixed-bed process. When a batch process is utilized, the resin is mixed with the epichlorohydrin and allowed to remain in contact therewith for about 0.01 to about 10 hours, preferably from about 0.1 to about 1 hours, and then separated by conventional means, e.g., filtration or centrifugation. In a continuous process the epichlorohydrin is preferably passed through a fixed bed of resin at liquid hourly space velocities ranging from about 0.1 to about 100 hours-1, and preferably from about 0.5 to about 2.5 hours-1. Tempertures of contact are not critical and are determined by the temperature stability of the resin and the freezing point of the epichlorohydrin. Temperatures are between about -25° C. and about 150° C.
The process of this invention will be further described by the following illustrative embodiments which are provided for illustration and are not to be construed as limiting the invention.
ILLUSTRATIVE EMBODIMENTS
A series of resins (50 gram portions) shown in Table I were washed with 500 ml of deionized water, 250 ml of reagent grade methanol, 500 ml of reagent grade acetone and then dried in a vacuum at about 50° C. overnight.
                                  TABLE I                                 
__________________________________________________________________________
                                      Avg                                 
                              Surface Area                                
                                      Pore Diameter                       
Source          Type    Porosity                                          
                              m.sup.2 /gm                                 
                                      Angstroms                           
__________________________________________________________________________
Resin #1 Rohm and Haas XAD-4                                              
                Polystyrene                                               
                        0.51  780     50                                  
Resin #2 Rohm and Haas XAD-7                                              
                Acrylic ester                                             
                        0.55  450     90                                  
Resin #3 Rohm and Haas XAD-8                                              
                Acrylic ester                                             
                        0.52  140     235                                 
__________________________________________________________________________
A 29.5×7/16 inch glass column was packed (wet) with 20 cc of the appropriate resin prepared as above. Epichlorohydrin was allowed to pass through the resin by gravity at a liquid hourly space velocity of approximately 1-2 hours-1. After 20 ml of epichlorohydrin had passed through the column, the next 50 ml sample of epichlorohydrin was collected. The color index of the material was measured using ASTM D-1209-69. The concentration of 2,3-butanedione was measured with UV light absorptions in comparison with standard samples of 2,3-butanedione of known concentration. The epoxide values were measured by .[.NaI-isopropyl alcohol-acetic acid peroxide titration method.]. .Iadd.wet epoxide titrations (Anal. Chim. Acta, 31, 38 (1964).Iaddend.. The results are shown in Table II.
              TABLE II                                                    
______________________________________                                    
        Color  2,3 Butanedione                                            
                             Epoxide                                      
        Index  ppm           Value, % w                                   
______________________________________                                    
No resin used                                                             
          40-50    25            99.0                                     
Resin #1  25-30    20            98.9                                     
Resin #2  15-20     0            99.1                                     
Resin #3  25-30    15            98.9                                     
______________________________________                                    
Thus it can be seen that the resin of this invention (Resin #2) significantly lowers the color index, removes substantially all of the 2,3-butanedione impurity without adversely affecting the epoxide value whereas other similar resins do not do so.

Claims (1)

    What is claimed is: .[.1. The process of removing 2,3-butanedione impurity from epichlorohydrin which comprises contacting said epichlorohydrin with a macroreticular poly(t-butyl acrylate) adsorbent resin having a pore volume between about 0.48 and about 0.57, an average pore diameter between about 80 and about 100 angstroms and a surface area between about 400 to about 500 square meters per gram..]. .[.2. The process of claim 1 wherein the resin has a pore volume between about 0.50 and about 0.55, an average pore diameter between about 85 and about 95 angstroms and a surface area
  1. between about 425 to about 475 square meters per gram..]. 3. The process of claim .[.1.]. .Iadd.4 .Iaddend.where the resin is contained in a fixed-bed and said epichlorohydrin is passed through said bed at a liquid hourly space velocity ranging between about 0.1 to about 100 hours-1. .Iadd. 4. The process of removing 2,3-butanedione impurity from epichlorohydrin which comprises contacting said epichlorohydrin with an acryclic ester resin having a porosity of 0.55, a surface area of 450 m2 /gm and an average pore diameter of 90 angstroms.
US06/152,245 1978-01-30 1980-05-22 Epichlorohydrin purification process Expired - Lifetime USRE30818E (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US06/152,245 USRE30818E (en) 1978-01-30 1980-05-22 Epichlorohydrin purification process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/873,312 US4127593A (en) 1978-01-30 1978-01-30 Epichlorohydrin purification process
US06/152,245 USRE30818E (en) 1978-01-30 1980-05-22 Epichlorohydrin purification process

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US05/873,312 Reissue US4127593A (en) 1978-01-30 1978-01-30 Epichlorohydrin purification process

Publications (1)

Publication Number Publication Date
USRE30818E true USRE30818E (en) 1981-12-08

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Family Applications (1)

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US06/152,245 Expired - Lifetime USRE30818E (en) 1978-01-30 1980-05-22 Epichlorohydrin purification process

Country Status (1)

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