Process for hydrogenating dichloroisopropyl ether

Abstract

Convert dichloroisopropyl ether into a halogenated derivative by contacting the dichloroisopropyl ether with a source of hydrogen and a select heterogeneous hydrogenation catalyst under process conditions selected from a combination of a temperature within a range of from 50 degrees centigrade ( C.) to 350 C., a pressure within a range of from atmospheric pressure (0.1 megapascals) to 1000 pounds per square inch (6.9 MPa), a liquid feed volume flow to catalyst mass ratio between 0.5 and 10 L/Kg*h and a volume hydrogen/volume liquid ratio between 100 and 5000 ml gas/ml liquid. The halogenated derivative is at least one of 1-chloro-2-propanol and 1,2-dichloropropane 1, and glycerin monochlorohydrin.

Claims

1. A process for converting dichloroisopropyl ether into a halogenated derivative that comprises contacting the dichloroisopropyl ether with a source of hydrogen and a heterogeneous hydrogenation catalyst selected from a group consisting of a ruthenium on carbon catalyst, a copper/chromium/manganese/barium catalyst, a copper/calcium supported on silica catalyst and a copper/zinc catalyst under process conditions selected from a combination of a temperature within a range of from 50 degrees centigrade ( C.) to 350 C., a pressure within a range of from atmospheric pressure (0.1 megapascals) to 1000 pounds per square inch (6.9 MPa), a liquid feed volume flow to catalyst mass ratio between 0.5 and 10 L/Kg*h and a volume hydrogen/volume liquid ratio between 100 and 5000 ml gas/ml liquid, the halogenated derivative at least one of 1-chloro-2-propanol and 1,2-dichloropropane, and glycerin monochlorohydrin.

2. The process of claim 1, wherein the combination includes at least one of a temperature of from 100 C. to 300 C., a pressure of from 10 psi (0.069 megapascal (MPa) to 200 psi (1.38 MPa, a liquid feed volume flow to catalyst mass ratio within a range of from 1 L/Kg*h to 8 L/Kg*h, and a volume hydrogen/volume liquid ratio of from 350 ml gas/ml liquid to 3500 ml gas/ml liquid.

3. The process of claim 1, wherein the combination includes at least one of a temperature of from 150 C. to 250 C., a pressure of from 10 psi (0.069 MPa) to 20 psi (0.138 MPa), a liquid feed volume flow to catalyst mass ratio within a range of from 1.4 L/Kg*h to 5 L/Kg*h, and a volume hydrogen/volume liquid ratio of from 600 ml gas/ml liquid to 2700 ml gas/ml liquid.

Description

EXAMPLE 1

(1) Perform catalyst testing in a glass-lined inch (6.35 millimeter (mm)) reactor placed in an oven. Use a Teledyne ISCO pump for liquid feed to the reactor and use mass flow controllers for hydrogen and nitrogen feeds. Use 0.2 grams (g) to 0.3 g of catalyst and hold the catalyst in place using quartz chips. Purge the reactor to remove oxygen, then reduce the catalyst under flowing hydrogen (10 standard cubic centimeters per minute (sccm) flow rate) at 350 C. and atmospheric pressure for two hours (hr). Heat the reactor to a desired initial temperature that varies with the catalyst as shown in Table 1 below, pressure the reactor to 30 pounds per square inch (206.8 pascals (Pa)) and then start the liquid feed flow. Typical reaction conditions at such a pressure are temperatures of 100 C., 150 C., 200 C., 250 C. and 300 C. with a feed of 10 sccm of hydrogen and 0.45 millimeters per minute (ml/min) of a DCIPE feedstream (99.7 wt % DCIPE and 0.3 wt % 2,3-dichloro-2-propanol). Additional reaction condition sets include a hydrogen feed of 20 sccm and a DCIPE flow rate of either 0.45 ml/min or 0.90 ml/min. See Table 1 below for catalyst test results in terms of liquid product composition in terms of propionaldehyde (PA), acetone (Ac), 1-chloropropane (1-CP), 1-chloro-2-propanol (CPOH), 1,2-dichloropropane (DCP), and IPE using the temperature, H.sub.2 flow and DCIPE flow also shown in Table 1.

(2) Catalyst (Cat) A (NobleMax 410, Clariant) contains 3 wt % ruthenium, 92 wt % active carbon in granule form and 5 wt % water, all wt % being based upon total catalyst weight (Clariant), in an amount of 0.153 g. Cat B (G-99 B-0, Clariant) contains 36.51.0 wt % copper, 321.0 wt % chromium, 2.30.3 wt % manganese, 2.00.2 wt % barium and has a surface area of 35.010.0 m.sup.2/g in an amount of 0.2993 g. Cat C (Cu0860, BASF) contains 50.0 wt %-70.0 wt % copper oxide, 10.0 wt %-30.0 wt % calcium oxide, 10.0 wt %-30.0 wt % silica, 0.0 wt %-10.0 wt % palygorskite (mg(Al.sub.0.5-1Fe.sub.0-0.5)Si.sub.4(OH)O10.4H.sub.2O) and has a surface area of 60 m.sup.2/g and a density of 1.11 g/cm.sup.3 in an amount of 0.1897 g. Cat D (G-132A, Clariant) contains 30.03.0 wt % copper oxide, 60.03.0 wt % zinc oxide and 8.01.0 wt % alumina in an amount of 0.2211 g.

(3) TABLE-US-00001 TABLE 1 DCIPE DCIPE T H.sub.2 Flow Flow Conv Liquid Product (wt %) Cat ( C.) (sccm) (ml/hr) (%) PA Ac 1-CP CPOH DCP IPE A 250 20 0.45 68.1 14.7 0.0 2.5 76.1 4.5 2.2 A 250 20 0.9 45.8 2.7 12.8 4.3 64.4 11.6 4.2 B 150 10 0.45 7.3 8.2 0.9 0.0 90.9 0.0 0.0 B 200 10 0.45 4.7 5.4 1.6 0.0 81.5 11.5 0.0 B 250 10 0.45 30.8 4.7 4.5 0.0 49.3 38.7 2.8 B 300 10 0.45 47.1 6.0 5.5 0.0 28.9 56.9 2.7 B 200 20 0.45 0.5 7.5 5.2 0.0 74.7 12.6 0.0 B 200 20 0.9 0.7 6.9 37.9 0.0 42.6 12.6 0.0 C 300 10 0.45 53.8 8.2 4.7 1.3 35.4 48.8 1.6 C 250 20 0.45 3.5 11.5 5.7 0.0 66.3 16.5 0.0 C 250 20 0.9 0.2 9.9 5.5 0.0 63.4 21.2 0.0 C 250 10 0.45 11.4 9.3 5.0 0.0 63.8 21.9 0.0 C 250 10 0.45 10.1 8.7 4.8 0.0 66.4 20.1 0.0 C 250 10 0.45 9.4 9.9 5.9 0.0 63.5 20.7 0.0 D 100 10 0.45 9.2 7.3 2.4 0.0 90.3 0.0 0.0 D 150 10 0.45 31.0 5.5 2.4 0.0 72.9 15.5 3.7 D 200 10 0.45 41.4 6.9 4.9 1.9 59.7 24.4 2.2 D 200 20 0.45 15.7 5.8 1.8 0.0 80.8 11.6 0.0 D 200 10 0.9 4.1 11.7 4.8 0.0 73.3 10.3 0.0 D 250 10 0.45 43.3 5.3 6.3 1.8 40.3 44.2 2.1 D 250 20 0.45 8.2 8.4 4.0 0.0 68.0 19.6 0.0 D 250 10 0.9 3.3 12.1 5.6 0.0 61.8 20.5 0.0

(4) The data in Table 1 show that 1-chloro-2-propanol and 1,2-dichloropropane are the principal products obtained during hydrogenation using the catalysts and conditions shown in and preceding Table 1.

EXAMPLE 2

(5) Replicate Example 1 with changes. As one change, use a PCD bottoms stream as a liquid feedstream that contains PO-propionaldehyde-acetone=0.43 wt %; propylene dichloride=30.35 wt %; epichlorohydrin=4.50 wt %; dichloropropanol=10.4 wt %; DCIPE=53.4 wt %; and impurities=0.93 wt %. As a second change, use a feed flow of 0.45 ml/hr for all runs. As a third change, alter the catalyst amounts to 0.1182 g for Cat A, 0.3005 g for Cat B, 0.1923 g for Cat C and 0.2213 g for Cat D.

(6) TABLE-US-00002 TABLE 2 H.sub.2 DCIPE T Flow Conv Liquid Product (wt %) Cat ( C.) (sccm) (%) PA Ac 1-CP CPOH DCP IPE 2-GMCH 1,3-DCOH 2,3-DCOH A 200 10 17.2 4.6 0.5 0.8 5.4 39.8 1.4 31.1 3.1 13.3 A 250 10 27.3 4.6 0.9 0.0 4.1 34.7 1.2 37.9 4.7 11.9 A 300 10 44.0 4.2 1.3 0.0 5.1 31.3 1.0 41.9 4.4 10.8 A 250 20 29.5 2.6 0.3 0.0 7.9 35.8 1.3 29.3 6.2 16.6 B 150 10 31.2 1.3 0.1 0.0 9.0 34.0 1.1 24.8 12.2 17.5 B 200 10 30.4 1.4 0.3 0.0 7.0 25.8 1.3 44.2 8.2 11.8 B 250 10 43.0 1.8 0.8 0.0 5.8 19.4 1.2 59.0 5.6 6.4 C 150 10 58.4 1.9 0.1 0.0 6.9 37.1 1.3 23.5 9.5 19.7 C 200 10 39.7 1.7 0.1 0.0 7.0 32.9 1.4 26.7 8.6 21.6 C 250 10 48.9 5.0 0.9 0.0 2.7 31.8 1.1 41.4 5.8 11.3 D 150 10 39.1 3.4 0.2 0.0 4.6 37.4 1.4 30.3 7.6 15.1 D 200 10 23.8 3.6 0.5 0.0 3.9 35.2 1.4 33.9 7.3 14.2 D 250 10 46.6 3.9 1.5 0.0 6.7 29.1 1.0 43.5 5.2 9.1

(7) The data in Table 2 show that the catalysts are active in converting DCIPE to a product stream that contains 1,2-dichloropropane and 2-GMCH as principal products.