Strong acid catalyst composition

Abstract

A catalyst prepared by polymerizing 0-98 weight % butylstyrene; 0-80 weight % vinyl toluene; 1.5-25 weight % divinyl benzene having 1-98 weight % of ethyl vinyl benzene; and 0-80 weight % styrene. Copolymer beads are made, sulfonated, and used as a catalyst.

Claims

1. A catalyst comprising macroporous sulfonated copolymer beads having polymerized monomer units consisting of: 5-75 weight % of butyl styrene; 1.5-25 weight % divinyl benzene having 1-98 weight % of ethyl vinyl benzene; and 0-80 weight % styrene wherein the catalyst is not impregnated with metal.

2. The catalyst of claim 1 wherein the butylstyrene comprises at least 10 weight %, and the divinyl benzene comprises 1.8-25 weight % of the catalyst.

3. The catalyst of claim 1 wherein the butylstyrene comprises t-butyl styrene.

4. The catalyst of claim 2 wherein the butylstyrene comprises at least 25 weight %.

Description

EXAMPLES

Example 1: Polymers with Vinyl Toluene

(1) An aqueous suspending mixture of 437.5 grams of DI water, 1.2 grams of 50% NaOH, 1.7 grams of Boric Acid, 8.0 grams of a 20% solution of CATFLOC C (Calgon Corp.), and 0.9 grams of gelatin (CAS number 9000-70-8) was made by dissolving the gelatin in the DI water at 40 C., adding the CATFLOC C solution, NaOH, and the boric acid and stiffing until the boric acid was dissolved. The pH of the aqueous solution was adjusted to between 9.7 and 10.0 with 20 weight percent NaOH. The suspending mixture was charged to a stainless steel pressure reactor. An organic phase of a mixture of 154.5 grams of methyl-styrene, 64.2 grams of 63% DVB (DVB-63), 219 grams of porogen (either 2,2,4-trimethyl pentane or methyl-isobutylcarbinol), and 3.0 grams of 75% benzoyl peroxide was added to the pressure reactor, which was then pressurized to 7 psi with nitrogen, and sealed. The agitator speed was adjusted to give an average particle size of 600 microns. After 30 minutes of stirring at 25 C., the reactor was heated to 79 C. over 70 minutes and then held at 79 C. for 135 minutes. After 30 minutes at 79 C., the agitation rate was increased by 25 rpm and held there for the remaining time. After the reaction time was complete and the reactor had cooled to room temperature, it was unsealed and the contents were washed several times with DI water to remove the suspending mixture. The beads were stripped of the porogen by placing the beads and a volume of water twice the volume of the beads in a three necked flask equipped with overhead stirrer and distillation head and heating the stiffing mixture quickly to 97 C., then slowly raising the temperature to the boiling point and holding the temperature at the boiling point until no further porogen distilled out. After cooling, the beads were poured into a pan and the excess water was removed using a filter stick. The beads were placed in a drying oven at 50 C. overnight to remove remaining porogen and water. The dry beads were screened and the fraction between 20 and 50 mesh was kept.

Example 2: Polymers with Styrene

(2) In a similar manner to Example 1, polymers were made where styrene replaced some or all of the methyl-styrene. Examples are a) 58.5 grams methyl-styrene and 58.5 grams styrene; b) 29.3 grams of methyl-styrene and 87.8 grams of styrene; and c) 117 gram of styrene.

Example 3: Polymers with t-Butylstyrene

(3) In a similar manner to example 1, polymers were made where tert-butylstyrene replaced the methyl-styrene. Examples are a) 117 grams t-butylstyrene, 48.8 grams of DVB-63, and 166 grams of either porogen; b) 89.3 grams of t-butylstyrene, 27.4 grams of styrene, 48.6 grams of DVB-63, and 166 grams of porogen; and c) 44.8 grams of t-butylstyrene, 72.2 grams styrene, 48.6 grams of DVB-63, and 166 grams of porogen.

Example 4: Polymers with t-Butylstyrene and Styrene

(4) In an another example of polymers containing both t-butylstyrene and styrene, an aqueous phase of 838.5 grams of DI water, 160 grams of a 0.75 weight percent solution of carboxymethyl methyl-cellulose, and 1.6 grams of a 65 weight % solution of sodium dichromate was charged to a stainless steel pressure vessel. An organic phase of 264.9 grams of styrene, 88.3 grams of t-butylstyrene, 146.8 grams of DVB-63, 1.25 grams of a 50 weight % solution of tert-butyl peroctoate, 0.4 grams of tert-butyl perbenzoate, and 500 grams of either 2,2,4-trimethylpentane or methyl isobutylcarbinol was added to the reactor. The reactor was purged of air by pressurizing the reactor with nitrogen to 30 psi and releasing the pressure three times, and the reactor was sealed. The agitation was set to a speed that would give an average particle size of 600 microns. After stirring for 30 minutes at 25 C., the reactor was heated to 80 C. over 120 minutes and held at 80 C. for 720 minutes, then heated to 110 C. over 60 minutes and held at 110 C for 180 minutes before being cooled to room temperature. The resultant beads were washed several times with DI water to remove the suspending mixture. After washing, the beads were placed in a pan and the excess water was removed using a filter stick, and then the beads were placed in a fume hood for several days until the water and porogen had evaporated. The dry beads were screened and the fraction between 20 and 50 mesh was kept.

Example 5: Sulfonation of the Polymer Beads

(5) A three-necked flask equipped with an overhead stirrer and addition funnel was loaded with 50 grams of screened copolymer and 250 ml of 20% Oleum (104% H.sub.2SO.sub.4) at room temperature. The temperature was raised over about sixty minutes to 120 C., and maintained at that temperature for 180 minutes. The reaction was allowed to cool and then hydrated by a drop-wise addition of water. Typical properties for the sulfonated resins are found in Table 1.

Example 6: Catalyzed Reaction Between Ethanol and Isobutene

(6) A small stainless steel column was filled with a mixture of dried catalyst beads and quartz of similar diameters. The ratio of catalyst to quartz was varied to keep the amount of conversion of the isobutylene to less than 10%. The column was maintained at 60 C. A flow of ethanol was started through the column, and once the temperature and pressure stabilized, the isobutylene was mixed with the ethanol and the formation of ETBE was followed via GC. Relative conversion levels of the isobutylene are found in Table 1.

(7) TABLE-US-00001 TABLE 1 Reactivity ETBE Example Porogen WRC/MHC WVC DWC Synthesis 1 MIBC 46.2 2.6 5.6 67 2,2,4-TMP 51.3 2.3 5.6 70 2a MIBC 68.2 1.33 5.4 96 2,2,4-TMP 69.2 1.3 5.7 89 2b MIBC 68.8 1.3 5.4 106 2,2,4-TMP 73 1.2 5.5 108 2c MIBC 52.1 2.11 5.33 100 2,2,4-TMP 52.5 2.05 5.33 3a MIBC 72.3 1.01 4.82 2,2,4-TMP 56 1.55 4.56 25 3b MIBC 67.2 1.27 4.96 49 2,2,4-TMP 3c MIBC 66.5 1.35 5.36 2,2,4-TMP 67.7 1.17 5.29 4 MIBC 66.5 1.35 5.36 2,2,4-TMP 67.6 1.26 5.07

Example 7: Esterification of Free Fatty Acids (FFA)

(8) The catalytic lab conversions were carried out in small sealed bottles that were then sealed in larger secondary bottles as the secondary containment. Once the reactants were mixed and the primary and secondary containment bottles sealed, the samples were placed in an Orbital Shaker with heated water bath located in a fume hood. The samples were shaken at 40 C. for 6 hours and then cooled overnight before handling. The bottles were removed from the shaker and inspected while still in the secondary for leaks or breakage. Once they were found to be in a safe condition, the secondary bottles were opened in a fume hood and the primary reactants were inspected. Samples of the reaction mixture were pipetted into sample bottles and labeled for GC analysis of the reaction mixtures. The integration values comparing the percentage of residual free fatty acid found after the reaction and the conversion rate for the esterified product were reported.

(9) Table 3, summarizes the comparative FFA to ester conversion rates for the various resin types as challenged by varied FFA/alcohol pairs. As the base line case, the myristic acid (C-14) and methanol showed essentially no variation in the esterification conversion rate under the conditions applied no matter which strong acid cation resin was applied. But by increasing the chain length of both the FFA to either stearic acid (C-18) or palmitic acid (C-14) and increasing the chain length of the alcohol to ethanol or butanol, variations in the conversion rates for the various resins were measured. Table 2 shows the comparative macroporous cation exchange resins

(10) TABLE-US-00002 TABLE 2 Capacity *Type Sample WRC % meq/ml or g DOWEX DR-2030 4.7 DWC (The Dow Chemical Comp., Midland, MI) DOWEX CM-4 (The Dow Chemical Comp., Midland, MI) 3/47 XUR-1525-L09-032 86.2 0.5 WVC 6/44 XUR-1525-L09-033 73.4 1.0 WVC 8/40 XUR-1525-L09-034 68.8 1.2 WVC 8/43 XUR-1525-L09-035 71.5 1.0 WVC *nominal weight % divinylbenzene/isooctane in organic phase

(11) TABLE-US-00003 TABLE 3 Resin FFA Alcohol Area % Area % Resin weight g weight g ml FFA Ester Stearic Acid, C-18 Ethanol DR-2030 0.5 3.0 25 38 62 CM-4 0.5 3.0 25 54 46 3/47 0.5 3.0 25 35 65 6/44 0.5 3.0 25 48 52 8/40 0.5 3.0 25 58 42 8/43 0.5 3.0 25 66 34 2 weight % 0.5 3.0 25 19 81 DVB/tBS (Example 4) Sulfuric Acid 3.0 25 <1 100 Control Stearic Acid, C-18 Butanol DR-2030 0.5 5.0 25 43 57 CM-4 0.5 5.0 25 48 52 3/47 0.5 5.0 25 45 55 6/44 0.5 5.0 25 59 41 8/40 0.5 5.0 25 62 38 8/43 0.5 5.0 25 69 31 2 weight % 0.5 5.0 25 28 72 DVB/tBS (Example 4) Sulfuric Acid 5.0 25 <1 99 Control Palmitic Acid, C-16 Ethanol DR-2030 0.5 3.0 25 63 36 CM-4 0.5 3.0 25 58 42 3/47 0.5 3.0 25 55 45 6/44 0.5 3.0 25 67 33 8/40 0.5 3.0 25 75 25 8/43 0.5 3.0 25 77 23 2 weight % 0.5 3.0 25 32 68 DVB/tBS (Example 4) Sulfuric Acid 0.5 3.0 25 <1 99 Control All Resins Myristic Methanol 0.3 99.7 Acid, C-14

(12) When FFA (stearic, palmitic) was reacted with ethanol or butanol, the 2 weight % DVB/tBS (Example 4) had much higher FFA conversion to esters than the other resins. Only homogeneous sulfuric acid had higher FFA conversion to esters. When myristic acid and methanol were reacted together no significant difference could be seen between catalysts, i.e. the FFA conversion to ester.

Example 8: Improved Thermal Stability

(13) A sample of resin in water was sealed in a stainless steel bomb and heated to 205 C. for 24 hours. After cooling to room temperature, the resin was removed and analyzed for ion exchange capacity and water content. The results from the testing are found in Table 4. Amberlyst 35 Wet and Amberlyst XE781 were provided from The Dow Chemical Company, Midland, Mich.

(14) TABLE-US-00004 TABLE 4 Thermal Stability Testing @205 C./24 hour Hold Before After Change MHC WC VC MHC WC VC WC VC Catalyst (96) (eq/kg) (eq/L) (96) (eq/kg) (eq/L) % Loss % Loss Amberlyst 35 Wet 53.3 5.36 2.08 56.5 2.96 0.94 44.78 54.81 Amberlyst XE781 55.8 2.75 0.94 57.9 2.71 0.85 1.45 9.57 2a 51.2 5.58 2.28 56.8 3.65 1.21 34.59 46.93 3c 67.2 4.96 1.27 63.2 4.23 1.19 14.72 6.30 3b 56 4.56 1.55 52.8 2.00 0.69 56.14 55.48

Example 9: tBS/Styrene/DVB Polymer

(15) Polymerizations were conducted in a 1 gallon stainless steel reactor equipped with an agitator and jacket for heating and cooling. An aqueous phase of 712 g DI water, 305 g 1% carboxymethylmethylcellulose, and 1.6 g 60% sodium dichromate was placed in the reactor. A monomer/initiator phase of 800 g t-butylstyrene, 30.3 g 63% divinylbenzene, 2.5 g t-butylperoctoate, and t-butylperbenzoate was placed in the reactor. The monomer/initiator phase was sized by the agitator. The reactor was purged with nitrogen and then sealed. The temperature profile was 80 C. for 15 hours followed by 110 C. for 5 hours. The polymer was washed with DI water and air dried. Additional polymerizations were varying the t-butylstyrene to styrene ratio. The divinylbenzene concentration was kept constant at approximately 2.4 mole percent, and the 80 C reaction time was reduced to 7 hours. Sulfonations were conducted as follows. Fifty g of polymer were placed in glass three necked flask equipped with an agitator and infrared heating lamps. 400 ml of 96 weight % sulfuric acid was placed in the flask and the agitator was started to slurry the polymer. 20 ml of ethylene dichloride was added to the flask and allowed to swell the polymer for 30 minutes. The reactor was gradually heated to 115 C. and held at 115 C. for 2 hours. The reactor was cooled to room temperature and the resin was gradually hydrated with water over 3 hours. The resin was backwashed with DI water and analyzed. As shown in Table 5, the 100% t-butyl styrene resin was not fully sulfonated as shown by unreacted core under microscopic examination.

(16) TABLE-US-00005 TABLE 5 Cation Exchange Resin Properties for tBS/Styrene/DVB Polymer % t-butyl % Mole % WRC DWC % Rings % styrene styrene DVB % meq/g Sulfonated disubstitution 100 0 2.4 71.5 4.57 <100* 14.3* 75 25 2.4 73.8 5.02 100 18.0 50 50 2.4 72.0 5.03 100 6.3 25 75 2.5 70.6 5.09 98.3 2.0 0 100 2.4 75.7 5.14 91.6 8.4 *Beads were not sulfonated all the way to the core, but had exchange capacity higher than would be obtained if all the rings in the sulfonated zone were only singlely sulfonated.

Example 10: Pd Impregnated t-butylstyrene Sulfonated Resin Catalyst

(17) Macroreticular t-butylstyrene and DVB crosslinked macroreticular sulfonated resin (t-Bu-DVB-Pd) with 14% of crosslinking density was Pd impregnated. The level of Pd in the resin as measured by ICP was 2.0%-w dry basis of the resin.

Example 11: Pd Impregnated Macroreticular Styrenic Sulfonated Resin Catalyst

(18) A comparative strong acid macroreticular styrenic resin at the same level of crosslinker density was Pd impregnated to 2.0%-w Pd dry basis of resin.

Example 12: Methyl Isobutyl Ketone Synthesis Comparative Results

(19) Both resins from Example 10 and Example 11 were packed in a reactor. The reactor was a continuous flow through reactor with 30 ml of resin. The resins were preconditioned with hydrogen for 24 hours at 1 MPa at 100 C. to reduce the Pd to zerovalent metal. The reaction was run for 8 hours by flowing acetone at 1 LHSV (h.sup.1) and hydrogen at 200 sccm at a pressure of 2 MPa and temperature of 80 C. Gas chromatography was used to quantify acetone, methyl isobutyl ketone (MIBK), and isopropanol (IPA) molecules. Isopropanol is an unwanted reaction side product and MIBK is the main product of reaction. Acetone conversion, MIBK yield, and selectivities are reported in Table 6.

(20) TABLE-US-00006 TABLE 6 MIBK MIBK IPA Conversion Yield Selectivity Selectivity* Resin (%) (%) (%) (%) Exam- t-Bu-DVB- 14 14 98 1.2 ple 10 Pd Exam- Sty-DVB-Pd 12 11 92 6.4 ple 11 (*Selectivity (weight %) is % molecule produced/total produced molecules in weight % units).