Styrene-divinylbenzene strong-acid cation-exchange resin catalyst is widely used in petrochemical industry and field of fine chemical, as is used for processes such as esterification, etherificate, aromatisation and olefin hydration.The subject matter that this resinoid catalyst exists is the coming off of sulfonic acid group in course of reaction, particularly exists under the situation at high temperature and water, and coming off of sulfonic acid group is particularly serious.Coming off in a large number of sulfonic acid group not only makes catalyst activity reduction and etching apparatus.Sulfonic acid group coming off from the phenyl ring is to cause owing to the aromatic rings of cationic ion-exchange resin is protonated.In order to prevent the protonated of phenyl ring, common way is to introduce electron withdraw group, slows down coming off of sulfonic acid group.
BP GB1,393,594 with chlorostyrene and the synthetic heatproof cationic ion-exchange resin of divinylbenzene copolymerization.
U.S. Pat 4,269,943 to adopt the styrene-divinylbenzene copolymer contain divinylbenzene 12% be raw material, 78 ℃ of following swellings 30 minutes, fed chlorine 3 hours with carbon tetrachloride under 10 ℃ of catalysis of iodine and stirring condition, is warming up to 20 ℃ again, kept 2-3 hour.Isolated fluorinated copolymers is washed successively with NaOH solution, water and methyl alcohol, and through 90 ℃, 15 hours dryings obtain the copolymer of chloride 20-40%.This copolymer and 99% sulfuric acid and dichloroethanes are positioned in the reactor, stir 2 hours down in 60 ℃, reaction temperature are risen to 120 ℃ then, keep 19 hours.Afterwards, product is through three dilutions ..., be washed with water to PH>4 at last, activation makes the transition and obtains exchanging equivalent is 3-4mol/kg(F), the heatproof cationic ion-exchange resin of moisture 40-60.
Similar techniques also has JP83-80307, patents such as JP88-63535.The catalyst that above-mentioned the whole bag of tricks makes still has considerable sulfonic acid group to split away off in application process.
The patent CN86102001A that Germany Texaco Inc. declares in China proposes, the strong-acid cation exchanger that core has been replaced by halogen is before using as catalyst, with the deionized water solution that contains 1 to 4 fat of carbon atom alcohol, under high temperature and pressure condition, carry out liquid phase and handle, be less than 25 milligrams of H until exfoliation rates
2SO
4/ (rise catalyst hour) and 7 milligrams of HCl/(rise catalyst hour) till.Though this method removes most of caducous sulfonic acid group in the strong-acid cation-exchange resin in advance, its catalytic activity also will be subjected to influence to a certain degree.In addition, this processing method needs special equipment and requires to remove the dissolved oxygen of handling in the water, and need reach 200-300 hour processing time.
Leonardus Petrus, Elze J.Stamhuls and Geet E.H.Joosten have tested the heat inactivation rule to strong-acid cation-exchange resin and chloride strong-acid cation-exchange resin under the different temperatures in water in Ind, Eng, Chem.Prod.Res.Dev1981.20.366-371.Show in 150-200 ℃ of scope, the loss of sulfonic acid group is relevant with styrene/divinylbenzene ratio in the resin, can be divided into quick loss and run off at a slow speed, speed is connected on the 85-95% that sulfonic acid group on the cinnamic phenyl ring accounts for total sulfonic acid group, and this sulfonic acid group is to run off at a slow speed; The sulfonic acid group that is connected on the phenyl ring of divinylbenzene accounts for 3-12%, and sulfonic acid group is with quick loss; Other had less than 3% exist with the sulfuric ester form, and it is fastest to run off.
The material purity that generally is used for the compound probability styrene-divinyl benzene resin is not high, and benzene feedstock ethene purity is about 99%, and its impurity mainly is ethylbenzene; The purity of raw material divinylbenzene is between 50-70%, and its major impurity has ethyl styrene, methyl styrene etc.Because the existence of above-mentioned impurity, make and contain a large amount of little molecule copolymer impurity in the styrene-divinylbenzene copolymer.In carrying out base exchange process, the part small molecular weight impurity forms barrier to the phenyl ring of styrene-divinylbenzene bulk copolymer, the ion exchange capacity of bulk copolymer is reduced, even effectively the catalytic activity component reduces.Phenyl ring in the above-mentioned small molecular weight impurity still can carry out halogenation and sulfonation simultaneously, when the cationic ion-exchange resin that is mingled with these small molecular weight impurities is used for chemical reaction process, under reaction condition, because the loss of small molecular weight impurity, take away the part active constituent, cause catalyst activity to reduce.
The object of the present invention is to provide a kind of method for preparing the halogen-containing strong-acid cation-exchange resin catalyst of good thermal stability.Comprise the purification process of the styrene-divinylbenzene copolymer structure of matter and the stabilization method of strong-acid cation-exchange resin sulfonic acid group.Another object of the present invention is pore volume and the specific surface that increases resin catalyst, and improves the pore size distribution situation.
The inventive method comprises: (1) is to the purification process of the styrene-divinylbenzene copolymer structure of matter; (2) (1) product is carried out halogenation; (3) (2) product is carried out sulfonation; (4) (3) product is carried out the sulfonic acid group stabilization processes.
1, to styrene-divinylbenzene copolymer structure of matter purification process, be with styrene-divinylbenzene copolymer organic solvent swelling, afterwards, carry out extracting with extractant, small molecular weight impurity is removed, wash at last and drying.
2, the styrene-divinylbenzene copolymer after the purification process is carried out halogenation.
3, the styrene-divinylbenzene copolymer after the halogenation is carried out sulfonation.
4, the styrene-divinylbenzene copolymer after the sulfonation is carried out the sulfonic acid group stabilization processes.
Detailed process of the present invention is as follows:
One, with styrene-divinylbenzene copolymer microballoon C
1-C
4Halogenated hydrocarbons swelling 0.5-5 hour, copolymer after the swelling moves into and fills in the container of benzene series solvent, quantity of solvent is 1.5-4 a times of copolymer volume, handled 3-20 hour 0.1-5.0MPa and 130-200 ℃, with extractings such as unsettled component and fragment in the copolymer in solvent, take out copolymer afterwards and handled 3-20 hour with absolute ethyl alcohol, make copolymer obtain purifying, then washing and dry in similarity condition.
Two, with traditional method the styrene-divinylbenzene copolymer through purification process is carried out halogenation.As with dichloroethanes swelling copolymer, add anhydrous ferric trichloride, constantly stir, temperature is controlled at below 20 ℃, slowly splashes into bromine, and bromine dropwises, and cools the temperature to 0 ℃, stirs 10 hours, filters, washs also dry then.
Three, with traditional method the styrene-divinylbenzene copolymer through bromination is carried out sulfonation, as not being higher than under 30 ℃ and the stirring condition, the oleum of slow Dropwise 5 0% in copolymer, under 30-50 ℃, kept 12 hours then, successively with deionized water, NaCl solution, hydrochloric acid and deionized water washing, obtain wet bromination strong-acid cation-exchange resin after the filtration.
Four, the halogenation strong-acid cation-exchange resin is placed in the glass container of autoclave, add about 1.5-4 doubly to the deionized water of resin volume (accumulation), airtightly be heated to 150-200 ℃, handled 8-16 hour under 0.5-1.6MPa pressure, this process need not to use deoxygenated water or adds alcohols material.Product after the processing washs through deionized water, promptly obtains the halogenation strong-acid cation-exchange resin catalyst of stabilisation." similar in appearance to the thing of frog's egg " alleged among the CN86102001A do not appear in the catalyst of handling through this method, and catalyst strength is unaffected.
Method of the present invention can be prepared the strong-acid cation-exchange resin catalyst of high-purity, high stability.This method process is simple, and the processing time is short, need not special reagent and isolated plant.Styrene-divinylbenzene copolymer structure purge process of the present invention can increase pore volume and specific area significantly, and the aperture is concentrated evenly, and halogen and sulfonic acid group content are improved.
Table 1 is that the styrene-divinylbenzene copolymer (microballoon) that contains divinylbenzene (DVB) 20% that Daxing County, Beijing resin processing plant produces is carried out structure purification process front and back physical arrangement correction data.
Table 2 is that the DVB12% styrene-divinylbenzene copolymer (microballoon) that Nankai University produces is carried out purification process front and back physical arrangement correction data.
Table 1
Table 2
Physical arrangement |
Surface area |
Pore volume |
Average pore size |
Copolymer |
m
2/g
|
ml/g |
10
-10m
|
The DVB12% copolymer |
0.3730 |
0.000263 |
28.1851 |
The purifying rear copolymer |
63.2663 |
0.25746 |
162.7796 |
Example 1
Get DVB12% specific area 0.373m
2/ g, pore volume 0.000263ml/g, aperture 28.18 * 10
-10Styrene-divinylbenzene copolymer microballoon 500 grams of m, with dichloroethanes swelling 2 hours at room temperature, copolymer after the filtration swelling, and be placed in 5 liters of autoclaves, add 2 liters of benzene, boost to 2.0MPa with nitrogen, be warming up to 180 ℃, stirred 16 hours, cooling, emit liquid, add 2 liters of absolute ethyl alcohols again, equally at 2.0MPa, be warming up to 180 ℃, stirring condition was handled 16 hours down, emit liquid after the cooling, the copolymer behind the taking-up purifying washs with deionized water, afterwards, in 70 ℃, 66.7KPa drying is 8 hours under the vacuum, copolymer yield 92%, the specific area 77.5m of purifying copolymer
2/ g, pore volume 0.376ml/g, aperture 194 * 10
-10M.
Get purified styrene-divinylbenzene copolymer 50 grams, place four-hole boiling flask, add 300 gram dichloroethanes, swelling 4 hours, add 3 gram anhydrous ferric trichlorides, be lower than under 20 ℃ of stirrings, slowly splash into 100 gram bromines, be cooled to 0 ℃ afterwards, stirred 10 hours, and filtered the back and washs successively with 1 liter of methyl alcohol, 2 liters of deionized waters, 1 liter of 2mol HCl, 3 liters of deionized waters, 1 liter of methyl alcohol, drying is 8 hours under 70 ℃, 66.7KPa vacuum, get brominated copolymer 95.5 grams, bromination rear copolymer weightening finish 91%.
Get brominated copolymer 50 grams, place four-hole boiling flask, added 250 gram dichloroethanes swellings 4 hours, take by weighing 50% oleum, 300 grams, under continuous stirring, slowly drip oleum, hierarchy of control temperature is not higher than 30 ℃, after dropwising, system temperature is adjusted to 33 ℃, reacts 12 hours, and product filters the back and washs successively with 4 liters of deionized waters, 1 liter of 5%NaCl, 4 liters of 2mol HCl, 3 liters of deionized waters, obtain 146 milliliters of bromination strong-acid cation-exchange resins, exchanging equivalent 1.11mol/l, water content 50%, dilation 2.07mol/g, warm apparent density 0.89kg/m
3, specific area 6.2m
2/ g, pore volume 0.44ml/g, aperture 175.9 * 10
-10M.
Get above-mentioned cationic ion-exchange resin 3ml, place the test tube of φ 10, add the 6ml deionized water, sealing test tube mouth, and put it in the autoclave that fills water, under 200 ℃, 1.6MPa condition, carry out 16,32,48,64 hours static tests, investigate the resin catalyst sulfonic acid group and run off result such as table 3.
Table 3
Time (hour) |
0 |
16 |
32 |
48 |
64 |
Exchanging equivalent (mol/1) |
1.11 |
0.93 |
0.88 |
0.85 |
0.84 |
Sulfonic acid group comes off, % |
0 |
16 |
20.7 |
23.4 |
25 |
Coming off of sulfonic acid group is in linear relation with the processing time, and this straight line is illustrated under 200 ℃, 1.6MPa condition, and sulfonic acid group belongs at a slow speed and runs off on the resin, and this linear extrapolation can get 12% sulfonic acid group and belong to quick loss part.
1.5 liters and 3 liters deionized waters of above-mentioned brominated strong-acid cation-exchange resin place in the glassware of autoclave, under 200 ℃ of 1.6MPa conditions, carry out 8 hours stabilization processes, wash with deionized water the cooling back, obtains the resin catalyst of exchanging equivalent 0.987mol/l.
Get 100 milliliters of above-mentioned exchanging equivalent 0.987mol/l resin catalysts, in φ 25 stainless steel reactors of packing into, 155 ℃, when 8.0MPa, water LHSV 1.25
-1, move 1536 hours continuously, investigate the loss law of sulfonic acid group.Result such as table 4.
Table 4
Time, hour |
0 |
415 |
1008 |
1536 |
Exchanging equivalent, mol/1 |
0.987 |
0.94 |
0.92 |
0.87 |
Operation is 1008 hours continuously, and the resin catalyst sulfonic acid group runs off 6.7%, and bleed rate is 6.49 milligrams of H
2SO
4/ (rising Cat hour).
The resin catalyst of above-mentioned exchanging equivalent 0.987mol/l, the 50 milliliters of fixed bed reactors of packing into carry out the n-butylene hydration reaction, reaction condition: 155-160 ℃, 8.0MPa, H
2/ C
= 4=2.5, nC
= 4-2=79%, nC
4During LHSV=1.32
-1, reaction was carried out 1500 hours, n-butene conversion per pass 5.5-6.5%, and the sec-butyl alcohol selectivity is greater than 98%, and the catalyst sulfonic acid group runs off 29%, and bleed rate is 20 milligrams of H
2SO
4/ (rise catalyst hour).
Get 800 milliliters of above-mentioned exchanging equivalent 0.987mol/l resin catalysts, at φ 30mm, in long 3 meters fixed bed reactors, at 155 ℃, 8.0MPa, water/alkene=2.5, nC
= 4-2=79%, nC
= 4During LHSV=1.0
-1Turned round 252 hours continuously under the condition, n-butene conversion per pass 10%, the sec-butyl alcohol selectivity is greater than 98%, and the catalyst sulfonic acid group runs off 2.7%.
Comparative example 1
Get DVB12%, specific area 0.373m
2/ g, pore volume 0.000263ml/g, aperture 28.18 * 10
-10M presses example 1 bromination process bromination without styrene-divinylbenzene copolymer microballoon 50 grams of structure of matter purification process, obtains brominated copolymer 76.5 grams, bromination rear copolymer weightening finish 53%.Obviously, the copolymer without the physical arrangement purification process is obviously reduced by the bromination ability under the same conditions.
Example 2
Get DVB20%, specific area 72.75m
2/ g, pore volume 0.285ml/g, aperture 156.9 * 10
-10Styrene-divinylbenzene copolymer pearl ball 500 grams of m are handled by example 1 structure of matter purification process, obtain specific area 75.167m
2/ g, pore volume 0.362ml/g, aperture 192.6 * 10
-10The purifying copolymer of m.Get above-mentioned purifying copolymer 75 grams, press the bromination process of example 1 and handle, obtain brominated copolymer 134 grams, bromination weightening finish 78.7%.
Comparative example 2
Get DVB20%, specific area 72.75m
2/ g, pore volume 0.285ml/g, aperture 156.9 * 10
-10The styrene of m-divinyl copolymer microsphere 75 grams without structure of matter purification process, is pressed the bromination process bromination of example 1, obtains brominated copolymer 120 grams, brominated copolymer weightening finish 60%, and its bromination amount is starkly lower than the bromination amount of example 2.
Example 3
Get DVB10%, specific area 7.49m
2/ g, pore volume 0.03975ml/g, aperture 212.28 * 10
-10Styrene-divinylbenzene copolymer microballoon 500 grams of m carry out the processing of structure of matter purifying by the method for example 1, obtain specific area 21.06m
2/ g, pore volume 0.114ml/g, aperture 217.6 * 10
-10The purifying copolymer of m.Get above-mentioned purifying copolymer 250 grams, the bromination process bromination of pressing example 1 obtains brominated copolymer 482 grams, bromination weightening finish 92.8%.
Example 4
Get the styrene-divinylbenzene copolymer microballoon of DVB8%, carry out structure of matter purification process, obtain specific area 17.7m by the method for example 1
2/ g, pore volume 0.099ml/g, aperture 223.5 * 10
-10The purifying copolymer of m.Get above-mentioned purifying copolymer 1 68 grams, according to example 1 bromination process bromination, the addition of controlling bromine simultaneously is 268.8 grams, obtains brominated copolymer 288 grams, brominated copolymer weightening finish 71.4%.
Get above-mentioned brominated copolymer microballoon 250 grams, press example 1 method of sulfonating sulfonation, get 200 milliliters of sulfonated copolymers, record exchanging equivalent 1.38mol/l, surface area 13.44m
2/ g, pore volume 0.0826ml/g, aperture 245.7 * 10
-10M, water content 48.76%, wet apparent density 0.86kg/m
3
Method by example 1 is carried out the active group stabilization processes to above-mentioned sulfonated copolymer, makes the cation exchange resin catalyst of exchanging equivalent 1.30mol/l.
Get 50 milliliters of above-mentioned catalyst, in the evaluating apparatus of 50 milliliters of the reactor volumes of packing into, at 155 ℃, 8.0MPa, water/alkene=2.5, nC
= 4-2=79%, nC
= 4During LHSV=1.32
-1Carry out the n-butylene hydration reaction under the condition, n-butene conversion per pass 5.65-6%, the sec-butyl alcohol selectivity is greater than 98%.Operation is 1400 hours continuously, does not see catalyst activity reduction.When operation 174 hours, record resin catalyst exchanging equivalent 1.29mol/l.5.63 milligrams of H of the bleed rate of sulfonic acid group
2SO
4/ rose Cat hour.
Example 5
Get the styrene-divinylbenzene copolymer microballoon of DVB8% and DVB10%, make strong-acid cation-exchange resin catalyst A and B respectively, its materialization property such as table 5 according to the method for example 1.
Table 5
Above-mentioned catalyst A, B carry out propylene hydration test respectively on the reaction unit of 50 milliliters of reactors, 130 ℃, when 8.0MPa, water/alkene=15, propylene LHSV=0.2
-1Carry out result such as table 6 under the condition.
Table 6
Catalyst |
Propylene rate of rotation % |
The isopropyl alcohol selectivity, % |
The isopropyl alcohol space-time yield, g/1h |
A |
67.69 |
98 |
100.2 |
B |
74.27 |
98 |
110.0 |
Comparative example 3
With the strong-acid cation-exchange resin catalyst K of Bayer A.G
2411, K
2611, under the reaction condition identical, carry out the propylene hydration test with example 5.Catalyst K
2411And K
2611Materialization property such as table 7.Propylene hydration result of the test such as table 8.
Table 7
|
K
2411 |
K
2611 |
Exchanging equivalent, mol/1 |
1.25 |
1.35 |
Granularity, mm |
0.315-1.66 |
0.3-1.25 |
Wet apparent density, g/1 |
720-820 |
700-800 |
Moisture content, %(is heavy) |
60-65 |
50 |
Specific area, m
2/g
|
25 |
40 |
The aperture, 10
-10m
|
500 |
650 |
Table 8
Catalyst |
Propylene conversion, % |
The isopropyl alcohol selectivity, % |
The isopropyl alcohol space-time yield, g/l.h |
K
2411 |
55.72 |
98 |
82.5 |
K
2611 |
66.21 |
98 |
98.0 |