CN1030321C - Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst - Google Patents
Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst Download PDFInfo
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- CN1030321C CN1030321C CN 92101543 CN92101543A CN1030321C CN 1030321 C CN1030321 C CN 1030321C CN 92101543 CN92101543 CN 92101543 CN 92101543 A CN92101543 A CN 92101543A CN 1030321 C CN1030321 C CN 1030321C
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- styrene
- catalyst
- multipolymer
- exchange resin
- high temperature
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title abstract description 18
- 239000002253 acid Substances 0.000 title description 19
- 239000003729 cation exchange resin Substances 0.000 title description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000031709 bromination Effects 0.000 claims abstract description 21
- 238000005893 bromination reaction Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 9
- 238000000638 solvent extraction Methods 0.000 claims abstract 4
- 230000008961 swelling Effects 0.000 claims description 11
- 150000001555 benzenes Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- HLTUZPFCDXKNKS-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene ethene Chemical compound C(=C)C1=C(C=CC=C1)C=C.C=C HLTUZPFCDXKNKS-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 238000005341 cation exchange Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003456 ion exchange resin Substances 0.000 abstract 1
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 1
- 239000011806 microball Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 26
- 239000011148 porous material Substances 0.000 description 21
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 11
- 206010042674 Swelling Diseases 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 230000026030 halogenation Effects 0.000 description 7
- 238000005658 halogenation reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 241000973497 Siphonognathus argyrophanes Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing ion exchange resin catalysts with high temperature resistance. Solvent extraction is carried out on raw materials of styrene-divinylbenzene copolymer micro balls at high temperature under certain pressure; then, bromination and sulfonation are carried out; finally, a catalyst is obtained by treating deionized water at the high temperature; the specific surface area, the hole diameter and the hole volume numerical value of the catalyst are higher than those of a catalyst prepared by an ordinary method. The catalyst of the present invention has the advantages of high reactivity and high temperature resisting performance, and obviously enlarges the service life.
Description
The present invention relates to high temperature resistant strong-acid cation-exchange resin catalyst, particularly the preparation method of vinylbenzene-divinylbenzene crosslink multipolymer strong-acid cation-exchange resin catalyst.
Vinylbenzene-divinylbenzene strong-acid cation-exchange resin catalyst is widely used in petrochemical complex and field of fine chemical, as is used for processes such as esterification, etherificate, aromizing and olefin hydration.The subject matter that this resinoid catalyzer exists is the coming off of sulfonic acid group in reaction process, 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 nucleus of Zeo-karb is protonated.In order to prevent the protonated of phenyl ring, common way is to introduce electron-withdrawing group, slows down coming off of sulfonic acid group.
English Patent GB1,393,594 with chlorostyrene and the synthetic heatproof Zeo-karb 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 tetracol phenixin under 10 ℃ of catalysis of iodine and agitation 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 multipolymer of chloride 20-40%.This multipolymer and 99% sulfuric acid and ethylene dichloride are positioned in the reactor, stir 2 hours down in 60 ℃, temperature of reaction are risen to 120 ℃ then, keep 19 hours.Afterwards, reaction 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 Zeo-karb of moisture 40-60.
Similar techniques also has JP83-80307, patents such as JP88-63535.The catalyzer 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 lnc. declares in China proposes, to core by halogen substituted strong-acid cation exchanger before using as catalyzer, 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 catalyzer hour) and 7 milligrams of HCl/(rise catalyzer 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 treatment process needs specific equipment and requires to remove dissolved oxygen in the treating water, and need reach 200-300 hour treatment 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 differing temps in water in Ind, Eng, Chem.Prod.Res.Dev1981.20.366-371.Show in 150-200 ℃ of scope, in the resin loss of sulfonic acid group relevant with vinylbenzene/divinylbenzene ratio, 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, vinyl toluene etc.Because the existence of above-mentioned impurity, make and contain a large amount of small molecules multipolymer 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 vinylbenzene-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 Zeo-karb that is mingled with these small molecular weight impurities is used for chemical reaction process, under reaction conditions, 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 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 treatment.
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 treatment.
Detailed process of the present invention is as follows:
One, with styrene-divinylbenzene copolymer microballoon C
1-C
4Halohydrocarbon swelling 0.5-5 hour, multipolymer after the swelling moves into and fills in the container of benzene series solvent, quantity of solvent is 1.5-4 a times of multipolymer volume, handled 3-20 hour 0.1-5.0MPa and 130-200 ℃, with extractings such as unsettled component and fragment in the multipolymer in solvent, take out multipolymer afterwards and handled 3-20 hour with dehydrated alcohol, make multipolymer 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 ethylene dichloride swelling multipolymer, add FERRIC CHLORIDE ANHYDROUS, 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 agitation condition, the oleum of slow Dropwise 5 0% in multipolymer, 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 Containers 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 de-oxygenised water or adds alcohols material.Product after the processing washs through deionized water, promptly obtains the halogenation strong-acid cation-exchange resin catalyst of stabilization." similar in appearance to the thing of frog's egg " alleged among the CN86102001A do not appear in the catalyzer 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.Present method process is simple, and the treatment 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 surface 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 structure correlation data.
Table 2 is that the DVB12% styrene-divinylbenzene copolymer (microballoon) that Nankai University produces is carried out purification process front and back physical structure correlation data.
Table 1
Physical structure surface-area pore volume mean pore size
Multipolymer m
2/ g ml/g 10
-10m
Multipolymer 72.7528 0.2854 156.966 before the purifying
Purifying rear copolymer 75.1672 0.36206 192.672
Table 2
Physical structure surface-area pore volume mean pore size
Multipolymer m
2/ g ml/g 10
-10m
DVB12% multipolymer 0.3730 0.000263 28.1851
Purifying rear copolymer 63.2663 0.25746 162.7796
Fig. 1 is that the styrene-divinylbenzene copolymer of DVB20% that Daxing County, Beijing resin processing plant is produced carries out graph of pore diameter distribution before and after the structure purifying.Dotted line represents to handle the front aperture distribution among the figure, and solid line represents to handle the back aperture distribution plan.
Fig. 2 is the DVB12% styrene-divinylbenzene copolymer graph of pore diameter distribution that Nankai University produces.
Fig. 3 carries out structure purification process back aperture distribution plan to the DVB12% styrene-divinylbenzene copolymer that Nankai University produces.
Example 1
Get DVB12% specific surface area 0.373m
2/ g, pore volume 0.000263ml/g, aperture 28.18 * 10
-10Styrene-divinylbenzene copolymer microballoon 500 grams of m, with ethylene dichloride swelling 2 hours at room temperature, multipolymer 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 dehydrated alcohols again, equally at 2.0MPa, be warming up to 180 ℃, agitation condition was handled 16 hours down, emit liquid after the cooling, the multipolymer behind the taking-up purifying washs with deionized water, afterwards, in 70 ℃, 66.7KPa drying is 8 hours under the vacuum tightness, copolymer yield 92%, the specific surface area 77.5m of purifying multipolymer
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 ethylene dichloride, swelling 4 hours, add 3 gram FERRIC CHLORIDE ANHYDROUS, 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 tightness, 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 ethylene dichloride swellings 4 hours, take by weighing 50% oleum, 300 grams, under continuously 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%, swelling capacity 2.07mol/g, warm volume density 0.89kg/m
3, specific surface area 6.2m
2/ g, pore volume 0.44ml/g, aperture 175.9 * 10
-10M.
Get above-mentioned Zeo-karb 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/l) 1.11 0.93 0.88 0.85 0.84
Sulfonic acid group comes off, and % 0 16 20.7 23.4 25
Coming off of sulfonic acid group is in linear relation with the treatment 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 straight-line 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 treatment, 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 LHSV1.25
-1, move 1536 hours continuously, investigate the loss law of sulfonic acid group.Result such as table 4.
Table 4
Time, hours 0 415 1,008 1536
Exchanging equivalent, mol/l 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 reactor of packing into carry out the n-butylene hydration reaction, reaction conditions: 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 per pass conversion 5.5-6.5%, and the sec-butyl alcohol selectivity is greater than 98%, and the catalyzer sulfonic acid group runs off 29%, and bleed rate is 20 milligrams of H
2SO
4/ (rise catalyzer hour).
Get 800 milliliters of above-mentioned exchanging equivalent 0.987mol/l resin catalysts, at φ 30mm, in long 3 meters fixed-bed reactor, at 155 ℃, 8.0MPa, water/alkene=2.5, nC
= 4-2=79%, nC
= 4During LHSV=1.0
-1Continuous operation is 252 hours under the condition, n-butene per pass conversion 10%, and the sec-butyl alcohol selectivity is greater than 98%, and the catalyzer sulfonic acid group runs off 2.7%.
Comparative example 1
Get DVB12%, specific surface 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 multipolymer without the physical structure purification process is obviously reduced by the bromination ability under the same conditions.
Example 2
Get DVB20%, specific surface 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 surface area 75.167m
2/ g, pore volume 0.362ml/g, aperture 192.6 * 10
-10The purifying multipolymer of m.Get above-mentioned purifying multipolymer 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 surface area 72.75m
2/ g, pore volume 0.285ml/g, aperture 156.9 * 10
-10The vinylbenzene 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 surface 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 surface area 21.06m
2/ g, pore volume 0.114ml/g, aperture 217.6 * 10
-10The purifying multipolymer of m.Get above-mentioned purifying multipolymer 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 surface area 17.7m by the method for example 1
2/ g, pore volume 0.099ml/g, aperture 223.5 * 10
-10The purifying multipolymer of m.Get above-mentioned purifying copolymer 1 68 grams, according to example 1 bromination process bromination, the add-on 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 volume density 0.86kg/m
3
Method by example 1 is carried out the active group stabilization treatment to above-mentioned sulfonated copolymer, makes the cation exchange resin catalyst of exchanging equivalent 1.30mol/l.
Get 50 milliliters of above-mentioned catalyzer, 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 per pass conversion 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
A B
Moisture, %(is heavy) 48.7 44.71
Exchanging equivalent, mol/l 1.38 1.53
Granularity, mm 0.3-1.25 0.3-1.25
Wet 0.86 0.82
Volume density
G/ml does 0.44 0.45
The aperture, 10
-10M 245.7 254.7
Pore volume, ml/g 0.0826 0.1010
Specific surface area, m
2/ g 13.44 15.85
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
Catalyzer propylene rate of rotation, % Virahol selectivity, % Virahol space-time yield, g/lh
A 67.69 98 100.2
B 74.27 98 110.0
Comparative example 3
With the strong-acid cation-exchange resin catalyst K2411 of Bayer A.G, K2611, under the reaction conditions identical, carry out the propylene hydration test with example 5.Materialization property such as the table 7 of catalyzer K2411 and K2611.Propylene hydration test-results such as table 8.
Table 7
K2411 K2611
Exchanging equivalent, mol/l 1.25 1.35
Granularity, mm 0.315-1.66 0.3-1.25
Wet volume density, g/l 720-820 700-800
Moisture content, %(is heavy) 60-65 50
Specific surface area, m
2/ g 25 40
The aperture, 10
-10M 500 650
Table 8
The catalyzer propylene conversion, % Virahol selectivity, % Virahol space-time yield, g/lh
K2411 55.72 98 82.5
K2611 66.21 98 98.0
Claims (5)
1, the high temperature resistant strongly acidic cation-exchange method for preparing catalyst of a kind of stupid ethene-divinylbenzene, its feature comprises:
A, swollen styrene-divinylbenzene copolymer microballoon were 0.1-5.0MPa and 130-200 ℃ of benzene series solvent extraction 3-20 hour;
B, step (A) product bromination;
C, the sulfonation of step (B) product;
D, step (C) product handled 8-16 hour with deionized water under 150-200 ℃ and 0.5-1.6MPa.
2,, it is characterized in that the styrene-divinylbenzene copolymer microballoon before the benzene series solvent extraction, uses C according to the method for claim 1
1-C
4Halohydrocarbon swelling 0.5-5 hour.
3, according to the method for claim 1, it is characterized in that the multipolymer after the sulfonation, handle with the deionized water of 1.5-4 times of volume.
4, according to the method for claim 1 or 2, it is characterized in that the multipolymer behind the benzene series solvent extraction, handled 3-20 hour 0.1-5.0MPa and 130-200 ℃ with dehydrated alcohol.
5, according to the method for claim 1 or 2, the consumption that it is characterized in that the benzene series solvent is 1.5-4 a times of multipolymer volume.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101543 CN1030321C (en) | 1992-03-13 | 1992-03-13 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101543 CN1030321C (en) | 1992-03-13 | 1992-03-13 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
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| CN1030321C true CN1030321C (en) | 1995-11-22 |
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-
1992
- 1992-03-13 CN CN 92101543 patent/CN1030321C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116178150A (en) * | 2023-03-13 | 2023-05-30 | 深圳飞扬骏研新材料股份有限公司 | Method for continuously producing diethyl maleate with low trans content |
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