CN1238111C - High exchange capacity resin catalyst and its preparation method - Google Patents
High exchange capacity resin catalyst and its preparation method Download PDFInfo
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- CN1238111C CN1238111C CN 200310123894 CN200310123894A CN1238111C CN 1238111 C CN1238111 C CN 1238111C CN 200310123894 CN200310123894 CN 200310123894 CN 200310123894 A CN200310123894 A CN 200310123894A CN 1238111 C CN1238111 C CN 1238111C
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- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 150000001555 benzenes Chemical class 0.000 claims abstract description 11
- 239000012188 paraffin wax Substances 0.000 claims abstract description 11
- 238000006277 sulfonation reaction Methods 0.000 claims description 34
- 239000004088 foaming agent Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 241001566735 Archon Species 0.000 claims description 20
- 150000008282 halocarbons Chemical class 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 230000002522 swelling effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 abstract description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006266 etherification reaction Methods 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000000638 solvent extraction Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a strong acidic macroporous cationic resin catalyst and a preparation method thereof. The resin catalyst is prepared from styrene and divinylbenzene by polymerization in the mode of straight chain paraffin of C8 to C20 and benzene derivatives as mixed pore-forming agents. The resin catalyst has the macropores communicated by small pores and is directly sulfonated by sulfuric acid with the concentration higher than 100%. Thus, the resin catalyst of the present invention has the advantages of high catalytic activity, long service life and exchange capacity higher than 5.25 mmol/g [H]. The present invention overcomes the defects of low exchange capacity, low catalytic activity and short service life of a resin catalyst for preparing MTBE from isobutylene and methanol by etherification in the prior art.
Description
Technical field
The present invention relates to a kind of high-capacity resin Catalysts and its preparation method, specifically, the present invention relates to a kind of high-exchange-capacity macropore strong acid cation exchange resin catalyst that is used for etherificate, olefin hydration and preparation method thereof.
Background technology
As solid acid catalyst, the macropore strong acid cation resin because its corrosion-resistant requirement to equipment material is looser, catalytic activity is high, product purity is high, easily separated, cost is low etc., and plurality of advantages has replaced liquid acid catalyst gradually, is widely used in organic synthesis industry such as etherificate, esterification, alkylation, olefin hydration.Especially in recent years along with the rapid increase of market to MTBE (methyl tertiary butyl ether(MTBE)) demand, a large amount of MTBE devices are gone into operation in succession, emerge the resin catalyst of many brands in this field especially, for example A-15, M-31, D005, CT-175, S-54 etc.
The production process of these resin catalysts generally comprises polymerization, solvent extraction and sulfonation three big steps.
(1) polymerization: styrene, divinylbenzene, pore-foaming agent, initator etc. are dropped in the polymerization reaction kettle by certain prescription batching mixing, containing the aqueous phase suspension copolymerization of certain dispersant, the copolymer Archon is through washing, dry, the Archon that sieves into desired particle size.
(2) solvent extraction: the pore-foaming agent in the above-mentioned Archon is extracted with organic solvent.
(3) sulfonation: Archon also dry behind the above-mentioned solvent extraction is obtained the macropore strong acid cation resin catalyst with certain density sulfuric acid sulfonation, washing.
In actual production and application process, all there are some shortcomings to some extent in above-mentioned resin and production technology thereof, and (1) catalytic activity is lower.The catalytic activity of resin depends mainly on the pore structure and the acidity of resin, and the then main and polymerization formula of pore structure especially pore-foaming agent kind and addition has direct relation.Disclosed at present pore-foaming agent has Chinese patent CN1032017A, CN1151334A, the former proposes the part or all of replace organic solvent of water and prepares making large-pore white balls used as pore-foaming agent, catalytic resin is made in sulfonation then, when because of semi-finished product, product intensity relatively poor, can not satisfy the catalytic reaction requirement, so fail really to obtain commercial Application always.The latter proposes with the pore of low-carbon (LC) alcohols, because of this class pore-foaming agent is dissolved in or soluble in water mostly, thereby polymer dispersion system is required harsh, operating difficulties, balling ratio is on the low side.Above-mentioned its pore-foaming agent of MTBE etherificate catalytic resin of having used on industrial production nearly all adopts traditional poor solvent pores such as liquid wax, in various prescriptions, although can change size and other pore structure parameter in copolymer aperture by the liquid wax of selecting the different trades mark, but only depend on molecule gap (gel pore) UNICOM between macropore that causes out and the macropore, this molecule gap can only allow the less ion of volume pass through, reactant and the product molecule bigger for volume then are difficult to pass through, therefore cause the intragranular diffusional resistance to increase, catalytic activity reduces.(2) catalyst is shorter service life, and in the MTBE etherificate catalytic resin of having reported, exchange capacity is generally lower, is generally 4.6-5.0mmol/g[H], this not only influences its catalytic activity, and generally be no more than 10 months service life.
Summary of the invention
Problems such as above-mentioned exchange capacity is lower, catalytic activity is low in order to solve in the present invention, service life is short have proposed a kind of catalytic activity height, long service life, exchange capacity and have been higher than 5.25mmol/g[H] MTBE etherificate macropore strong acid cation resin catalyst and preparation method thereof.
A kind of high-capacity resin catalyst is characterized in that:
(1) it is a kind of macroporous strong-acid cation-exchange resin, and making the parent styrene of this resin and the pore-foaming agent of divinylbenzene copolymer Archon is to use C
8～C
20Linear paraffin is made the mixing pore-foaming agent that poor solvent pore-foaming agent and benzene analog derivative are made the good solvent pore-foaming agent;
(2) use C
5～C
13Alkane solvents under 25～80 ℃, carry out the extraction of pore-foaming agent in the copolymer Archon and the hole purifies;
(3) making large-pore white balls used after the hole purifies is that the high-concentration sulfuric acid sulfonation with 98～106% forms under the swelling of halogenated hydrocarbons.
Described high-capacity resin Preparation of catalysts method may further comprise the steps:
(1) uses C
8～C
20Linear paraffin and benzene analog derivative do to mix pore-foaming agent, adopt conventional polymerization that styrene and divinylbenzene are carried out suspension copolymerization and make making large-pore white balls usedly, wash then, dry, screening; Weight sum in styrene and divinylbenzene is 1 weight portion, and wherein the parts by weight of key component are:
Styrene 0.6～0.9 weight portion, divinylbenzene 0.1～0.4 weight portion, C
8～C
20Linear paraffin 0.2～0.5 weight portion, benzene analog derivative 0.05～0.2 weight portion;
(2) with the product C of step (1)
5～C
13Alkane solvents go out pore-foaming agent 25～80 ℃ of following extractings, and dry; The volume ratio of solvent and Archon is 5～10: 1;
(3) with the product of step (2) sulfuric acid sulfonation under the swelling action of halogenated hydrocarbons with mass percent concentration 98～106%;
(4) with product 50% Dilution of sulphuric acid of step (3), extremely neutral with the pure water washing again, obtain product.
C described in the step (1)
8～C
20Linear paraffin be liquid wax, white oil or their mixture, described benzene analog derivative is benzene,toluene,xylene or their mixture.Poor solvent can cause out macropore, and good solvent can cause out macropore and aperture, and aperture can connect both macropores.Poor solvent C
8-C
20Linear paraffin be liquid wax or white oil etc., good solvent benzene analog derivative is a benzene,toluene,xylene etc.The screening of step (1) can be carried out as required, removes granule and oarse-grained Archon through screening.Granule produces the resistance that strengthens in application process, bulky grain produces certain intergranular space in application process, and bulk density is little, increases the volume of reactor.The industrial particle of generally selecting 0.3～1.3mm for use.
C described in the step (2)
5～C
13Alkane solvents be the 120# industrial naptha.The consumption of solvent does not have strict restriction, is generally more than 3 times of Archon quality.But consumption is too big, and production cost strengthens, and generally is controlled at below 10 times.
The sulfonation of described step (3) is the product that step (2) obtains directly to be added in the mixed liquor of the sulfuric acid of mass percent concentration 100～106% and halogenated alkane carry out sulfonation, the weight ratio of 100～106% sulfuric acid, halogenated hydrocarbons and step (2) product is 3～10: 0.3～1.0: 1, the sulfonation time is 5～24 hours, and sulfonation temperature is 25～140 ℃.
The product that the sulfonation of described step (3) also can obtain step (2) adds halogenated hydrocarbons, under the stirring suspension state, slowly add mass percent concentration and be 100～106% sulfuric acid and carry out sulfonation, the weight ratio of halogenated hydrocarbons, 100～106% sulfuric acid and step (2) product is 3～10: 0.8～3: 1, sulfonation temperature is 25～140 ℃, and the sulfonation time is 5～24 hours.
The sulfonation of described step (3) also can add the product of step (2) in the mixed liquor of the sulfuric acid of mass percent concentration 90～100% and halogenated alkane 80～120 ℃ of following sulfonation 8～24 hours, extract sulfate liquor out, add mass percent concentration again and be 100～106% oleum and carried out sulfonation 8～24 hours at 25～140 ℃; (step (2) product): (90～100% sulfuric acid): halogenated hydrocarbons: the weight ratio of (100～106% oleum) is 1: 3～10: 0.3～1.0: 3～10.
Described halogenated hydrocarbons is monochlorethane, dichloroethanes, carbon tetrachloride or its mixture.
Described resin catalyst can be applied in the process of etherificate, olefin hydration.
Described resin catalyst specifically can be applied in the process of isobutene etherificate system methyl tertiary butyl ether(MTBE), iso-amylene etherificate tert amyl methyl ether(TAME), light petrol etherificate, preparing tert-butanol from isobutylene by hydration, iso-amylene hydration system tert-pentyl alcohol.
Resin catalyst of the present invention and preparation method thereof has following outstanding advantage.
(1) add good solvent mixing pore in poor solvent, the aperture that is caused out by good solvent between the macropore that poor solvent is caused out connects mutually, has increased the activated centre of inside, duct greatly, thereby has improved catalytic activity.
(2) adopt low-carbon paraffin or 120
#Industrial naptha is as the extractant of polymerization Archon pore-foaming agent.According to " similar compatibility principle " in the physical chemistry, its extracting to pore-foaming agent is more thorough than the benzene series solvent extraction ground that Chinese patent CN1076385A proposes.
(3) Archon that obtains of step (2) resin exchange capacity is exceeded more than 15% than other similar catalytic resin, so its catalytic activity all significantly improves with the sulfuric acid Direct Sulfonation of high concentration than other similar catalytic resin with service life.
The specific embodiment
In order to describe resin catalyst of the present invention and preparation method thereof in more detail, further specify with embodiment below, but claim scope of the present invention is not limited to these embodiment.
Embodiment 1
(1) polymerization: in 30 liters polymeric kettle, add 16 premium on currency, be heated to 45 ℃, under stirring, add 150g sodium carbonate, 300g magnesium sulfate, 40g gelatin and 0.1g methine orchid respectively, be stirred to the dissolving back and add by 7760g styrene, 1100g divinylbenzene (content is 50%), 50g benzoyl peroxide, 2500g 300
#The oil phase that liquid wax and 1770g toluene mix is warming up to 75 ℃ of afterreactions and generated spherical product in 10 hours, is warming up to 90 ℃ again and boils ball 4 hours, the Archon 10220g that filter, wash, dry, screening obtains 0.315-1.120mm:
(2) solvent extraction: the Archon that step (1) is obtained is with 120 of 5 times of volumes
#Industrial naptha goes out pore-foaming agent in 50 ± 2 ℃ of following extractings, and oven dry obtains semi-finished product Archon 6645g;
(3) sulfonation: with 100 liters enamel reaction still, add the 19940g mass percent concentration successively and be the 6645g Archon that 102% sulfuric acid and 3300g dichloroethanes and step (2) obtain, insulation is 6 hours after being warming up to 110 ± 1 ℃, reduce to normal temperature then, slowly add entry dilution, when acid concentration reduces to 5% when following, filter, to neutral, being dried to water content is 10%, obtains resin catalyst of the present invention with the pure water washing.The physicochemical property of resin catalyst is listed table 1 in.
The resin catalyst of use preparation carries out isobutene in fixed bed and methanol etherification prepares MTBE, estimates the activity and the selectivity of used resin catalyst, and the mol ratio of isobutene and methyl alcohol is 1: 1, and result of the test is listed in table 2.
Measure the exchange capacity of the resin catalyst of preparation, and its normal pressure is boiled (82.5 ℃) with the tert-butyl alcohol (analyzing pure) and measure exchange capacity after boiling after 500 hours, calculate its sulfonic exfoliation rates, the results are shown in table 3.
Embodiment 2
Polymerization, the solvent extraction step of polymerization among the preparation method, solvent extraction step and embodiment 1 are identical; In sulfonation procedure, stirred swelling 2 hours in the 6645g Archon adding 30000g dichloroethanes with gained, the sulfuric acid 8000g in dripping 102% below 60 ℃ dropwised afterreaction 15 hours, neutrality, drying are lowered the temperature, dilute, filter, are washed to same procedure by embodiment 1.
Identical with embodiment 1, with physicochemical property, evaluation result with take off sulphur speed and list in table 1,2,3 respectively.
Embodiment 3
Polymerization, the solvent extraction step of polymerization among the preparation method, solvent extraction step and embodiment 1 are identical; In sulfonation procedure, the 6645g Archon of gained is added 98% sulfuric acid and 2400g dichloroethanes of 5 times of quality, dissolved rising 2 hours, be warming up to 80 ± 1 ℃, be incubated 6 hours, rise to 110 ± 1 ℃, be incubated 4 hours, reduce to normal temperature, add 106% oleum after the filtration again, be warming up to 110 ± 1 ℃, be incubated 6 hours, reduce to normal temperature again, slow thin up, filter, be washed to neutrality, drying.
Identical with embodiment 1, with physicochemical property, evaluation result with take off sulphur speed and list in table 1,2,3 respectively.
Comparative Examples 1
Physicochemical property index, etherification activity and the selectivity of the A-15 type MTBE etherificate resin catalyst that U.S. Rhom and Hass is produced, take off sulphur speed and list in table 1,2,3 respectively.
Comparative Examples 2
Physicochemical property index, etherification activity and the selectivity of the M-31 type MTBE etherificate resin catalyst that Bayer A.G is produced, take off sulphur speed and list in table 1,2,3 respectively.
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 |
| Exchange capacity (mmol/g[H]) | 5.35 | 5.28 | 5.30 | 4.70 | 4.63 |
| Butt density (kg/m 3) | 580 | 580 | 585 | 590 | 590 |
| The swelling ratio | 1.42 | 1.35 | 1.35 | 1.3-1.4 | 1.3-1.4 |
| Average pore radius (* 10 μ m) | 168 | 180 | 159 | 190 | 240 |
| Specific area (m 2/g) | 35.71 | 35.68 | 38.70 | 68.86 | 49.50 |
| Pore volume (ml/g) | 0.301 | 0.333 | 0.350 | 0.323 | 0.285 |
| Granularity (mm) | 0.3-0.9 | 0.3-0.9 | 0.3-0.9 | 0.3-1.2 | 0.3-1.2 |
From the result of table 1 as can be seen, the exchange capacity of resin catalyst of the present invention is higher than 5.25mmol/g[H].
Table 2
| Experimental condition | Isobutene conversion (%)/selectivity (%) | |||||
| Temperature (℃) | Air speed (h -1) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 |
| 40℃ | 1.0 | 93.59/99.50 | 93.60/99.50 | 93.83/99.50 | 89.19/99.13 | 87.40/99.18 |
| 3.0 | 90.42/99.80 | 91.20/99.70 | 91.50/99.80 | 84.14/99.50 | 84.50/99.50 | |
| 5.0 | 87.33/97.90 | 88.61/97.30 | 88.50/99.30 | 77.51/97.45 | 75.93/98.90 | |
| 60℃ | 1.0 | 97.13/99.90 | 97.50/99.50 | 97.83/99.67 | 95.34/98.50 | 96.95/99.20 |
| 3.0 | 97.76/99.50 | 97.45/99.40 | 97.62/99.80 | 95.24/98.43 | 96.05/98.89 | |
| 5.0 | 96.35/99.10 | 97.00/99.40 | 97.40/99.50 | 93.77/98.91 | 96.76/99.10 | |
| 80℃ | 1.0 | 93.52/99.30 | 93.80/99.67 | 93.89/99.50 | 92.45/98.70 | 92.68/97.45 |
| 3.0 | 93.26/99.43 | 93.56/98.90 | 93.50/99.90 | 92.40/98.70 | 92.64/98.20 | |
| 5.0 | 93.20/99.46 | 93.40/98.90 | 93.40/99.70 | 92.20/98.34 | 92.59/98.50 | |
From the result of table 2 as can be seen, the activity of resin catalyst of the present invention and selectivity all are higher than the resin catalyst of Comparative Examples.
Table 3
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 |
| Boil preceding exchange capacity (mmol/g[H]) | 5.35 | 5.28 | 5.30 | 4.70 | 4.63 |
| Exchange capacity after boiling (mmol/g[H]) | 5.13 | 5.10 | 5.10 | 4.45 | 4.20 |
| Take off sulphur speed mmol[H]/gh | 4.4×10 -4 | 3.6×10 -4 | 4.0×10 -4 | 5.0×10 -4 | 8.6×10 -4 |
From the data of table 3 as can be seen, the sulfonic exfoliation rates of resin catalyst of the present invention is starkly lower than the resin catalyst of two Comparative Examples, illustrates that the service life of resin catalyst of the present invention is longer than Comparative Examples.
Claims (8)
1. high-capacity resin catalyst is characterized in that:
(1) it is a kind of macroporous strong-acid cation-exchange resin, and making the parent styrene of this resin and the pore-foaming agent of divinylbenzene copolymer Archon is to use C
8～C
20Linear paraffin is made the mixing pore-foaming agent that poor solvent pore-foaming agent and benzene analog derivative are made the good solvent pore-foaming agent;
(2) use C
5～C
13Alkane solvents under 25～80 ℃, carry out the extraction of pore-foaming agent in the copolymer Archon and the hole purifies;
(3) making large-pore white balls used after the hole purifies is that the high-concentration sulfuric acid sulfonation with 98～106% forms under the swelling of halogenated hydrocarbons.
2. the preparation method of the described resin catalyst of claim 1 is characterized in that it may further comprise the steps:
(1) uses C
8～C
20Linear paraffin and benzene analog derivative do to mix pore-foaming agent, adopt conventional polymerization that styrene and divinylbenzene are carried out suspension copolymerization and make making large-pore white balls usedly, wash then, dry, screening; Weight sum in styrene and divinylbenzene is 1 weight portion, and wherein the parts by weight of key component are:
Styrene 0.6～0.9 weight portion, divinylbenzene 0.1～0.4 weight portion, C
8～C
20Linear paraffin 0.2～0.5 weight portion, benzene analog derivative 0.05～0.2 weight portion;
(2) with the product C of step (1)
5～C
13Alkane solvents go out pore-foaming agent 25～80 ℃ of following extractings, and dry; The volume ratio of solvent and Archon is 5～10: 1;
(3) with the product of step (2) sulfuric acid sulfonation under the swelling action of halogenated hydrocarbons with mass percent concentration 98～106%;
(4) with product 50% Dilution of sulphuric acid of step (3), extremely neutral with the pure water washing again, obtain product.
3. preparation method according to claim 2 is characterized in that described C
8～C
20Linear paraffin be liquid wax, white oil or their mixture, described benzene analog derivative is benzene,toluene,xylene or their mixture.
4. preparation method according to claim 2 is characterized in that, the C in the step (2)
5～C
13Alkane solvents be the 120# industrial naptha.
5. preparation method according to claim 2, it is characterized in that, the sulfonation of step (3) is the product that step (2) obtains directly to be added in the mixed liquor of the sulfuric acid of mass percent concentration 100～106% and halogenated alkane carry out sulfonation, the weight ratio of 100～106% sulfuric acid, halogenated hydrocarbons and step (2) product is 3～10: 0.3～1.0: 1, the sulfonation time is 5～24 hours, and sulfonation temperature is 25～140 ℃.
6. preparation method according to claim 2, the sulfonation that it is characterized in that step (3) is that the product that step (2) obtains is added halogenated hydrocarbons, under the stirring suspension state, slowly add mass percent concentration and be 100～106% sulfuric acid and carry out sulfonation, the weight ratio of halogenated hydrocarbons, 100～106% sulfuric acid and step (2) product is 3～10: 0.8～3: 1, sulfonation temperature is 25～140 ℃, and the sulfonation time is 5～24 hours.
7. preparation method according to claim 2, it is characterized in that, the sulfonation of step (3) is that the product of step (2) is added in the mixed liquor of the sulfuric acid of mass percent concentration 90～100% and halogenated alkane 80～120 ℃ of following sulfonation 8～24 hours, extract sulfate liquor out, add mass percent concentration again and be 100～106% oleum and carried out sulfonation 8～24 hours at 25～140 ℃; (step (2) product): (90～100% sulfuric acid): halogenated hydrocarbons: the weight ratio of (100～106% oleum) is 1: 3～10: 0.3～1.0: 3～10.
8. according to claim 5,6,7 described preparation methods, it is characterized in that described halogenated hydrocarbons is monochlorethane, dichloroethanes, carbon tetrachloride or its mixture.
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| CN 200310123894 CN1238111C (en) | 2003-12-31 | 2003-12-31 | High exchange capacity resin catalyst and its preparation method |
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| CN102755904B (en) * | 2011-04-26 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of acidic molecular sieve and resin composite catalyst |
| CN102755903B (en) * | 2011-04-26 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of acidic molecular sieve and resin composite catalyst |
| CN102319586B (en) * | 2011-06-10 | 2012-10-17 | 凯瑞化工股份有限公司 | Resin catalyst used in alkylation reaction of isobutene and butylene and preparation method thereof |
| CN102614916B (en) * | 2012-02-28 | 2013-11-13 | 同济大学 | Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene |
| CN103586075B (en) * | 2013-11-26 | 2015-07-08 | 凯瑞环保科技股份有限公司 | Light petrol etherification catalyst and preparation method thereof |
| CN107138177A (en) * | 2017-05-26 | 2017-09-08 | 丹东明珠特种树脂有限公司 | Methanol extraction water depickling resin catalyst prepared by methyl tertiary butyl ether(MTBE) and preparation method thereof |
| CN107626347A (en) * | 2017-09-26 | 2018-01-26 | 丹东明珠特种树脂有限公司 | Resin catalyst for light gasoline etherification and preparation method thereof |
| CN108558612A (en) * | 2018-04-25 | 2018-09-21 | 陈久仓 | A kind of preparation method of methyl tertiary butyl ether(MTBE) |
| CN110586185B (en) * | 2019-09-27 | 2022-07-12 | 凯瑞环保科技股份有限公司 | Tert-butyl alcohol methanol etherification resin catalyst and preparation method thereof |
| CN111111792A (en) * | 2020-01-07 | 2020-05-08 | 凯瑞环保科技股份有限公司 | Strong acid cation exchange resin for adsorbing iron and preparation method and application thereof |
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