CN104368377A - Preparation and applications of ZSM11 molecular sieve catalyst containing aluminium phosphate binder - Google Patents
Preparation and applications of ZSM11 molecular sieve catalyst containing aluminium phosphate binder Download PDFInfo
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- CN104368377A CN104368377A CN201310352097.8A CN201310352097A CN104368377A CN 104368377 A CN104368377 A CN 104368377A CN 201310352097 A CN201310352097 A CN 201310352097A CN 104368377 A CN104368377 A CN 104368377A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a preparation method and applications of a ZSM11 molecular sieve catalyst containing an aluminum phosphate binder. The preparation method comprises the following steps: subjecting prepared original superfine rare earth-ZSM-11 molecular sieve powder to ion exchange, drying, baking so as to obtain H-rare earth-ZSM-11 molecular sieves; mixing a phosphoric acid solution with boehmite so as to obtain a binder, evenly mixing the binder and the obtained molecular sieves, drying, burning, and finally carrying out a water steam treatment so as to obtain the target catalyst. The provided catalyst is used to catalyze reactions between ethylene and benzene to prepare ethyl benzene in an atmosphere of dry gas. The provided catalyst has the following advantages: (1) the ethylene conversion rate is prominently improved, compared to that of reactions catalyzed by a molecular sieve catalyst containing aluminum oxide; (2) the selectivity of ethyl benzene and ethylation products is high; (3) the xylene content is low.
Description
Technical field
The present invention relates to the catalyst field of producing ethylo benzene, be specifically related to a kind of preparation method and application of ZSM11 molecular sieve catalyst of phosphoric acid al binder.
Background technology
Alkylaromatic hydrocarbon is the intermediate products having extensive use, wherein most importantly ethylbenzene and isopropylbenzene, ethylbenzene produces cinnamic critical materials, and styrene is the important monomer of synthesized polymer material, be mainly used in producing polystyrene and copolymer A BS resin, AS resin, butadiene-styrene rubber and unsaturated polyester etc., in recent ten years, ethylbenzene production capacity in the world doubles many, in recent years, the demand of China to this plastics also increases day by day, only China in 2010 to cinnamic demand more than 4,000,000 tons/year.
Catalytic cracked dry gas is the tail gas of refinery's by-product, wherein containing ethene 12-25% (volume fraction), burns, cause the waste of resource and the pollution of environment mainly as combustion gas or torch of setting fire.At present, China's catalytic cracking unit scale occupies second place of the world, the ethene considerable amount in dry gas.If by itself and benzene-alkylation ethylbenzene, the cinnamic disparities between supply and demand in domestic market can be relaxed, the effective utilization also can opening up catalytic cracked dry gas by way of, for oil refining enterprise increases economic efficiency.
The multiple process being raw material ethylbenzene with ethene and benzene has been developed since the '30s end.The mid-1970s, Mobil company of the U.S. reports and adopts HZSM-5 molecular sieve catalyst to carry out benzene and pure ethylene alkylated reaction for vapor phase method in USP3751506.USP4,107,224 disclose a kind of under HZSM-5 zeolite catalyst exists with the ethene diluted for raw material gas phase legal system gets the process of ethylbenzene, rare ethene also can take from the tail gas of the catalytic cracking unit of refinery, but this tail gas need remove H before being used as raw material
2s, CO
2, H
2o and C
2above residue.
US3962364 discloses a kind of P elements carries out modification catalyst to ZSM-5 zeolite, and by modification, the stability of catalyst to the selective and catalyst of benzene and ethylene reaction obtains certain raising.The conversion ratio of ethene can reach 98%, ethylizes selectively to reach 98.99%.Steam treatment is disclosed ethylating selective in time reacting to improve catalyst in US4016218.
CN00111720.3 discloses a kind of method improving benzene and ethene vapor-phase alkylation ZSM-5 catalyst stability, after steam treatment is carried out to ZSM-5 molecular sieve catalyst, use organic acid process again, overcome the shortcoming of the not high enough and catalyst activity poor stability of conversion of ethylene preferably, can preferably in industrial production.
Disclose in CN99112833.8 and USP6093866 a kind of under rare earth-HZSM-5/ZSM-11 cocrystallized zeolite catalyst exists rare ethene and/or propylene and benzene react the method producing ethylbenzene and/or propyl benzene.With the catalysis drying gas from refinery, do not need to refine in advance, catalysis drying gas and benzene, at multistage, carry out vapour phase hydrocarbonylation in cold shock alkylation reaction device, and the diethylbenzene of by-product carries out liquid phase reverse alkylation at fixed bed reactors.
The molecular sieve of usual synthesis is superfine Powdered, only has several microns.But for a kind of catalyst of commercial Application, require that catalyst has certain shape and mechanical strength.If not, many bad consequences can be caused at the central pressure due to load of application and even be forced to stop.Tiny molecular sieve powder, in order to meet application request, often needs to form difform molecular sieve catalyst together with inorganic binder (clay, aluminium oxide).In order to ensure that difform molecular sieve catalyst has corresponding mechanical strength, binding agent is absolutely necessary shaping assistant.The binder material adding inertia in powdered molecular sieve catalyst can make shaping of catalyst, thus improve its mechanical strength [R.Jasra required in commercial Application, N.Choudary, S.Bhat, Sep.Sci.Tech.26 (1991) 885-930].Although the relative inertness of binding agent own, and can the Molecular regulator proton exchange performance of sieve after catalyst mix, while physical occupy molecular sieve duct thus change in forming process its porosity [F.Dorado, R.Romero,
appl.Cata.A, 236 (2002) 235-243].Focused mostly in silica and aluminium oxide to the research of binding agent in the past, wherein in alumina binder, aluminium atom enters framework of molecular sieve and makes molecular sieve acid amount increase [C.D.Chang, S.D.Hellring, J.N.Miale, K.D.Schmitt, P.Brigandi, E.Wu, J.Chem.Soc., Faraday Trans.181 (1985) 2215-2224], in like manner, silica binder then makes its acid amount reduce [X.Wu, A.Alkhawaldeh, R.Anthony, Stud.Surf.Sci.Cata.143 (2000) 217-225], intensity declines; Also the report about Novel phosphoric acid aluminium (PAlO) binding agent is had in recent years, Y.-J.Lee etc. report PAlO base ZSM-5 extruded catalyst and react for preparing propylene from methanol, result shows, molecular sieve mechanical strength is significantly improved after adding PAlO binding agent, binding agent does not show autocatalytic activity, and do not introduce added acid position, P simultaneously by adding appropriate amount regulates the acidity of catalyst to reach the effect [Y.J.Lee improving propene yield, Y.W.Kim, N.Viswanadham, K.-W.Jun, J.W.Bae, Appl.Cata.A, 374 (2010) 18-25].B.Kraushaar-Czarnetzki seminar reports PAlO base ZSM-5 extruded catalyst and reacts for preparing propylene from methanol, and result shows that AlPO4/ZSM-5 catalyst shows excellent activity, Propylene Selectivity and carbon accumulation resisting ability.And binding agent specific surface is actively low, do not show activity, the generation of methane and carbon distribution can not be promoted, in addition PAlO binding agent can not play calorization to molecular sieve, therefore the Si/Al ratio of ZSM-5 molecular sieve can be controlled, thus optimization of catalysts acidity [M.Menges, B.Kraushaar-Czarnetzki, Micr.Meso.Mate.164 (2012) 172-181].
Above-mentioned PAlO binding agent has plurality of advantages, but is only limitted to ZSM-5 molecular sieve system.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application of ZSM11 molecular sieve catalyst of phosphoric acid al binder, compared with alumina binder catalyst, can be improved significantly by conversion of ethylene on phosphoric acid al binder catalyst of the present invention; Ethylbenzene and the selective height of ethylation products; Xylene content is low.
The invention provides a kind of preparation method of ZSM11 molecular sieve catalyst of phosphoric acid al binder, concrete grammar step is:
(1) by the hydrochloric acid of superfine rare-earth-ZSM-11 molecular sieve 0.2-0.8mol/L for preparing or ammonium nitrate solution in 60-80 DEG C of exchange, in 500 ~ 550 DEG C of roasting 3 ~ 5h after drying, make H-rare earth-ZSM-11 molecular sieve;
(2) phosphoric acid solution and boehmite are according to phosphorus al mole ratio P/Al=0 ~ 2(preferably 0.2 ~ 1.5), mix the gluey aluminum phosphate binder of preparation, after adding the dilution of a small amount of water, add the H-rare earth-ZSM-11 molecular sieve that (1) obtains, molecular sieve and binding agent butt weight ratio are 2 ~ 6(preferably 3 ~ 5), 120 ~ 150 DEG C of dryings after mixing, 550 ~ 650 DEG C of roasting 5 ~ 7h, water vapour 450-650 DEG C of process 2-6h, obtained catalyst Z PAlO-x of the present invention.
Put it briefly, catalyst provided by the invention is by superfine rare-earth-ZSM-11 molecular sieve through ion-exchange, and dry, roasting becomes H-type molecular sieve, then adds aluminum phosphate binder, dry, roasting and the obtained required catalyst of steam treatment.
The benzene feedstock that the present invention uses is industrial purified petroleum benzin, also can be the mixture of benzene and ethene and benzene-alkylation product.Unstripped gas is the dry gas (being referred to as catalysis drying gas) of catalytic cracking or catalytic pyrolysis, and benzene does not need dehydration, and generally moisture is 100-1000ppm, catalysis drying gas does not need purification, as not desulfurization, do not dewater, not deoxidation, not de-COx etc., catalysis drying gas containing ethene 10-60%v, containing H
2s100-5000ppm, containing COx1.0-5.0%v, containing oxygen 0.1-1.5%v, moisture is 1000-4000ppm.The conversion ratio of ethene is more than 95%, and the selective >80% of ethylbenzene, ethylize selective >98%, and in pure ethylbenzene, xylene content is less than 1000ppm.
By catalyst prepared by the present invention, ethene in catalysis drying gas and benzene alkylation reaction can be obtained high selectivity ethylo benzene.Compared with the molecular sieve catalyst of only salic binding agent, on phosphoric acid al binder catalyst, conversion of ethylene can be improved significantly; Ethylbenzene and the selective height of ethylation products; Xylene content is low.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Comparative example 1
By a certain amount of particle diameter 350nm rare earth-ZSM11 molecular sieve (content of rare earth accounts for 1.2 heavy % of rare earth-ZSM-11 molecular sieve), at 80 DEG C, exchange 3 times with the ammonium nitrate solution of 0.8mol/L, wash 2 times, 120 DEG C of dryings, 540 DEG C of roasting 3h, obtain H-type molecular sieve; Salpeter solution and boehmite are 0.8 to stir according to Al mol ratio in N in nitric acid and boehmite, add the molecular sieve catalyst that previous step prepares, molecular sieve butt and boehmite butt weight ratio are 4, stir, in 550 DEG C of roasting 5h after 130 DEG C of dryings, then water vapour 550 DEG C process 2h, gained catalyst is denoted as Cat-A.
Embodiment 1
By a certain amount of particle diameter 350nm rare earth-ZSM11 molecular sieve (content of rare earth accounts for 1.2 heavy % of rare earth-ZSM-11 molecular sieve), at 80 DEG C, exchange 3 times with the ammonium nitrate solution of 0.8mol/L, wash 2 times, 120 DEG C of dryings, 540 DEG C of roasting 3h, obtain H-type molecular sieve; Phosphoric acid solution and boehmite (are called for short P/Al mol ratio according to Al mol ratio in P in phosphoric acid and boehmite, as follows) be 0.8 to stir, add the molecular sieve catalyst that previous step prepares, molecular sieve butt and boehmite butt weight ratio are 4, stir, in 550 DEG C of roasting 5h after 130 DEG C of dryings, then water vapour 550 DEG C process 2h, gained catalyst is denoted as Cat-B.
Embodiment 2
By a certain amount of particle diameter 150nm rare earth-ZSM-11 molecular sieve (content of rare earth accounts for 2.5 heavy % of rare earth-ZSM-11 molecular sieve), at 75 DEG C of temperature, exchange 3 times with the hydrochloric acid solution of 0.3mol/L, wash 2 times, 120 DEG C of dryings, 530 DEG C of roasting 4h, obtain H-type molecular sieve; Phosphoric acid solution and boehmite are 0.2 to stir according to P/Al mol ratio, add the molecular sieve catalyst that previous step prepares, molecular sieve butt and boehmite butt weight ratio are 3, stir, in 600 DEG C of roasting 3h after 140 DEG C of dryings, then water vapour 500 DEG C process 5h, gained catalyst is denoted as Cat-C.
Embodiment 3
By a certain amount of particle diameter 550nm rare earth-ZSM-11 molecular sieve (content of rare earth accounts for 4.2 heavy % of rare earth-ZSM-11 molecular sieve), at 75 DEG C of temperature, exchange 3 times with the ammonium nitrate solution of 0.7mol/L, wash 2 times, 120 DEG C of dryings, 510 DEG C of roasting 3h, obtain H-type molecular sieve; Phosphoric acid solution and boehmite are 0.6 to stir according to P/Al mol ratio, add the molecular sieve catalyst that previous step prepares, molecular sieve butt and boehmite butt weight ratio are 5, stir, in 630 DEG C of roasting 4h after 150 DEG C of dryings, then water vapour 600 DEG C process 2h, gained catalyst is denoted as Cat-D.Embodiment 4
By a certain amount of particle diameter 950nm rare earth-ZSM-11 molecular sieve (content of rare earth accounts for 1.2 heavy % of rare earth-ZSM-11 molecular sieve), at 75 DEG C of temperature, exchange 3 times with the hydrochloric acid solution of 0.5mol/L, wash 2 times, 120 DEG C of dryings, 530 DEG C of roasting 4h, obtain H-type molecular sieve; Phosphoric acid solution and boehmite are 1.0 to stir according to P/Al mol ratio, add the molecular sieve catalyst that previous step prepares, molecular sieve butt and boehmite butt weight ratio are 4, stir, in 630 DEG C of roasting 3h after 120 DEG C of dryings, then water vapour 580 DEG C process 2h, gained catalyst is denoted as Cat-E.
Embodiment 5
By a certain amount of particle diameter 700nm rare earth-ZSM-11 molecular sieve (content of rare earth accounts for 2.5 heavy % of rare earth-ZSM-11 molecular sieve), at 60 DEG C of temperature, exchange 3 times with the ammonium nitrate solution of 0.8mol/L, wash 2 times, 120 DEG C of dryings, 530 DEG C of roasting 4h, obtain H-type molecular sieve; Phosphoric acid solution and boehmite are 1.8 to stir according to P/Al mol ratio, add the molecular sieve catalyst that previous step prepares, molecular sieve butt and boehmite butt weight ratio are 3, stir, in 600 DEG C of roasting 6h after 135 DEG C of dryings, then water vapour 550 DEG C process 2h, gained catalyst is denoted as Cat-F.Comparative example 1 and embodiment 1 ~ 5 reaction evaluating
Be placed in respectively by the catalyst of comparative example 1 and embodiment 1 ~ 5 gained on the fixed bed reactors that internal diameter is 24mm continuous-flow and carry out catalyst performance evaluation, the loadings of catalyst is 5g, at N
2500 DEG C of activation 1h are warmed up to, then at N under atmosphere
2atmosphere drops to reaction temperature, and raw material is catalysis drying gas and benzene.Reacted product carries out gas-liquid separation through cooler cooling.Gas and product liquid are all with Agilent7890A chromatographic system analysis composition, and product liquid adopts PONA capillary column, hydrogen flame detector.
The composition of unstripped gas is as shown in table 1.The composition (wt%) of benzene feedstock used: benzene: 99.900; Toluene: 0.080; H
2o:0.015; Other: 0.005.Alkylation reaction condition and the results are shown in Table 2.As can be seen from the table in the condition and range investigated, the conversion ratio of the upper ethene of catalyst Cat-B ~ Cat-F of phosphoric acid al binder is more than 98%, ethylene synthesis ethylbenzene selectivity >80%, the selective >98% of ethylation products, the xylene content <1000ppm of pure ethylbenzene product, and the analog value on the ZSM11 molecular sieve catalyst Cat-A of only salic binding agent is respectively 93.2%, 77.3%, 96.2% and 1585ppm.
The composition (v%) of table 1 unstripped gas
| H 2 | N 2 | CO x | CH 4 | C 2H 4 | C 2H 6 | C 3H 6 | C 3H 8 | C 4H 10 | O 2 | H 2S(ppm) | H 2O(ppm) |
| 9.03 | 14.51 | 1.35 | 35.86 | 23.49 | 12.23 | 0.61 | 1.20 | 0.53 | 0.64 | 3800 | 1800 |
The catalytic reaction evaluation result of the various catalyst of table 2
Above-described embodiment is part preferred embodiment, is not to limit the present invention.As long as the condition in fact meeting the elaboration of summary of the invention part can realize the present invention, therefore, scope is as the criterion with the claim of application.
Claims (9)
1. a preparation method for the ZSM11 molecular sieve catalyst of phosphoric acid al binder, is characterized in that:
(1) superfine rare-earth-ZSM-11 molecular sieve hydrochloric acid prepared or ammonium nitrate solution are exchanged, then dry, roasting, makes H-rare earth-ZSM-11 molecular sieve;
(2) phosphoric acid solution and boehmite are mixed the gluey aluminum phosphate binder of preparation, after adding the dilution of a small amount of water, then add the H-rare earth-ZSM-11 that (1) obtains, mix rear drying, roasting, steam treatment, obtained required catalyst Z PAlO-x.
2. according to the preparation method of the ZSM11 molecular sieve catalyst of phosphoric acid al binder described in claim 1, it is characterized in that: in described step (1), the concentration of hydrochloric acid or ammonium nitrate solution is 0.2-0.8mol/L; The temperature exchanged is 60-80 DEG C.
3. according to the preparation method of the ZSM11 molecular sieve catalyst of phosphoric acid al binder described in claim 1, it is characterized in that: in described step (1), sintering temperature is 500 ~ 550 DEG C, and roasting time is 3 ~ 5h.
4. according to the preparation method of the ZSM11 molecular sieve catalyst of phosphoric acid al binder described in claim 1, it is characterized in that: in described step (2), phosphorus al mole ratio P/Al=0 ~ 2 of phosphoric acid solution and boehmite.
5. according to the preparation method of the ZSM11 molecular sieve catalyst of phosphoric acid al binder described in claim 4, it is characterized in that: phosphorus al mole ratio P/Al=0.2 ~ 1.5 of described phosphoric acid solution and boehmite.
6. according to the preparation method of the ZSM11 molecular sieve catalyst of phosphoric acid al binder described in claim 1, it is characterized in that: in described step (2), H-rare earth-ZSM-11 molecular sieve and binding agent butt weight ratio are 2 ~ 6.
7. according to the preparation method of the ZSM11 molecular sieve catalyst of phosphoric acid al binder described in claim 6, it is characterized in that: described H-rare earth-ZSM-11 molecular sieve and binding agent butt weight ratio are 3 ~ 5.
8. according to the preparation method of the ZSM11 molecular sieve catalyst of phosphoric acid al binder described in claim 1, it is characterized in that: in described step (2), baking temperature is 120 ~ 150 DEG C; Sintering temperature is 550 ~ 650 DEG C, and roasting time is 3 ~ 7h; Steam treatment temperature is 450-650 DEG C, and the steam treatment time is 2-6h.
9. the ZSM11 molecular sieve catalyst of phosphoric acid al binder that prepared by method described in claim 1 is applied to ethene and benzene ethylo benzene in catalysis drying gas.
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| CN106607075A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Fluid catalyst for preparing olefin and arene and application of fluid catalyst |
| CN108025298A (en) * | 2015-07-23 | 2018-05-11 | 雅宝公司 | FCC catalyst additive and adhesive |
| CN108246346A (en) * | 2018-01-26 | 2018-07-06 | 中国科学院大连化学物理研究所 | For methacrylaldehyde, the method for modifying of propionic aldehyde and ammonia reaction ZSM-11 molecular sieve catalysts |
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| WO2021012801A1 (en) * | 2019-07-19 | 2021-01-28 | 国家能源投资集团有限责任公司 | Olefin aromatization catalyst, preparation method therefor, and application thereof, and light olefin aromatization method |
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| CN108025298A (en) * | 2015-07-23 | 2018-05-11 | 雅宝公司 | FCC catalyst additive and adhesive |
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| CN112138710A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN112138710B (en) * | 2019-06-28 | 2022-01-04 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| WO2021012801A1 (en) * | 2019-07-19 | 2021-01-28 | 国家能源投资集团有限责任公司 | Olefin aromatization catalyst, preparation method therefor, and application thereof, and light olefin aromatization method |
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Application publication date: 20150225 |