CN103028433B - There is micropore and mesoporous ZSM-5 catalyst, its preparation method and use this catalyst cracking hydrocarbons to produce the method for light olefin - Google Patents
There is micropore and mesoporous ZSM-5 catalyst, its preparation method and use this catalyst cracking hydrocarbons to produce the method for light olefin Download PDFInfo
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- CN103028433B CN103028433B CN201210307167.3A CN201210307167A CN103028433B CN 103028433 B CN103028433 B CN 103028433B CN 201210307167 A CN201210307167 A CN 201210307167A CN 103028433 B CN103028433 B CN 103028433B
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- catalyst
- zsm
- mesoporous
- micropore
- phosphorus
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- 239000003054 catalyst Substances 0.000 title claims abstract description 521
- 238000000034 method Methods 0.000 title claims abstract description 148
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 117
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 65
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 238000005336 cracking Methods 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 109
- 239000002243 precursor Substances 0.000 claims abstract description 84
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 59
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 58
- 239000012265 solid product Substances 0.000 claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 52
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 104
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- 239000011574 phosphorus Substances 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 75
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- 150000001340 alkali metals Chemical class 0.000 claims description 52
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 52
- 150000002910 rare earth metals Chemical class 0.000 claims description 52
- 238000004523 catalytic cracking Methods 0.000 claims description 47
- 239000012688 phosphorus precursor Substances 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 42
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 41
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 37
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- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
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- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- 229910001491 alkali aluminosilicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000010956 selective crystallization Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides and there is micropore and mesoporous ZSM-5 catalyst, its preparation method and use this catalyst cracking hydrocarbons to produce the method for light olefin.Specifically, comprise (a) by the hydrocarbon mixture of C4 to C7 that produces after cat cracked naphtha cracking for the preparation of the method for ZSM-5 catalyst of the light olefin comprising ethene and propylene and form gel by the aging mixture solution comprising silica precursor and aluminum precursor; B () joins in described gel by may be formed mesoporous template by heat treatment, stir then aging; C () is by forming solid product by crystalline mixture aging in step (b); And (d) heat-treats described solid product thus removes template.Described ZSM-5 catalyst can comprise micropore and mesoporous, and can have good physics and chemistry character together with good porous.The productivity ratio of light olefin can be improved.
Description
Quoting of related application
This application claims and be filed in the Korean Patent Application No. 10-2011-0098694 of Korean Intellectual Property Office on September 29th, 2011 and be filed in the rights and interests of the Korean Patent Application No. 10-2011-0125643 of Korean Intellectual Property Office on November 29th, 2011, their disclosure by reference entirety is combined in this.
Technical field
The present invention relates to and there is micropore and mesoporous (mesopore, mesopore) ZSM-5 catalyst, its preparation method and the method by using this catalyst cracking hydrocarbons to produce light olefin, and more specifically, the method that the physical property comprising the ZSM-5 catalyst used in the method for the light olefin of ethene and propylene produces light olefin prepared by the hydrocarbon mixture related to by improving 4 to 7 carbon produced after being included in cracking naphtha by catalytic cracking.
Background technology
Ethene and propylene are the primary raw materials of petroleum chemicals, and for the preparation of polyethylene, polypropylene, acrylonitrile, polyvinyl chloride etc.So far, most of light olefin (such as ethene, propylene etc.) is prepared by the naphtha of pyrolysis as raw material under at least about the high temperature of 800 DEG C.But the total energy of consume in petro chemical industry about 40% can be consumed by producing the conduction of light olefin by naphtha pyrolysis, and therefore by producing the energy resource consumption of light olefin than being very high.In addition, create a large amount of carbon dioxide thus cause environmental pollution.
Therefore, due to pyrolysis under at least about the high temperature of 800 DEG C, use the cracking method of catalyst to attract a lot of concern as a kind of method of economize energy.When compared with the pyrolytic process of routine, use the catalyst cracking method of catalyst can to carry out under the lower temperature range of about 50-200 DEG C.Therefore, low-energy consumption can be fallen, and the generation of coke on pipeline inner wall can be suppressed thus the cycle of operation of extension fixture and life-span.In addition, the generation of carbon dioxide can be reduced, and environmental pollution can be down to minimum.Because the component of the alkene obtained like this can be controlled according to demand, the unbalanced problem of Supply and Demand about ethene and propylene can be solved.
For being produced the Typical catalyst systems of light olefin by catalytic cracking, can be divided three classes: acid catalyst, base catalyst and catalyst of transition metal oxide.After the representative instance based on often kind of antigravity system analyzes often kind of catalyst, the cracking process of acid catalyst is used to be considered to most economical process.Recently, the research in the catalytic cracking process using such acid catalyst is carried out energetically, and especially, zeolite is most widely used as catalyst.By changing chemical constituent, zeolite is easy to control its acidity, and has shape selective, and therefore has some advantages for the control conversion ratio of reactant and the productive rate of light olefin.The typical zeolite that can be applied to catalytic cracking comprises ZSM-5, USY, REY, beta-zeolite etc.
Different from Conventional zeolites, such as there is Wessalith CS and the erionite of 8 yuan of annular apertures, have about in hole
the faujasite of the supercage of 12 rings, X zeolite and Y and there is the modenite of two-dimentional pore structure, due to
the straight channel of size and
the pore structure of the three dimensional intersection in the sinusoidal duct of size, ZSM-5 catalyst has the medium sized hole of 10 rings and homogeneous aperture and structure.Therefore, when comparing with other zeolite facies, ZSM-5 catalyst has better shape selective and lower level of deactivation, and has the good heat endurance according to high Si/Al ratio.Therefore, ZSM-5 catalyst is used in the conversion reaction, the alkylated reaction of toluene, the isomerization reaction of dimethylbenzene etc. of methyl alcohol, and is typically used as by catalyst (H.Krannila etc., the J.Catal.vol.135 of cat cracked naphtha for the preparation of light olefin, p115,1992).In addition, by using ZSM-5 catalyst crack n-hexane to be used for producing ethene and propylene, confirm that reaction rate and the response path acidity to a great extent by catalyst activity position affects (R.L.V.Mao, Micropor and Mesopor, Mater.vol.28, p9,1999).Especially, the selective of final reacting product and productive rate can be determined according to the character of catalyst and performance, and the strategy therefore developing suitable catalyst for the target product of hope is very important.As mentioned above, because specific structure and good Acidity, ZSM-5 catalyst may be used for, in various reaction, comprising catalytic cracking reaction, isomerization reaction, esterification etc.But, when reacting at a condition of high temperature and high humidity, because dealuminization structure may divide and acidic site may reduce, cause lower catalytic activity.In order to improve the unstable state of catalyst under the reaction condition of high temperature and high humility, attempt the method for the various material of interpolation.Typically, manganese and phosphorus are joined in zeolite the heat endurance (people such as T.Blasco, J.Catal.vol.237, p267,2006) being used for improving catalyst.According to bibliography, when by using phosphate ion to carry out modified zeolite such as ZSM-5, phosphate ion (PO can be passed through
4 3-) carry out modification conduct in zeolite
the Si-OH-Al part worked in acid position.Then, P=O group can stablize unstable aluminium, and therefore dealuminization can be down to minimum.Even if use phosphorus to carry out to zeolite the hydrothermal stability that simple modification can improve catalyst, and can contribute to suppressing catalysqt deactivation for a long time, the increase of light-olefin production amount may be unsuitable.
An important thing be control reaction after the product distribution that obtains and the heat endurance making great efforts to improve catalyst.In order to make the output of light olefin maximize, needing the generation suppressing paraffin and aromatic compound, and needing the output making alkene to maximize.Improvement reducing reaction pressure, in the ratio etc. that improves reaction temperature, reduce reactant retention time and suitably control reactant and catalyst needs people such as (, Appl.CatalA.vol.223, p85,2002) M.A.denHollander.In addition, the output making great efforts to improve light olefin by development of new catalyst is also needed.As the part that this effort is attempted, implement by transition metal or rare earth metal being joined the method (people such as N.Rahimi, Appl.Catal.A.vol.398, p1,2011) carrying out Kaolinite Preparation of Catalyst in ZSM-5 catalyst.According to this bibliography, when transition metal (such as iron or chromium) is joined in ZSM-5, easily can carry out decomposition reaction by the dehydrogenation of reactant (i.e. hydro carbons), and therefore can produce even more substantial light olefin.When being joined in ZSM-5 by rare earth metal (such as neodymium, cerium, lanthanum etc.), the selective of light olefin can be increased.But, about the impact of rare earth metal on the selective improvement of light olefin, there is various viewpoint.When using metal (such as transition metal and rare earth metal), can the porch of zeolite pore be positioned at by having large-sized metallic atom and this hole can be blocked.In this case, reactivity can reduce.Therefore, there is the metal-modified existence restriction of the pure ZSM-5 of micropore character.In order to overcome this restriction, preparation is needed to have the ZSM-5 of micropore and mesoporous character.
U.S. Patent number 6,033,555 disclose the method obtaining light olefin from hydrocarbon feed, are included in the first step and produce light olefin by catalytic cracking, then carry out pyrolysis thus production ethene at second step to continuous print gas.The productive rate of light olefin can be improved according to this method, but, the economic problems about the cost setting up an operation multistep process etc. may be left.
International Patent Publication No. WO00/31215 discloses use and comprises ZSM-5 and/or ZSM-11(as active component) and the catalyst of a considerable amount of inert material (as matrix) for the production of the catalytic cracking process of light olefin.But the productive rate of propylene is too low and be less than about 20wt%.
Korean patent registration No. 0979580 relates under the stringent condition of high temperature and high humility, by the molded catalyst of cracking naphtha for the preparation of light olefin, and discloses the hydrocarbon cracking catalyst and preparation method thereof for the preparation of light olefin.Passed through the MnO of about 0.01-5.0wt% by spraying dry
2and the P of about 1-15wt%
2o
5be impregnated into the mixture slurry obtained in zeolite, clay and inorganic oxide simultaneously, then fire, obtain catalyst.Because come modified zeolite and inorganic oxide with manganese and phosphorus in this catalyst simultaneously, the hydrothermal stability of the spherical mold controlling catalyst obtained like this can be improved, and can passivation zeolite acidic site thus obtain light olefin by the hydro carbons (as naphtha) of catalytic cracking C4 or more by higher productive rate.But, owing to employing the raw material comprising various hydro carbons, product wider distribution, and it is selective relatively to reduce ethene and propylene.
U.S. Patent number 5,171,921 disclose comprise about 1-3wt% phosphorus, comprise its Si/Al than the ZSM-5 catalyst of the about 10-25wt% for about 20-60 and the preparation of molded catalyst comprising adhesive (such as kaolin, bentonite etc.), and disclose under the reaction temperature of about 550-600 DEG C, from the paraffin and olefin(e) compound of C3-C20, optionally prepare the method for C2-C5 alkene.But ZSM-5 catalyst has the feature of the little micropore comprising about below 1nm.When the reactant with large-size participates in reaction, because hole characteristic molecular diffusion may be restricted, and this may be the primary factor of limiting catalyst reactivity.Therefore, when using above-mentioned catalyst to carry out the catalytic cracking of C3-C20 hydrocarbon mixture, then think that the reactivity of this catalyst is bad.Even when improving the hydrothermal stability of catalyst by interpolation phosphorus, once deposit at the porch Formed of micropore, then greatly may reduce the activity of catalyst.
U.S. Patent number 6,656,345 disclose the method preparing light olefin from the hydro carbons comprising about 10-70wt% alkene and about 5-35wt% paraffin.The aperture of the catalyst used in this approach is about
and this catalyst is the zeolite (MFI, MEL, MTW, TON, MTT, FER, MFS etc.) with about 200 or larger Si/Al ratios.Because aperture is very little in this case, the diffusion of reactant may be unsmooth.Owing to not considering hydrothermal stability, the inactivation of catalyst can be described.
U.S. Patent number 7,304,194 disclose the method for carrying out alkylated reaction by being used in the catalyst introducing phosphorus in ZSM-5 catalyst.In order to improve hydrothermal stability, introducing phosphorus and carrying out steam treatment.But, unexposed by adding the effect that phosphorus obtains.
U.S. Patent number 6,835,863 disclose the process of molded catalyst using in naphtha cracking processes and comprise about 5-75wt%ZSM-5 and ZSM-11 catalyst, about 25-29wt% silica (silica) or kaolin and about 0.5-10wt% phosphorus.But, the concrete parent material of unexposed phosphorus and the hydrothermal stability of molded catalyst in this patent, and do not use the catalyst with meso pore characteristics.
U.S. Patent Publication No. 20060011513 discloses the technology coming modified zeolite (comprising ZSM-5, β, mordenite, ferrierite etc.) by the one in lanthanide series, Sc, Y, La, Fe and Ca.But, the particular chemical of unexposed metal phosphate, the explanation for its function is incomplete, and the unexposed technology for improving olefins yield.
U.S. Patent number 7,531,706 disclose use has rare earth metal, manganese or the zirconium modified catalyst together with the pentasil type zeolite of phosphorus to prepare the method for light olefin.The metal of modification it is reported and improves the hydrothermal stability of catalyst and the productive rate of light olefin.But the explanation for metal concrete function is not enough, and an object only points to the durability improving zeolite.
The people such as non-patent literature 1(X.Gao, SolidStateSci.Vol.12, p1278,2010) disclose the method being prepared light olefin by the ZSM-5 catalyst of preparation display meso pore characteristics from butylene.But, by desilication method for the preparation of mesoporous ZSM-5 catalyst, and therefore greatly reduce acidic character and ZSM-5 structural stability, and think that this catalyst exists restriction in the application.
The people such as non-patent literature 2(Z.Song, Appl.Catal.A, Vol.384, p201,2010) disclose method by using the ZSM-5 catalyst comprising phosphorus to prepare propylene from ethanol.The acidic site carrying out modified catalyst by introducing phosphorus is used for improving the selective of propylene.But, fully being openly separated and explanation to often kind of acidic site function of highly acid position and faintly acid position.In addition, when without the productive rate greatly reducing alkene when steam treatment, and other process is therefore needed.
The people such as non-patent literature 3(T.F.Degnan, Micropor.andMesopor.Mater.Vol.35-36, p245,2000) disclose by phosphorus being joined ZSM-5 catalyst catalytic cracking reaction in improve the technology of hydrothermal stability.Dealuminzation from the framework of ZSM-5 catalyst is prevented under the function of phosphorus is described as be in high reaction temperature.But, the unexposed impact on acidity of catalyst.
The people such as non-patent literature 4(G.Zhao, J.Catal, vol.248, p29,2007) be improve hydrothermal stability for by being incorporated in HZSM-5 by phosphorus.In fact, improve hydrothermal stability by introducing phosphorus.But the phosphorus of introducing plugs the entrance of micropore, and greatly reduces its surface area and pore volume.As can be known from the results, there is restriction in phosphorus in raising light-olefin production amount.
The people such as non-patent literature 5(J.Lu, Catal.Commun.vol.7, p199,2006) be research for preparing light olefin method to the catalytic cracking reaction by iso-butane.Based on ZSM-5 zeolite, and be produced with the catalyst of iron modification and for reaction in.The iron modification of catalyst it is reported and the acidity that improve catalyst causes the increase of light-olefin production amount.But along with the increase of iron, activity reduces rapidly.This is the reunion due to the iron atom caused because of the micropore character of ZSM-5.In addition, any explanation to catalyst hydrothermal stability is not shown.
The people such as non-patent literature 6(W.Xiaoning, J.RareEarths, vol.25, p321,2007) be for for use comprise rare earth metal ZSM-5 catalyst from butane for light olefin, for the impact of rare earth metal on acidity of catalyst, and for the research that the change of acidity of catalyst affects reactivity.But, do not consider the impact of rare earth metal on alkaline matter, and the acid-alkaline of unexposed catalyst is on the impact of cracking reaction mechanism.
Because ZSM-5 catalyst has the little micropore of about below 1nm, when large-sized reactant participates in reaction, molecular diffusion may be restricted, and this restriction may become the primary factor limiting this catalytic reaction activity.Therefore, the catalysqt deactivation that mesoporous zeolite is used for slowing down because molecular diffusion effect causes is being made great efforts to prepare.For the preparation (people such as K.R.Kloetstra manufacturing the research of mesoporous zeolite and start from MCM-41/FAU composite, Micropor.Mater.vol.6, p287,1996), and comprise and use epoxy resin to prepare the mesoporous ZSM-5 catalyst (people such as M.Fujiwara, Micropor.andMesopor.Mater.vol.142, p381,2011).International Patent Publication No. WO97/04871 discloses with acid solution process zeolite catalyst, and then this acid-treated zeolite catalyst is used for the method in cracking reaction.According to disclosed method, because eliminate impurity and expand hole, improve the selective of butylene.But, so far, there is no the report that preparation has the method for the ZSM-5 catalyst of the selective and simple manufacture method of gratifying light olefin.
Recently, due to oil price rise and the trend using heavy crude, the natural gas cracking unit for obtaining ethene from more cheap natural gas more relative to naphtha is established in addition.In this case, natural gas cracking unit optionally can produce ethene, and the Supply and Demand of propylene may be caused uneven.Different from the western countries having a large amount of natural gas, most of crude oil import country (comprising Korea S) relies on naphtha pyrolysis and is disadvantageous in minimizing greenhouse gas emission.In Korea S, the ethene produced by naphtha cracking processes can up to about 5,000,000 tons/year, and can up to 700 as the C 5 fraction of byproduct emission, 000 ton/year.But this accessory substance is not effectively utilised.Therefore, highly needing the technology of exploitation for controlling ethylene/propene demand and supply, needing the technology of light olefin restructuring procedure, and highly need to use C 5 fraction to carry out light olefin reconstruct as raw material.
Summary of the invention
The invention provides the hydrocarbon mixture with carbon number 4-7 obtained after cracking naphtha by catalytic cracking, for the preparation of the preparation method of ZSM-5 catalyst of light olefin comprising ethene and propylene, wherein this ZSM-5 catalyst has the physics and chemistry character of conventional catalyst, and display even better porous thus improve the productive rate of light olefin.
Present invention also offers the preparation method of the ZSM-5 catalyst of the optimum condition with the maximize yield making ethene and propylene, the catalyst prepared by the method, and use this catalyst preparing to comprise the method for the light olefin of ethene and propylene.
According to an aspect of the present invention, the method that preparation has micropore and mesoporous ZSM-5 catalyst is provided.The light olefin comprising ethene and propylene prepared by the hydrocarbon mixture that this catalyst is used for being had by catalytic cracking 4 to 7 carbon.This hydrocarbon mixture produces after naphtha cracking processes.Described method comprises (a) and forms gel by the aging mixture solution comprising silica (silica) precursor and aluminum precursor; B () joins in described gel by may be formed mesoporous template by heat treatment, stir and then aging; C () is by forming solid product by crystalline mixture aging in step (b); And (d) heat-treats described solid product thus removes template.
In the exemplary embodiment, can by comprising the mixture solution that every method is come in preparation process (a) below: (a-1) by monovalent metal hydroxide and tetrapropyl ammonium halide dissolves in distilled water; (a-2) add silica precursor thus form uniform mixture; And the aluminum precursor of liquid phase is added drop-wise in described uniform mixture by (a-3).
In the exemplary embodiment, described silica precursor can be cataloid (Ludox), and described aluminum precursor can be selected from by sodium aluminate (NaAlO
2), aluminum nitrate (Al (NO
3)
3), aluminium secondary butylate, tert-butyl alcohol aluminium, three aluminium secondary butylates, three tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide composition at least one of group.
In the exemplary embodiment, described template can be carbon dust or nanometer polymerization composition granule.
In the exemplary embodiment, carbon dust or nanometer polymerization composition granule can have have about 2-50nm diameter spherical, square, rectangle and cylindrical at least one shape.
In the exemplary embodiment, described nanometer polymer can be at least one being selected from the group be made up of Merlon, polystyrene, polyethylene, polypropylene, poly-(oxirane), poly-(expoxy propane), polyactide and polymethyl methacrylate.
In the exemplary embodiment, based on 100 parts of silica precursors by weight, the amount of template can be by weight about 5-80 part.
In the exemplary embodiment, the Si/Al atomic ratio with micropore and mesoporous ZSM-5 catalyst can be about 5-300.
In the exemplary embodiment, the heat treatment in step (d) can be carried out at the temperature of about 300-750 DEG C, continues about 3-10 hour.
In the exemplary embodiment, described method may further include after completing steps (d), and (d-1) replaces the cation of described heat treated solid product; And (d-2) solid product to described cation replacement is heat-treated.
In the exemplary embodiment, can be comprised by use and being selected from by ammonium nitrate (NH
4nO
3), ammonium chloride (NH
4cl), ammonium carbonate ((NH
4)
2cO
3) and ammonium fluoride (NH
4the solution of at least one of the group F) formed is to carry out cationic displacement.
In the exemplary embodiment, the heat treatment in step (d-2) can be carried out at the temperature of about 400-700 DEG C, continues about 3-10 hour.
According to a second aspect of the present invention, described method be may further include (e) and is incorporated in described heat treated solid product by phosphorus precursor by dipping method or ion-exchange process.
In the exemplary embodiment, the dipping method of phosphorus precursor can comprise (e-1), with water, described phosphorus precursor hydration obtained hydration solution; (e-2) solid product heat treated in step (d) to be joined in this hydration solution thus to flood with this hydration solution; And (e-3) is dry and heat-treat by the solid product of this dipping.
In the exemplary embodiment, described phosphorus precursor can be selected from by phosphoric acid (H
3pO
4), mono phosphoric acid ester ammonium ((NH
4) H
2pO
4), Diammonium phosphate (DAP) ((NH
4)
2hPO
4) and ammonium phosphate ((NH
4)
3pO
4) at least one of group that forms.
In the exemplary embodiment, based on by weight 100 parts there is micropore and mesoporous ZSM-5 catalyst, the amount of phosphorus precursor can be by weight about 0.01-10 part.
In the exemplary embodiment, based on by weight 100 parts there is micropore and mesoporous ZSM-5 catalyst, the amount of phosphorus precursor can be by weight about 0.1-1.5 part.
In the exemplary embodiment, the heat treatment in step (e-3) can be carried out at the temperature of about 500-750 DEG C, continues about 1-10 hour.
According to a third aspect of the present invention, described method may further include, and Rare earth metal precursors or alkali metal precursor, by dipping method or ion-exchange process, are incorporated in the heat treated solid product comprising described phosphorus precursor by (f).
In the exemplary embodiment, the dipping method of step (f) middle rare earth metal precursor or alkali metal precursor can comprise: (f-1) in water by described Rare earth metal precursors or alkali metal precursor hydration; (f-2) join comprise comprising the solid product of phosphorus in step (e) in the Rare earth metal precursors of described hydration or the solution of alkali metal precursor to use this solution impregnation; And (f-3) is dry and heat-treat by the solid product of this dipping.
In the exemplary embodiment, described rare earth metal can be at least one being selected from the group be made up of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu).
In the exemplary embodiment, alkali metal can be at least one being selected from the group be made up of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and caesium (Cs).
In the exemplary embodiment, based on the atomic ratio relative to phosphorus, rare earth metal or alkali-metal amount can be about less than 2.
In the exemplary embodiment, the heat treatment in step (f-3) can be carried out at the temperature of about 500-750 DEG C, continues about 1-10 hour.
In the exemplary embodiment, described hydrocarbon mixture can comprise C 5 fraction.
According to another aspect of the present invention, provide there is micropore and mesoporous ZSM-5 catalyst.The light olefin comprising ethene and propylene prepared by the hydrocarbon mixture that this catalyst is used for being had by catalytic cracking 4 to 7 carbon.Described hydrocarbon mixture produces after naphtha cracking processes, and by using carbon dust or nanometer polymerization composition granule to carry out Kaolinite Preparation of Catalyst as template.
In the exemplary embodiment, Kaolinite Preparation of Catalyst can be carried out by the method comprising step (a) to (d), and this catalyst can have about 360-410m
2the specific area of/g, about 0.1-0.2cm
3volume, the about 0.05-0.3cm with the micropore of about below 1nm diameter of/g
3the mesoporous volume with about 2nm or larger diameter of/g and be about 130-145 μm of ol-NH according to the temperature programmed desorption of ammonia
3the acidity of/g-catalyst.
In the exemplary embodiment, based on by weight 100 parts there is micropore and mesoporous ZMS-5 catalyst, described catalyst may further include about 0.01-10 part phosphorus precursor by weight.
In the exemplary embodiment, Kaolinite Preparation of Catalyst can be carried out by the method comprising step (a) to (e), and this catalyst can have about 340-400m
2the specific area of/g, about 0.05-0.2cm
3volume, the about 0.05-0.2cm with the micropore of about below 1nm diameter of/g
3the mesoporous volume with about 2nm or larger diameter of/g, according to the temperature programmed desorption of ammonia at faintly acid position about 80-95 μm ol-NH
3the acidity of/g-catalyst and at highly acid position about 15-50 μm ol-NH
3the acidity of/g-catalyst and analyze the Carbon deposition amount of about 2-7wt% according to the CHNS after catalyst reaction 40 hours.
In the exemplary embodiment, based on the atomic ratio relative to phosphorus, described catalyst may further include rare earth metal or the alkali metal of about less than 2 amounts.
In the exemplary embodiment, based on the atomic ratio relative to phosphorus, described catalyst may further include rare earth metal or the alkali metal of the amount of about 0.1-1.5.
In the exemplary embodiment, Kaolinite Preparation of Catalyst can be carried out by the method comprising step (a) to (f), and described catalyst can have about 300-400m
2the specific area of/g, about 0.05-0.2cm
3volume, the about 0.05-0.15cm with the micropore of about below 1nm diameter of/g
3the mesoporous volume with about 2nm or larger diameter of/g, according to the temperature programmed desorption of ammonia at faintly acid position about 70-90 μm ol-NH
3the acidity of/g-catalyst, at highly acid position about 20-45 μm ol-NH
3the acidity of/g-catalyst and about 2-30 μm ol-CO
2the basicity of/g-catalyst.
In the exemplary embodiment, described hydrocarbon mixture can comprise C 5 fraction.
According to another aspect again of the present invention, provide the method that the light olefin comprising ethene and propylene prepared by the hydrocarbon mixture having 4 to 7 carbon by catalytic cracking.Described hydrocarbon mixture produces after naphtha cracking processes, and described hydrocarbon mixture is at about 1-20h
-1weight hourly space velocity (WHSV) under, under the temperature range of about 300-700 DEG C, react having under micropore and mesoporous ZMS-5 catalyst.
In the exemplary embodiment, described hydrocarbon mixture can comprise C 5 fraction.
Accompanying drawing explanation
Explain its illustrative embodiments by reference to accompanying drawing, above-mentioned and other feature and advantage of the present invention will become clearer, wherein:
Fig. 1 is the flow chart preparing micropore and mesoporous ZSM-5 catalyst method for illustration of first embodiment conceived according to the present invention;
Fig. 2 is the flow chart for illustration of being prepared in the process of the mixture solution of step (a) in the preparation method of micropore and mesoporous ZSM-5 catalyst according to the present invention's design;
Fig. 3 conceives in the method preparing micropore and mesoporous ZSM-5 catalyst, with the flow chart of the process of the heat treated solid product of cation replacement for illustration of according to the present invention;
Fig. 4 is the flow chart preparing the method for micropore and mesoporous ZSM-5 catalyst for illustration of second embodiment conceived according to the present invention;
Fig. 5 is the flow chart for illustration of flooding the process of phosphorus precursor in the method preparing micropore and mesoporous ZSM-5 catalyst according to the present invention's design;
Fig. 6 is the flow chart preparing the method for micropore and mesoporous ZSM-5 catalyst for illustration of the 3rd embodiment conceived according to the present invention;
Fig. 7 is the flow chart for illustration of flooding the process of Rare earth metal precursors or alkali metal precursor in the method preparing micropore and mesoporous ZSM-5 catalyst according to the present invention's design;
Fig. 8 is a curve map, describes the x-ray analysis result according to embodiment 1 to 5 and comparing embodiment ZSM-5 catalyst;
Fig. 9 is a curve map, describes the x-ray analysis result according to embodiment 3 and 6 to 9, ZSM-5 catalyst;
Figure 10 is a curve map, describes the x-ray analysis result according to embodiment 7 and 11 to 14, ZSM-5 catalyst;
Figure 11 is a curve map, describes the x-ray analysis result according to embodiment 15 to 17, ZSM-5 catalyst;
Figure 12 A and 12B is curve map, describes according to embodiment 1 to 5 and the N2 adsorption of comparing embodiment ZSM-5 catalyst and the result of desorption curve figure (12A) and graph of pore diameter distribution (12B);
Figure 13 A to 13F is the photo figure of the ZSM-5 catalyst crystal structure obtained by high-resolution transmission electron microscope according to embodiment 3,5 and comparing embodiment;
Figure 14 is a curve map, describes the experimental result of N2 adsorption according to embodiment 7 and 11 to 14, ZSM-5 catalyst and desorption;
Figure 15 is a curve map, describes according to embodiment 1 to 5 and comparing embodiment, the experimental result of the temperature programmed desorption of ammonia of ZSM-5 catalyst;
Figure 16 is a curve map, describes the experimental result of the temperature programmed desorption of ammonia according to embodiment 1 and 6 to 10, ZSM-5 catalyst;
Figure 17 is a curve map, describes the experimental result of the temperature programmed desorption of ammonia according to embodiment 7 and 11 to 14, ZSM-5 catalyst;
Figure 18 is a curve map, describes the experimental result of the temperature programmed desorption of ammonia according to embodiment 15 to 17, ZSM-5 catalyst;
Figure 19 is a curve map, describes the experimental result of the temperature programmed desorption of ammonia according to embodiment 7 and 11 to 14, ZSM-5 catalyst;
Figure 20 is a curve map, describes the hydrogen transfer activity according to the measurement of embodiment 7 and 11 to 14, ZSM-5 catalyst and alkaline relation;
Figure 21 is a curve map, describes the conversion ratio by use ZSM-5 catalyst C 5 fraction and the productive rate of light olefin (ethene+propylene) according to embodiment 1 to 5 and comparing embodiment;
Figure 22 A and 22B is curve map, describes according to embodiment 3 and 6 to 10, and comparing embodiment, according to the time of ZSM-5 catalyst, and the process of the conversion ratio of C 5 fraction, the selective of light olefin and productive rate change;
Figure 23 A and 23B is curve map, describes according to embodiment 3 and 6 to 10, according to the acidity of the highly acid position of ZSM-5 catalyst, and the conversion ratio of C 5 fraction and the productive rate of light olefin;
Figure 24 A to 24F is according to embodiment 3,7 and 9, carrying out reacting the photo figure of the crystal structure continuing the ZSM-5 catalyst obtained by use high resolution TEM after 40 hours;
Figure 25 A and 25B is curve map, describes according to the Acidity of Aikalinity of embodiment 7 and 11 to 14, ZSM-5 catalyst the impact of reactivity; And
Figure 26 is a curve map, describes according to embodiment 7 and 11 to 14, the relation of lanthanum/between phosphorus atoms ratio and light olefins yields on ZSM-5 catalyst.
Detailed description of the invention
With reference now to accompanying drawing, more fully the present invention will be described, which show the embodiment of citing of the present invention.Term is only the target of the embodiment in order to concrete example is described as used herein, is not intended to limit the present invention.Unless otherwise defined, otherwise as used herein all terms (comprising technology and scientific terminology) have the identical meanings usually understood with those of ordinary skill in field belonging to the present invention.It should be further understood that these terms, such as define in conventional dictionary those, should be interpreted as that there is the implication consistent with their implication in the context and association area of this description, and should not make an explanation with Utopian or too formal implication, unless defined so clearly at this.The embodiment of various citing will be described more fully, which show the embodiment of some citings.But the present invention can embody with multiple different form, and should not be construed as the embodiment being limited to the citing proposed at this.More properly, the embodiment providing these citings makes description of the present invention become thorough and complete, and fully scope of the present invention can be conveyed to those skilled in the art.
In this manual, " micropore " represents the character with about below 1nm aperture (diameter), consider the common ZSM-5 catalyst with about below 1nm micropore, and " mesoporous (mesopore) " represents to have about more than 1nm, the character of preferred more than 2nm aperture (diameter).But the numerical value in aperture can not have restrictive sense, but the relative value according to the preparation condition of catalyst etc. can be represented.Hereinafter, " mesoporous " in this description only represents the hole with about more than 2nm aperture (diameter).
First embodiment
Fig. 1 is the flow chart preparing the method for micropore and mesoporous ZSM-5 catalyst for illustration of first embodiment conceived according to the present invention, Fig. 2 is for illustration of conceiving the flow chart preparing the mixture solution process of preparation process (a) in the method for micropore and mesoporous ZSM-5 catalyst according to the present invention, and Fig. 3 is for illustration of preparing the flow chart by the process of the heat treated solid product of cation replacement in the method for micropore and mesoporous ZSM-5 catalyst according to the present invention's design.
See Fig. 1, according to the method preparing micropore and mesoporous ZSM-5 catalyst in the first embodiment, the method preparing micropore and mesoporous ZSM-5 catalyst comprises (a) and forms gel (step S100) by the mixture solution of aged silica precursor and aluminum precursor; B () joins in described gel by may be formed mesoporous template by heat treatment, stir and then aging (step S200); C () is by forming solid product (step S300) by crystalline mixture aging in step (b); And (d) heat-treats described solid product thus removes template (step S400).
The hydro carbons with C4 to C7 that micropore and mesoporous ZSM-5 catalyst may be used for being produced after carrying out naphtha cracking processes by catalytic cracking that has prepared by the first embodiment prepares the light olefin comprising ethene and propylene.Preferably, the C 5 fraction that this catalyst may be used for being obtained after carrying out naphtha cracking processes by catalytic cracking prepares the light olefin comprising ethene and propylene.
Normally, by using organic cation as template, in alkali alumino silicate reaction mother liquor, hydro-thermal ZSM-5 catalyst can be synthesized.According to conceiving the method preparing ZSM-5 catalyst according to the present invention, form gel by the aging mixture solution comprising silica precursor and aluminum precursor, and then can form mesoporous template by heat treatment and add as in the gel in step (a) and (b).Can remove by the heat treatment operation fired carried out subsequently the template added, and mesoporous and micropore can be formed.Detailed description will be provided hereinafter.
Produce uniform crystalline solid product for ease of being stirred in the gel mixture formed in the step S100 of (a) by the template added subsequently, the method for optimizing for the preparation of the mixture solution for the formation of gel may be needed.See Fig. 2, the mixture solution in preparation process (a) can be carried out by the method comprising the following: (a-1) is by monovalent metal hydroxide and tetrapropyl ammonium halide dissolves in distilled water (step S110); (a-2) silica precursor is added to form homogeneous mixture (step S120); And the aluminum precursor of liquid phase is added drop-wise in described uniform mixture (step S130) by (a-3).
Monovalent metal hydroxide can comprise NaOH (NaOH), potassium hydroxide (KOH) etc., and tetrapropyl ammonium halide can comprise 4-propyl bromide, 4-propyl ammonium chloride etc.
The preparation process of mixture solution in step (a) will be explained.First, monovalent metal hydroxide and tetrapropyl ammonium halide can be dissolved completely in (step S110) in distilled water, and then can add silica precursor thus form mixture (step S120).In this case, mixture is needed to have homogeneous state.Silica precursor can comprise cataloid, and can be particularly be selected from by
hS-40,
aS-40 and
at least one in the group of HS-30 composition.After this, aluminum precursor is joined (step S130) in homogeneous mixture.In this case, it is desirable to aluminum precursor to join lentamente in homogeneous mixture.Particularly, can dropwise aluminum precursor be joined in homogeneous mixture.Aluminum precursor can be selected from by sodium aluminate (NaAlO
2), aluminum nitrate (Al (NO
3)
3), aluminium secondary butylate, tert-butyl alcohol aluminium, three aluminium secondary butylates, three tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide composition group at least one.
The mixture solution obtained so is suitably stirred, and mixture (step S100) that is then aging thus formation gel state.Can by room temperature by mixture solution stir about 1-3 hour, and then at room temperature aging about 2-10 hour obtain the mixture of gel state.
Then, as illustrated in step (b), template is joined (step S200) in the mixture of gel state.After addition, when heat treatment catalyst, template can be formed mesoporous.As mesoporous template may be formed, soft template (such as surfactant) and hard template (such as carbon, polymeric material) can be described.But hard template may be favourable, because easily can remove hard template by thermal decomposition, and the morphology Control of hard template can be favourable.In addition, when compared with soft template, hard template provides larger hole and less expensive.
In the exemplary embodiment, hard template can comprise carbon dust or nanometer polymerization composition granule.Consider that availability, structure control aspect etc. can suitably be selected and combine hard template.Particularly, for carbon dust, the product with various shape and granularity is commercially available, and is easy to obtain.In addition, carbon dust is easy to store and process.For nanometer polymerization composition granule, heat decomposition temperature is lower than carbon dust, and its surface treatment is easier to.Therefore, when considering structure control aspect, nanometer polymerization composition granule is preferred.
Can have for the formation of mesoporous any shape as the carbon dust of template or nanometer polymerization composition granule, and not limit, comprise spherical, square, rectangle, cylindrical etc.When considering adsorption and desorption favourable on the catalyst activity position of catalytic cracking production (hydro carbons of C4 to C7), the size (diameter) of template can be about 2-50nm.
When only may be formed mesoporous during heat-treating the catalyst comprising nanometer polymerization composition granule, nanometer polymerization composition granule can comprise any material and not limit.Particularly, nanometer polymerization composition granule can comprise Merlon, polystyrene, polyethylene, polypropylene, poly-(oxirane), poly-(propane oxide), polyactide, polymethyl methacrylate etc.Preferably, Merlon or the polystyrene by retaining a small amount of residue during heat treatment removal process can be used in.
In addition, can the amount of Control architecture, make mesoporous can development well pro rata with template addition.Based on 100 parts of silica precursors by weight, the amount of template can be by weight about 5-80 part.When the amount of template be less than by weight 5 parts time, the mesoporous volume formed like this may be not satisfied, and when quantity exceed by weight 80 parts time, catalyst activity position may be reduced, and catalytic activity may some reduction.Mesoporous character can be improved by adding a large amount of template and being removed subsequently.But, the mitigation of the molecular diffusion restriction caused according to the space size due to the adsorption and desorption for C4 to C7 hydrocarbon mixture, product etc., the raising of catalyst reaction activity may not character always with mesoporous proportional.When noting adding the amount of carbon dust in template (KetjenBlackCo.), based on 100 parts of silica precursors by weight, the reactivity of catalyst can be increased to 80 parts by weight.But, when carbon dust amount exceed by weight 80 parts time, do not find the improvement degree of catalyst reaction activity.
In advance at about 100-150 DEG C by template drying about 1-5 hour, and at room temperature by mixture stir about 1-5 hour, and then at room temperature aging about 1-5 hour to prepare crystallisation step.
Template can be added in the forming step of gel phase mixture.But in this case, template addition may increase relatively, and very meticulous Chemical Control may be needed to realize selective crystallization of zeolites.Therefore, this process is undesired.Confirm by template is joined in the mixture of gel phase quantitatively, stirred and aging simple procedure, can obtain having the preparation of the ZSM-5 catalyst of even better reactivity.
By adding the having among micropore and mesoporous ZSM-5 catalyst of Template preparation, can select that preferably there is micropore and mesoporous ZSM-5 catalyst, making the atomic ratio of its Si/Al (molar ratio) be about 5-300.When Si/Al atomic ratio is less than 5, catalyst activation change may not greatly be affected.But, along with catalyst acidity increases, inactivation can be caused by coking etc.When Si/Al atomic ratio is more than 300, the acidity of catalyst may be not satisfied, and the conversion ratio of catalytic cracking C4 to C7 hydrocarbon mixture may reduce.
Then will by template be joined in gel, stir and aging preparation crystalline mixture thus form solid product (step S300).Crystallization can be carried out, such as Hydrothermal Synthesis, Microwave synthesize, dry glue established law etc. by using the method for application usually.By crystallization, zeolite around template, carbon dust or nanometer polymerization composition granule, thus can grow into larger monocrystalline.
After this, solid product heat-treated and remove template thus formed mesoporous (step S400).In this case, the solid product by obtaining as the crystallization process of preprocessing process is filtered, with distilled water washing for several times, and at about 100-120 DEG C drying about 5-15 hour.The solid product of drying is crushed, and heat-treats by firing about 3-10 hour at about 300-750 DEG C.Continue about 4-6 hour at about 500-600 DEG C for firing the preferred firing condition of template completely.By heat treatment, zeolite mono-crystalline structures can become comprise by carbon formed mesoporous.
According to preparation, there is the method for mesoporous ZSM-5 catalyst, can the step (step S410) of the heat treated solid product of enforcement cation replacement further as shown in Figure 3.Normally, enforcement cation replacement is so that with proton (H
+) exchange with sodium ion (Na
+) zeolite of replacing.When compared with other cations, increase by the acid strength of the zeolite catalyst of proton exchange, and catalyst is effectively applied to cracking process.Particularly, cation can be replaced by solid product being put into solution at about 70-90 DEG C, and then within stir about 2-4 hour under same temperature conditions, carry out cation replacement.The aqueous solution of cation replacement filtered and washs, and cation replacement process can be repeated 1-3 time.As the solution for cation replacement, at least one can be selected from by ammonium nitrate (NH
4nO
3), ammonium chloride (NH
4cl), ammonium carbonate ((NH
4)
2cO
3) and ammonium fluoride (NH
4f) group formed.
In addition, further heat treatment process (step S420) can be carried out to the solid product of cation replacement.Can heat-treat by solid product being fired at about 400-700 DEG C about 3-10 hour.When heat treatment temperature is lower than 400 DEG C, the ammonium salt of first replacing zeolite catalyst can not be removed fully, and the acid strength of zeolite can be reduced.When heat treatment temperature is more than 700 DEG C, catalyst can be pulverized, and
acidic site may disappear.When heat treatment time is less than 3 constantly little, may be difficult to remove salt, and when heat treatment time is constantly little more than 10, may power loss be caused.Preferably, can heat-treat the solid product of cation replacement after drying about 5-15 hour at about 100-120 DEG C.
Micropore and mesoporous character can be comprised according to mesoporous ZSM-5 catalyst prepared by the first embodiment of the present invention's design simultaneously.These catalyst properties can improve the diffusion of reactant and intermediate, thus improve the productive rate comprising the light olefin of ethene and propylene of the hydrocarbon mixture production from C4 to C7.Particularly, having micropore and mesoporous ZSM-5 catalyst can prepare as template by using carbon, and can have about 360-410m
2the specific area of/g, about 0.1-0.2cm
2volume, the about 0.05-0.3cm with the micropore of about below 1nm diameter of/g
3the mesoporous volume with about more than 2nm diameter of/g and be about 130-145 μm of ol-NH according to the temperature programmed desorption of ammonia
3the acidity of/g-catalyst.
The light olefin comprising ethene and propylene prepared by the hydrocarbon mixture that prepared by the first embodiment conceived by the present invention have micropore and mesoporous ZSM-5 catalyst may be used for the C4 to C7 produced after naphtha cracking processes by catalytic cracking.In this case, can pass through under the reaction temperature of about 300-700 DEG C, having under micropore and the existence of mesoporous ZSM-5 catalyst, at about 1-20h
-1weight hourly space velocity (WHSV) condition under make hydrocarbon mixture react prepare light olefin.When weight hourly space velocity is less than 1h
-1time, can conversion ratio be increased, but may reduce because side reaction is selective.When weight hourly space velocity is more than 20h
-1time, can conversion ratio be reduced and can catalyst life be reduced.
Second embodiment
Fig. 4 is the flow chart preparing micropore and mesoporous ZSM-5 catalyst method for illustration of second embodiment conceived according to the present invention, and Fig. 5 is for illustration of preparing according to the present invention's design the flow chart flooding phosphorus precursor process in the method for micropore and mesoporous ZSM-5 catalyst.
See Fig. 4, the method having micropore and a mesoporous ZSM-5 catalyst according to the second embodiment preparation comprises (a) and forms gel (step S100) by the aging mixture solution comprising silica precursor and aluminum precursor; B template joins in gel by (), stir and then aging (step S200); C () forms solid product (step S300) by mixture aging in crystallisation step (b); D () is heat-treated described solid product thus is removed template (step S400); E phosphorus precursor is incorporated into (step S500) in heat treated solid product by dipping method or ion-exchange process by ().
Be similar to prepare according to the first embodiment there is micropore and mesoporous ZSM-5 catalyst, prepare according to C4 to the C7 hydrocarbon mixture that micropore and mesoporous ZSM-5 catalyst may be used for being produced after carrying out cracking naphtha by catalytic cracking that has prepared by the second embodiment the light olefin comprising ethene and propylene.Preferably, the C 5 fraction that micropore and mesoporous ZSM-5 catalyst may be used for being produced after cracking naphtha by catalytic cracking that has prepared according to the second embodiment prepares the light olefin comprising ethene and propylene.May be used for the second embodiment because the entirety considered as the step (a) to (d) as described in is in the first embodiment formed, illustrate hereinafter and will concentrate in step (e) to avoid repeat specification.
According to the second embodiment of the present invention's design, can by phosphorus precursor being incorporated in the heat treated solid product in step (d) to carry out modified ZSM-5 catalyst to obtain to prepare to have the method for micropore and mesoporous ZSM-5 catalyst with phosphorus.
The introducing of phosphorus precursor can be performed by dipping method or ion-exchange process.When consideration controls acidic site, particularly during highly acid position, can preferred dipping method.
See Fig. 5, such as, by method below, phosphorus precursor can be impregnated in ZSM-5 catalyst.Phosphorus precursor hydration (step S510) can be made in water, and the heat treated solid product of step (d) can be joined to carry out flooding (step S520) in hydration solution, and then dry and heat-treat (step S530).
Especially, phosphorus precursor can be dissolved in the enough water (distilled water) of the phosphorus precursor for dissolving entire quantity (step S510), and at about 70-90 DEG C stir about 5-15 minute.Heat treated solid product can be added at 70-90 DEG C, and stir fully to flood (step S520).After by whole water evaporates, drying about 10-15 hour at about 90-110 DEG C, and can carry out firing at about 500-750 DEG C and continue about 1-10 hour (step S530) thus obtain catalyst.When compared with dipping at room temperature, at about 70-90 DEG C, carry out flooding the framework adding ZSM-5 catalyst be combined with phosphorus component.When firing temperature is less than 500 DEG C, the organic substance comprised in phosphorus precursor and inorganic substances fully can not be removed, and when firing temperature is more than 750 DEG C, specific consumption is bad, and the removal capacity possible deviation of the organic substance comprised in phosphorus precursor and inorganic substances.
Consider acidity and the Carbon deposition amount of the ZSM-5 catalyst of final preparation according to catalyst reaction, the introduction volume of phosphorus precursor can be set to optimum range.Based on 100 parts of ZSM-5 catalyst with micropore and mesoporous final generation in the quantitative range of template by weight, the introduction volume of phosphorus precursor can be by weight about 0.01-10 part, preferably can be by weight about 0.05-3 part, more preferably can be by weight about 0.1-1.5 part, and most preferably can be by weight about 0.1-1 part.
Phosphorus precursor can comprise phosphoric acid (H
3pO
4), mono phosphoric acid ester ammonium ((NH
4)
h2PO
4), Diammonium phosphate (DAP) ((NH
4)
2hPO
4) and ammonium phosphate ((NH
4)
3pO
4).
May further include before introduction phosphorus precursor according to the method that the second embodiment preparation of the present invention's design has micropore and a mesoporous ZSM-5 catalyst, the cation replacement step (step S410) of the heat treated solid product of step (d) and the solid product of cation replacement is heat-treated (step S420).Concrete method can be identical with described in the first embodiment.
Prepared by the second embodiment conceived by the present invention have micropore and mesoporous ZSM-5 catalyst can have micropore and mesoporous character simultaneously.These catalyst properties can improve the diffusion of reactant and intermediate, thus improve the productive rate comprising the light olefin of ethene and propylene of the hydrocarbon mixture production from C4 to C7.In addition, prepared by the second embodiment conceived by the present invention have micropore and mesoporous ZSM-5 catalyst can be introduced the phosphorus of optimised quantity thus produce the ZSM-5 catalyst with optimum acidity.When using the ZSM-5 catalyst hydrocarbon mixture be used for from C4 to C7 to prepare the light olefin comprising ethene and propylene, having micropore and mesoporous ZSM-5 catalyst can long-time stable and can have good activity.Particularly, based on by weight 100 parts there is micropore and mesoporous ZSM-5 catalyst, there is micropore and mesoporous ZSM-5 catalyst may further include about 0.1-10 part phosphorus precursor by weight, and about 340-400m can be had
2the specific area of/g, about 0.05-0.2cm
3the volume with the micropore of below 1nm diameter of/g, about 0.05-0.2cm
3the mesoporous volume with about more than 2nm diameter of/g, be about 80-95 μm of ol-NH according to the temperature programmed desorption of ammonia
3the acidity of the faintly acid position of/g-catalyst and about 15-50 μm ol-NH
3the acidity of the highly acid position of/g-catalyst and analyze the Carbon deposition amount of about 2-7wt% according to CHNS after catalyst reaction 40 hours.
The light olefin comprising ethene and propylene prepared by the hydrocarbon mixture that prepared by the second embodiment conceived by the present invention have micropore and mesoporous ZSM-5 catalyst may be used for the C4 to C7 produced after carrying out naphtha cracking processes by catalytic cracking.Concrete reaction condition can be identical with described in the first embodiment.
3rd embodiment
Fig. 6 is the flow chart preparing micropore and mesoporous ZSM-5 catalyst method for illustration of the 3rd embodiment conceived according to the present invention, and Fig. 7 is for illustration of preparing according to the present invention's design the flow chart flooding Rare earth metal precursors or alkali metal precursor process in the method for micropore and mesoporous ZSM-5 catalyst.
See Fig. 6, the method having micropore and a mesoporous ZSM-5 catalyst according to the 3rd embodiment preparation comprises (a) and forms gel (step S100) by the aging mixture solution comprising silica precursor and aluminum precursor; B template adds in gel by (), stir and then aging (step S200); C () is by forming solid product (step S300) by crystalline mixture aging in step (b); D () is heat-treated described solid product thus is removed template (step S400); E phosphorus precursor is incorporated in described heat treated solid product (step S500) by dipping method or ion-exchange process by (); And Rare earth metal precursors or alkali metal precursor to be incorporated into by dipping method or ion-exchange process in the solid product comprising phosphorus precursor (step S600) by (f).
Be similar to prepare according to first and the second embodiment there is micropore and mesoporous ZSM-5 catalyst, prepare according to C4 to the C7 hydrocarbon mixture that micropore and mesoporous ZSM-5 catalyst may be used for being produced after cracking naphtha by catalytic cracking that has prepared by the 3rd embodiment the light olefin comprising ethene and propylene.Preferably, the C 5 fraction that micropore and mesoporous ZSM-5 catalyst may be used for being produced after cracking naphtha by catalytic cracking that has prepared according to the second embodiment prepares the light olefin comprising ethene and propylene.May be used for the 3rd embodiment owing to considering as the step (a) to (d) as described in the first embodiment and the entirety as the step (e) as described in are in this second embodiment formed, illustrate hereinafter and will concentrate on step (f) to avoid repeat specification.
According to the 3rd embodiment of the present invention's design, can comprising in the solid product of phosphorus precursor to control acidity and the alkalescence of catalyst by Rare earth metal precursors or alkali metal precursor being incorporated into step (e), obtaining preparing the method with micropore and mesoporous ZSM-5 catalyst.Respectively or can side by side carry out the introducing of Rare earth metal precursors and alkali metal precursor, can catalyst property be obtained to illustrate by introducing often kind of metal simultaneously.
In order to introduce Rare earth metal precursors or alkali metal precursor, dipping method or ion-exchange process can be used.But, can contribute to controlling dipping method that is acid and alkalescence and make us wishing.
See Fig. 7, method Rare earth metal precursors or alkali metal precursor are impregnated in ZSM-5 catalyst can be performed by the similar procedure introducing phosphorus precursor.Particularly, by Rare earth metal precursors or alkali metal precursor hydration (step S610) in water, the solid product introducing phosphorus in step (e) is joined to perform dipping process (step S620) in hydration solution, and then that the product obtained like this is dry and heat-treat (step S630).
Especially, phosphorus precursor can be dissolved in the enough water (distilled water) for dissolving Rare earth metal precursors or alkali metal precursor completely (step S610), and can by solution stir about 5-15 minute at about 70-90 DEG C.Then, heat treated solid product can be added at about 70-90 DEG C and stir fully to flood.After by whole water evaporates, drying about 10-15 hour in an oven at about 90-110 DEG C, and can carry out firing at about 500-750 DEG C and continue about 1-10 hour (step S630).
In this case, according to the catalyst reaction of the ZSM-5 catalyst of final production, consider acidity, basicity and Carbon deposition amount, the introduction volume of Rare earth metal precursors or alkali metal precursor can be determined.Therefore, relative to the phosphorus within the scope of template addition, Rare earth metal precursors or the preferred introduction volume of alkali metal precursor can be the atomic ratios of less than 2.Preferred amount can be the atomic ratio of 0.1-1.5, and most preferred amount can be the atomic ratio of 0.5-0.9.
The rare earth metal comprised at Rare earth metal precursors can be selected from by lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), at least one of the group that terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu) form.Preferably, lanthanum can be selected.The alkali metal comprised at alkali metal precursor can be at least one being selected from the group be made up of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and caesium (Cs).Preferably, alkali metal can be the one in potassium, rubidium and caesium, and more preferably, alkali metal can be caesium.Especially, in order to select lanthanum as rare earth metal, lanthanum nitrate (La (NO can be introduced
3)
36H
2o) as Rare earth metal precursors, and in order to select lithium as alkali metal, lithium nitrate (LiNO can be introduced
3) as alkali metal precursor.
May further include before introducing phosphorus precursor according to the method that the 3rd embodiment preparation of the present invention's design has micropore and a mesoporous ZSM-5 catalyst, the cation replacement step (step S410) of the heat treated solid product of step (d) and the solid product of cation replacement is heat-treated (step S420).Concrete method can be identical with described in the first embodiment.
Prepared by the 3rd embodiment conceived by the present invention have micropore and mesoporous ZSM-5 catalyst can have micropore and mesoporous character simultaneously.These catalyst properties can improve the diffusion of reactant and intermediate, thus improve the productive rate comprising the light olefin of ethene and propylene that hydrocarbon mixture produces from C4 to C7.In addition, prepared by the 3rd embodiment conceived by the present invention have micropore can introduce the phosphorus of optimised quantity together with rare earth metal or alkali metal with mesoporous ZSM-5 catalyst, is used for producing the ZSM-5 catalyst with optimum acidity and basicity.When using the hydrocarbon of ZSM-5 catalyst from C4 to C7 to prepare the light olefin comprising ethene and propylene, having micropore and mesoporous ZSM-5 catalyst can long-time stable and can have good activity.Particularly, based on by weight 100 parts there is micropore and mesoporous ZSM-5 catalyst, there is micropore and mesoporous ZSM-5 catalyst and may further include rare earth metal relative to phosphorus about less than 2 atomic ratio or alkali metal, and about 300-400m can be had
2the specific area of/g, about 0.05-0.2cm
3volume, the about 0.05-0.15cm with the micropore of about below 1nm diameter of/g
3the mesoporous volume with about more than 2nm diameter of/g, be about 70-90 μm of ol-NH according to the temperature programmed desorption of ammonia
3acidity, the about 20-45 μm ol-NH of the faintly acid position of/g-catalyst
3the acidity of the highly acid position of/g-catalyst and about 2-30 μm ol-CO
2the basicity of/g-catalyst.
The light olefin comprising ethene and propylene prepared by prepared by the 3rd embodiment conceived by the present invention have micropore and C4 to the C7 hydrocarbon mixture that mesoporous ZSM-5 catalyst may be used for being produced after naphtha cracking processes by catalytic cracking.Specific reaction condition can be identical with described in the first embodiment.
Embodiment 1
Add 1.6g NaOH (SamchunChem) and be dissolved in 150ml distilled water.Then, 2.28g 4-propyl bromide (TPABr, sigma-Aldrich) is joined in this aqueous solution as the structure induced material of ZSM-5, then stir until TPABr dissolves completely.At room temperature in the aqueous solution comprising NaOH and TPABr, slowly drip cataloid (LudoxHS-40, Sigma-Aldrich) and stir, until form homogeneous mixture.By 0.78g sodium aluminate (NaAlO
2, Junsei) be dissolved in another 30ml distilled water, and stir 1 hour.By the solution obtained so lentamente and dropwise join in the solution comprising silica precursor (cataloid), and at room temperature stir 1 hour thus form gel.Based on 100 parts of silica precursors by weight, take 15 parts of carbon dusts (EC600JD, KetjenBlack) of predrying 3 hours in an oven at 110 DEG C by weight, join as template in gel, and then stir 3 hours.The solution of stirring is put into autoclave, and then at 160 DEG C Hydrothermal Synthesis continue 72 hours.After Hydrothermal Synthesis, the product produced like this is filtered and washs for several times with distilled water.Then, at 110 DEG C by dry for the solid sample of washing 10 hours.After drying, the solid product obtained like this is crushed, and then fires at 650 DEG C 10 hours to remove template (carbon).In order to carry out cation replacement to the solid product after drying, preparing the ammonium nitrate (Junsei) of 100ml1mol concentration and remaining on 80 DEG C.4g solid product is joined in ammonium nitrate, and stirs 3 hours at 80 DEG C.The aqueous solution of cation replacement filtered and washs, and then cation replacement process being carried out twice again.Dry 10 hours of the solid product that at 110 DEG C, cation replacement completed, and then at 650 DEG C, fire 5 hours thus produce there is micropore and mesoporous ZSM-5 catalyst.
Embodiment 2
Perform step in the same manner as in Example 1, except carbon addition is set to 30 parts by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 3
Perform step in the same manner as in Example 1, except carbon addition is set to 45 parts by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 4
Perform step in the same manner as in Example 1, except carbon addition is set to 60 parts by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 5
Perform step in the same manner as in Example 1, except carbon addition is set to 75 parts by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 6
Weighed by phosphorus precursor and be impregnated in the ZSM-5 catalyst obtained in embodiment 3, thus producing the ZSM-5 catalyst comprised based on 100 parts of final formation by weight, 0.17 part of phosphorus precursor has micropore and mesoporous ZSM-5 catalyst by weight.Phosphoric acid (85%, Sigma-Aldrich) is weighed, and is dissolved in 10ml distilled water.At 60 DEG C, the solution obtained like this is stirred 10 minutes, and then add the ZSM-5 catalyst that 1g obtains in embodiment 3.Keep stirring continuously at 60 DEG C to realize fully dipping.After distilled water is evaporated, at 100 DEG C dry 12 hours in an oven, and at 650 DEG C, carry out sintering procedure continue 3 hours thus produce that there is micropore and mesoporous ZSM-5 catalyst.
Embodiment 7
Perform step in the same manner as in Example 6, the pickup except phosphorus precursor is set to 0.3 part by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 8
Perform step in the same manner as in Example 6, the pickup except phosphorus precursor is set to 0.7 part by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 9
Perform step in the same manner as in Example 6, the pickup except phosphorus precursor is set to 1.4 parts by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 10
Perform step in the same manner as in Example 6, the pickup except phosphorus precursor is set to 2.7 parts by weight, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 11
In rare earth metal, select lanthanum (La), weigh in case have 0.3 lanthanum/phosphorus atoms ratio, and to be then incorporated into by dipping method in the ZSM-5 catalyst obtained in embodiment 7.By lanthanum nitrate (La (NO
3)
3-6H
2o, Sigma-Aldrich) weigh and be dissolved in 10ml distilled water, and stir 10 minutes at 60 DEG C.Add the catalyst that 1g produces in embodiment 1, and stir to realize abundant dipping continuously at 60 DEG C.After distilled water is evaporated, at 100 DEG C dry 12 hours in an oven, and at 650 DEG C, carry out sintering procedure continue 3 hours thus produce that there is micropore and mesoporous ZSM-5 catalyst.
Embodiment 12
Perform the step identical with embodiment 11, the pickup except lanthanum precursor is set to the lanthanum/phosphorus atoms ratio of 0.7, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 13
Perform the step identical with embodiment 11, the pickup except lanthanum precursor is set to the lanthanum/phosphorus atoms ratio of 0.9, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 14
Perform the step identical with embodiment 11, except the pickup of lanthanum precursor being set to the lanthanum/phosphorus atoms ratio of 1.2, thus production has micropore and mesoporous ZSM-5 catalyst.
Embodiment 15
In alkali metal, select lithium (Li), and lithium precursor is weighed, to have the lithium/phosphorus atoms ratio of 0.7, be then incorporated into by dipping method in the ZSM-5 catalyst obtained in embodiment 7.By lithium nitrate (LiNO
3, Sigma-Aldrich) weigh, and be dissolved in 10ml distilled water, and stir 10 minutes at 60 DEG C.Add the catalyst that 1g produces in embodiment 1, and stir to realize abundant dipping continuously at 60 DEG C.After by the evaporation of whole distilled water, at 100 DEG C dry 12 hours in an oven, and at 650 DEG C, carry out sintering procedure continue 3 hours thus produce that there is micropore and mesoporous ZSM-5 catalyst.
Embodiment 16
In alkali metal, select potassium (K), and potassium precursor is weighed in case have 0.7 potassium/phosphorus atoms ratio, be then incorporated into by dipping method in the ZSM-5 catalyst obtained in embodiment 7.By potassium nitrate (KNO
3, Sigma-Aldrich) weigh and be dissolved in 10ml distilled water, and stir 10 minutes at 60 DEG C.Add the catalyst that 1g produces in embodiment 1, and stir to realize abundant dipping continuously at 60 DEG C.After by the evaporation of whole distilled water, at 100 DEG C dry 12 hours in an oven, and at 650 DEG C, carry out sintering procedure continue 3 hours thus produce that there is micropore and mesoporous ZSM-5 catalyst.
Embodiment 17
In alkali metal, select caesium (Cs), caesium precursor is weighed in case have 0.7 caesium/phosphorus atoms ratio, be then incorporated into by dipping method in the ZSM-5 catalyst obtained in embodiment 7.By cesium nitrate (CsNO
3, Sigma-Aldrich) weigh and be dissolved in 10ml distilled water, and stir 10 minutes at 60 DEG C.Add the catalyst that 1g produces in embodiment 1, and stir to realize abundant dipping continuously at 60 DEG C.After by the evaporation of whole distilled water, at 100 DEG C dry 12 hours in an oven, and at 650 DEG C, carry out sintering procedure continue 3 hours thus produce that there is micropore and mesoporous ZSM-5 catalyst.
Comparing embodiment
Perform step in the same manner as in Example 1, except not using carbon as template to produce pure ZSM-5 catalyst.
Experiment 1: to the assessment with micropore and mesoporous ZSM-5 catalyst property
1. on the assessment of ZSM-5 catalyst crystal structure impact
(1) carbon is on the impact of ZSM-5 catalyst crystal structure
In order to assess the impact of carbon on the ZSM-5 catalyst crystal structure according to the first embodiment, X-ray diffraction analysis (D-MAX2500-PC, Rigaku) is carried out to the ZSM-5 catalyst produced by embodiment 1 to 5 and comparing embodiment.Result is shown in Figure 8.
See Fig. 8, for the catalyst produced in using carbon as the embodiment 1 to 5 of template and do not comprise carbon as the comparing embodiment of template in the catalyst produced, developed characteristic peak well.Can confirm from these results, carbon is not suppress to produce the factor of ZSM-5 catalyst crystal structure as template.
(2) phosphorus is on the impact of ZSM-5 catalyst crystal structure
In order to assess the impact of phosphorus on the ZSM-5 catalyst crystal structure according to the second embodiment, X-ray diffraction analysis (D-MAX2500-PC, Rigaku) is carried out to the ZSM-5 catalyst produced by embodiment 6 to 10.Result is shown in Figure 9.The result obtained for the ZSM-5 catalyst produced in embodiment 3 shows together, for comparing.
See Fig. 9, for the catalyst produced in the embodiment 6 to 10 introducing phosphorus and the catalyst produced in the embodiment 3 not comprising phosphorus, develop characteristic peak well.Meanwhile, along with phosphorus introduction volume increases, the relative sensitivity observing ZSM-5 catalyst characteristics peak reduces.Because made a part of framework distortion of the ZSM-5 be made up of-Si-O-Al-by the dealuminization caused owing to introducing phosphorus.Therefore, along with phosphorus introduction volume increases, the amount of dealuminization also increases and the relative sensitivity at ZSM-5 catalyst characteristics peak reduces.
(3) rare earth metal and alkali metal are on the impact of ZSM-5 catalyst crystal structure
In order to assess rare earth metal and alkali metal to the impact of the crystal structure of the ZSM-5 catalyst according to the 3rd embodiment, X-ray diffraction analysis (D-MAX2500-PC, Rigaku) is carried out to the ZSM-5 catalyst produced by embodiment 11 to 17.Result is shown in Figure 10 and 11.The result obtained for the ZSM-5 catalyst produced in embodiment 7 shows, together for comparing.
See Figure 10, for the catalyst produced in the embodiment 11 to 14 introducing phosphorus and lanthanum and the catalyst produced in the embodiment 7 comprising phosphorus, develop characteristic peak well.Meanwhile, along with lanthanum introduction volume increases, the relative sensitivity observing ZSM-5 catalyst characteristics peak reduces, as shown in Figure 10.Report, according to the chemical species existed in the channel in the XRD pattern of ZSM-5, under low angle, the intensity at ZSM-5 catalyst characteristics peak can greatly change (people such as L.Zhang, Catal, Lett.vol.130, p355,2009).Therefore, the relative sensitivity introducing the catalyst of lanthanum under low angle reduces can think to exist in the passage of the ZSM-5 catalyst produced that lanthanum chemical species causes.Owing to not observing the characteristic peak of lanthanum and lanthana in X-ray diffraction analysis, think that its size is very little thus can not be detected by X-ray diffraction analytical equipment.
See Figure 11, as in embodiment 15 to 17, for the alkali-metal catalyst of all introducings, find that the characteristic peak of ZSM-5 is formed well.Therefore, introduce alkali metal and be not considered to the structural change affecting ZSM-5.In addition, owing to not observing other peak except the characteristic peak of ZSM-5, can think that the size of the alkali metal particles introduced is very little, thus can not be detected by X-ray diffraction analytical equipment.
2. for forming the assessment with micropore and mesoporous ZSM-5 catalyst
(1) carbon is on the impact of micropore and mesoporous formation
The ZSM-5 catalyst produced in order to the first embodiment confirmed by conceiving according to the present invention forms micropore and mesoporous, the specific area of the ZSM-5 catalyst produced by embodiment 1 to 5 and comparing embodiment and pore volume, N2 adsorption and desorption curve and pore-size distribution are assessed, and observes crystal structure often opens photo figure.
First, measure specific area and the pore volume of the ZSM-5 catalyst produced in embodiment 1 to 5 and comparing embodiment, and be shown in Table 1.
< shows 1>
See table 1, with do not comprise according to comparing embodiment carbon as template catalyst compared with, use carbon to have larger mesopore volume as the catalyst of template according to embodiment 1 to 5.In addition, along with carbon amounts increases, the mesopore volume according to the catalyst of embodiment 1 to 5 increases significantly.But, comprise carbon does not affect catalyst significantly specific area as template.From found that, when using carbon as template, greatly can affect the porous of ZSM-5 catalyst, and carbon amounts can affect mesopore volume as central factor.
Figure 12 A and 12B is curve map, describe by using BET(ASAP-2010, MicrometricsInstrument) according to the N2 adsorption of ZSM-5 catalyst of embodiment 1 to 5 and comparing embodiment and the result of desorption curve figure (12A) and graph of pore diameter distribution (12B).
See Figure 12 A, the N2 adsorption of the catalyst produced by comparing embodiment and desorption curve figure show typical I type curve.That is, at (P/P
0adsorbed relatively large nitrogen near the relative pressure of)=0, and along with relative pressure increase, the increase of adsorption and desorption amount is less.But N2 adsorption and the desorption curve figure of the catalyst produced by embodiment 1 to 5 show IV type curve, wherein along with relative pressure increases, the amount of adsorption and desorption little by little increases.In addition, the hysteresis that the thermoisopleth measured between adsorption cycle is inconsistent with the thermoisopleth measured during desorption has been found.Find according to step of the present invention and use carbon to have as the ZSM-5 catalyst that template is produced to meet the mesoporous of the application's object.
See Figure 12 B, the catalyst display of being produced by comparing embodiment does not comprise the mesoporous pore-size distribution being less than about 2nm diameter.But the catalyst produced by embodiment 1 to 5 shows the mesoporous distribution with about 4nm diameter.
Show along with carbon amounts increases according to the catalyst of embodiment 1 to 5, the trend (see Figure 12 A) that per unit weight N2 adsorption increases and mesoporous clear observation (see Figure 12 B).Therefore, when using carbon as template, can prepare and there is mesoporous ZSM-5 catalyst.Especially, can change by controlling carbon amounts the multiple physical property comprising catalyst pores character.
Figure 13 A to 13F is the crystal structure photo figure of the ZSM-5 catalyst obtained by high resolution TEM (JEM-3010, Jeol) according to embodiment 3,5 and comparing embodiment.Figure 13 A and 13B is corresponding to the photo figure of the catalyst produced by comparing embodiment, Figure 13 C and the 13D photo figure corresponding to the catalyst produced by embodiment 3, and Figure 13 E and 13F is corresponding to the photo figure of the catalyst produced by embodiment 5.
See Figure 13 A to 13F, the catalyst produced by comparing embodiment shows the crystal structure of high density and atresia, is shown by sintering procedure by removing the hole forming this structure and produce together with the carbon of ZSM-5 crystal by embodiment 3 and 5 catalyst produced.Meanwhile, position instead of find the porous of catalyst of producing in embodiment 3 and 5 compared with the centre of heavy thickness having around the crystal with less thickness.
(2) phosphorus is on the impact of micropore and mesoporous formation
The ZSM-5 catalyst produced in order to the second embodiment confirmed by conceiving according to the present invention forms micropore and mesoporous, measures the specific area of the ZSM-5 catalyst produced by embodiment 6 to 10 and pore volume.Result is shown in Table 2.Show, for comparing together with the result of the catalyst produced by comparing embodiment and embodiment 3.
< shows 2>
See table 2, and do not comprise compared with ZSM-5 catalyst that carbon produced by comparing embodiment as template, the ZSM-5 catalyst using carbon to be produced by embodiment 3 and 6 to 10 as template has larger mesopore volume.As can be known from the results, carbon is used to be comprise the mesoporous catalyst meeting the application's object as the ZSM-5 catalyst of template.
Meanwhile, along with phosphorus amount increases, the physical property not very large change of catalyst, and specific area is reducing a little according near the amount of embodiment 10.When phosphorus is excessive, the phosphorus component of introducing may not be fully formed individual layer on the surface of the catalyst, but generating portion is assembled thus expanded its size thus block this some holes.For the ZSM-5 catalyst with micropore, due to the phosphorus plugging hole be introduced into, the acidic site in micropore may not work as active sites.But, for having mesoporous ZSM-5 catalyst, the phosphorus be introduced into can be suppressed to block larger hole thus reduce the reduction of catalytic activity.According to the present invention's design, when the mesoporous character of needs, phosphorus can be incorporated in ZSM-5 catalyst.By confirming this point, can propose the acidity and the Carbon deposition amount that consider ZSM-5 catalyst, preparation comprises the method that its best composition and quantity have micropore and mesoporous ZSM-5 catalyst.
(3) rare earth metal is on the impact of micropore and mesoporous formation
The ZSM-5 catalyst produced in order to the 3rd embodiment confirmed by conceiving according to the present invention forms micropore and mesoporous, adsorption and desorption experiment is carried out to the ZSM-5 catalyst produced by embodiment 11 to 14, and measures specific area and the pore volume of catalyst.Figure 14 is a curve map, describes by using BET(ASAP-2010, MicrometricsInstrument) experimental result of the ZSM-5 catalyst N2 adsorption that obtains and desorption.The specific area of ZSM-5 catalyst of this measurement device and the result of pore volume is used to be shown in Table 3.The result of the catalyst produced by embodiment 7 is shown together, for comparing.
< shows 3>
See Figure 14, N2 adsorption and the desorption curve figure of all catalyst produced as template by using carbon show IV type curve, wherein along with relative pressure (P/P
0) increase, adsorption and desorption amount little by little increases.In addition, the thermoisopleth measured between adsorption cycle and the inconsistent hysteresis of the thermoisopleth measured during desorption has been found.Find according to step of the present invention and to be had as the ZSM-5 catalyst that template is produced by use carbon and meet the mesoporous of the application's object.
See table 3, when compared with the ZSM-5 catalyst (embodiment 7) only introducing phosphorus, the ZSM-5 catalyst (embodiment 11 to 14) produced by introducing phosphorus and lanthanum has less specific area and micro pore volume and mesopore volume.Along with lanthanum introduction volume increases, cause micropore hole plug owing to introducing lanthanum, micro pore volume reduces greatly.But along with lanthanum amount increases, mesopore volume is without remarkable reduction.From these results, can thinking when compared with the ZSM-5 catalyst only with micropore character, can hole plug be suppressed by giving the mesoporous character of ZSM-5 catalyst.
3. the acidity of pair ZSM-5 catalyst and the assessment of alkalescence
(1) carbon is on the impact of acidity
In order to find the acidity with micropore and mesoporous ZSM-5 catalyst of producing according to the first embodiment of the present invention's design, and in order to confirm the impact of carbon on ZSM-5 acidity of catalyst, temperature programmed desorption experiment is carried out to the ZSM-5 catalyst produced by embodiment 1 to 5 and comparing embodiment, and calculates the acidity of the catalyst of preparation like this and compare.
Temperature programmed desorption experiment (BELCAT-B, BELJapan) is carried out for the ZSM-5 catalyst produced by embodiment 1 to 5 and comparing embodiment, and the result obtained like this is shown in Figure 15.From the peak area Figure 15, calculate the acidity of often kind of catalyst and be shown in Table 4.
< shows 4>
| Classification | Acidity (μm ol-NH 3/ g-catalyst) |
| Embodiment 1 | 139 |
| Embodiment 2 | 138 |
| Embodiment 3 | 139.5 |
| Embodiment 4 | 135 |
| Embodiment 5 | 133 |
| Comparing embodiment | 141 |
See Figure 15, according to the method for the Kaolinite Preparation of Catalyst of embodiment 1 to 5 and comparing embodiment, do not observe the difference of acid strength.In addition, see table 4, similar acidity is observed for the catalyst produced by embodiment 1 to 5 and comparing embodiment.From this result, confirm that the carbon as template does not affect acidity when preparing ZSM-5 catalyst.
(2) phosphorus is on the impact of acidity
In order to find the acidity with micropore and mesoporous ZSM-5 catalyst of producing according to the second embodiment of the present invention's design, and in order to confirm the impact of phosphorus on ZSM-5 acidity of catalyst, temperature programmed desorption experiment (BELCAT-B is carried out to the ZSM-5 catalyst produced by embodiment 6 to 10, BELJapan), and the result obtained like this be shown in Figure 16.From the peak area Figure 16, calculate the acidity of often kind of catalyst, and be shown in Table 5.The result of the catalyst produced by embodiment 3 is shown together, for comparing.See Figure 16, for all catalyst, find main desorption peaks at about 100-150 DEG C place and at an about 370-420 DEG C place.Peak 100-150 DEG C of place's display faintly acid position can be defined as, and the peak 370-420 DEG C of place's display highly acid position can be defined as.
< shows 5>
See table 5, along with phosphorus introduction volume increases, faintly acid position is without larger change, but highly acid position reduces a little.The phosphorus introduced seems and acidic site, is combined particularly people such as (, J.Catal.Vol.248, p29,2007) G.Zhao with highly acid position instead of faintly acid position.Therefore, along with phosphorus introduction volume increases, the acidity of highly acid position reduces.
(3) rare earth metal and alkali metal are on the impact of acidity
In order to confirm the impact with the acidity of micropore and mesoporous ZSM-5 catalyst that rare earth metal and alkali metal are produced the 3rd embodiment conceived according to the present invention, temperature programmed desorption experiment (BELCAT-B is carried out to the ZSM-5 catalyst produced by embodiment 11 to 17, BELJapan), and the result obtained like this be shown in Figure 17 and 18.Peak area from Figure 17 and 18, calculates the acidity of often kind of catalyst, and is shown in table 6 and 7.The result of the catalyst produced by embodiment 7 is shown in Figure 17 and table 6 together, and for comparing, and the result of the catalyst produced by embodiment 12 is shown in Figure 18 and table 7, together for comparing.See Figure 17 and 18, for all catalyst at about 100-150 DEG C and found main desorption peaks at an about 370-420 DEG C place.Peak 100-150 DEG C of place's display faintly acid position can be defined as, and the peak 370-420 DEG C of place's display highly acid position can be defined as.
< shows 6>
< shows 7>
See table 6, the change not observing acid strength is consistent with the increase of lanthanum introduction volume.But along with lanthanum introduction volume increases, faintly acid position and highly acid position are both reduced.The lanthanum introduced seems to be combined with a part of acidic site people such as (, Catal, Lett.vol.130, p355,2009) L.Zhang.Therefore, find that acidity reduces along with lanthanum introduction volume increases.
See table 7, based on the identical amount introducing metal, with the order of lanthanum, caesium, potassium and lithium, the acidity of catalyst reduces.For all catalyst, the acidity of faintly acid position does not show significant difference, but the acidity of highly acid position greatly reduces.The alkali metal introduced and the acidic site of catalyst, be considered to different from the combination degree of highly acid position particularly.
(4) rare earth metal is on the impact of alkalescence
In order to confirm the impact with micropore and mesoporous ZSM-5 catalyst alkalescence that rare earth metal is produced the 3rd embodiment conceived according to the present invention, carbon dioxide temperature programmed desorption experiment (BELCAT-B is carried out to the ZSM-5 catalyst produced by embodiment 11 to 14, BELJapan), and the result obtained like this be shown in Figure 19.From the peak area Figure 19, calculate the basicity of often kind of catalyst and be shown in Table 8.The result of the catalyst produced by embodiment 7 is shown together, for comparing.As shown in Figure 19, at an about 100-200 DEG C place, a characteristic peak is observed for all catalyst.
< shows 8>
| Basicity (μm ol-CO 2/ g-catalyst) | |
| Embodiment 7 | 4.3 |
| Embodiment 11 | 7.3 |
| Embodiment 12 | 11.7 |
| Embodiment 13 | 14.7 |
| Embodiment 14 | 24.5 |
See table 8, along with lanthanum amount increases, basicity increases.Owing to introducing lanthanum, seem to generate basic sites people such as (, Appl.Catal.A, vol.333, p202,2007) Y.Zhang on the surface of ZSM-5.
The cracking reaction of hydro carbons is usually known to be completed (people such as H.Krannila, J.Catal.vol.135, p115,1992) by monomolecular cracking and bimolecular cracking two kinds of mechanism.For monomolecular cracking, or easily can decompose hydro carbons by high reaction temperature thus produce multi-products, such as alkene by the β-cracking of acidity of catalyst position.For bimolecular cracking, and hydride between carbonium ion can be adsorbed on acidic site to shift to form larger carbonium ion by paraffin, and then can pass through β-cracking generation cracking reaction, aromatic compound can be formed by cyclization, maybe can form the isomers (people such as D.Mier by isomerization reaction, Ind.Eng.Chem.Res.vol.49, p8415,2010).Therefore, in order to be maximized by the output of light olefin, need the mechanism suppressing to be performed by bimolecular cracking, but need to activate the mechanism performed by monomolecular cracking.In these two kinds of mechanism, hydrogen transfer activity is the index for determining key reaction path.Hydrogen transfer activity can be determined by the paraffin/olefin ratio of particular hydrocarbon in the product of reaction starting stage generation.When hydrogen transfer activity is higher, namely when hydride ion capacity (capacity) is higher, bimolecular cracking mechanism is main, and can produce a large amount of aromatic compounds and paraffin.When hydrogen transfer activity is lower, namely when hydride ion capacity is lower, be main by the monomolecular cracking of direct β-cracking carbonium ion, and a large amount of light olefins can be generated.
In order to determine the impact of the alkalescence of ZSM-5 catalyst on above-mentioned hydride transfer activity, measure the hydride transfer activity of ZSM-5 catalyst produced according to embodiment 11 to 14, and the relation of itself and catalyst alkalescence is shown in Figure 20.Hydrogen transfer activity is shown by the ratio of (iso-butane+normal butane)/butylene.The result of the catalyst produced by embodiment 7 is shown together, for comparing.
See Figure 20, along with catalyst basicity increases, namely along with lanthanum introduction volume increases, hydride transfer activity reduces.From this result, hydride transfer activity can be controlled by being incorporated in ZSM-5 catalyst by the metal of display alkalescence, and by using this character effectively to prepare light olefin.
Experiment 2: for the assessment of light olefins yields and the analysis of catalytic activity by use with micropore and the production of mesoporous ZSM-5 catalyst crackene mixture.
(1) productive rate of carbon on light olefin and the impact of catalytic activity
In order to analyze by use produce according to the first embodiment of the present invention's design there is the light olefin that micropore and mesoporous ZSM-5 catalyst produced by catalytic cracking hydrocarbon mixture, ethene and propylene particularly, productive rate, be prepared reaction according to preparation feedback embodiment 1.Hydrocarbon mixture as reactant is C 5 fraction, and component ratio is shown in Table 9.
< shows 9>
| Chemical name | Component ratio (mol%) |
| Pentane | 33.4 |
| Isopentane | 25.0 |
| Amylene | 8.3 |
| Iso-amylene | 25.0 |
| Pentamethylene | 8.3 |
[preparation feedback embodiment 1]
In order to carry out the catalytic cracking of C 5 fraction, the ZSM-5 catalyst produced being put into reactor respectively, and at 500 DEG C, by nitrogen (40ml), catalyst was activated 1 hour according to embodiment 1 to 5 and comparing embodiment before reacting.After catalyst activation, reactant is reacted continually by the catalyst layer in reactor.The weight hourly space velocity (WHSV) of reactant remains on 3.5h
-1, and the catalytic cracking temperature of C 5 fraction is 500 DEG C.By gas chromatography, the product obtained after reaction is analyzed.The productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) is shown in table 10 and Figure 21.At this, calculated the productive rate of the conversion ratio of C 5 fraction, the selective of light olefin and light olefin (ethene+propylene) by equation 1 to 4.
< equation 1>
< equation 2>
< equation 3>
< equation 4>
The productive rate (%) of ethene and propylene
The conversion ratio of=C 5 fraction × (ethene selective+propylene selective)/100
< shows 10>
See table 10, by catalytic cracking C 5 fraction, also create methane, ethane, propane and butane and their isomers, and light olefin, such as ethene and propylene.And, except being undertaken except cracking by β-cracking, by the catalytic cracking mechanism of C 5 fraction, the hydrocarbon chain longer than C5 hydro carbons can be produced by the polymerisation between carbonium ion.
When prepare compare the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) according to the carbon amounts being used as template in ZSM-5 catalyst time, when with do not comprise according to comparing embodiment carbon as template catalyst compared with time, when using the catalyst using carbon as template according to embodiment, the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) increases.When compared with the pure ZSM-5 catalyst produced according to comparing embodiment, because comprise good development mesoporous by using carbon as the catalyst that template is produced according to these embodiments, the reactivity generation difference of catalyst.Comprise the good mesoporous catalyst of the development of producing according to these embodiments can relax in the catalytic cracking of C 5 fraction when use only comprise the pure ZSM-5 catalyst of below 1nm micropore time institute issuable reactant, product and intermediate diffusion limit.Therefore, when use comprises mesoporous catalyst, even better reactivity can be obtained.Along with carbon amounts increases, namely use the mesoporous catalyst comprising good development even further, the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) can increase.
Simultaneously, when the carbon amounts being used as template during preparing ZSM-5 catalyst be up to by weight 45 parts time (see embodiment 1 to 3), the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) increases, but, when carbon amounts increase above by weight 45 parts time (see embodiment 4 and 5), the conversion ratio of C 5 fraction and the productive rate of light olefin no longer increase.Joined the amount in the ZSM-5 catalyst produced according to embodiment 3 by carbon, the mesoporous character of catalyst is that adsorption and desorption C 5 fraction, product and intermediate provide sufficient space.Even if ZSM-5 catalyst comprises the mesopore volume (in the preparation process of catalyst carbon addition exceed by weight 45 part) larger than the ZSM-5 catalyst produced according to embodiment 3, also no longer show the activity limiting the catalyst reaction caused owing to relaxing diffusion and improve.In addition, as described in Figure 15 and table 4, according to the preparation method of catalyst, the acidity of catalyst is different from each other, and therefore, can ignore the acidity of catalyst to the impact of reactivity difference.The physical property being better than pure ZSM-5 catalyst is shown according to the mesoporous ZSM-5 catalyst that has that the first embodiment is produced as template by use carbon.From this result, there is mesoporous ZSM-5 catalyst cracking C 5 fraction prepare light olefin by using and be considered to very effective.In addition, can propose to consider that the best of productive rate adds carbon amounts, to obtain the most effective ZSM-5 catalyst for the preparation of light olefin.
(2) productive rate of phosphorus on light olefin and the impact of catalytic activity
In order to analyze by using have micropore and the mesoporous ZSM-5 catalyst produced according to the second embodiment of the present invention's design to produce light olefin by catalytic cracking hydrocarbon mixture, ethene and propylene particularly, productive rate, be prepared reaction according to preparation feedback embodiment 2.It is the C 5 fraction of the composition ratio had as display in table 9 above as the hydrocarbon mixture of reactant.
[preparation feedback embodiment 2]
In order to carry out the catalytic cracking of C 5 fraction, the ZSM-5 catalyst produced being put into reactor respectively, and at 650 DEG C, by nitrogen (40ml), catalyst was activated 1 hour according to embodiment 3,6 to 10 before reacting.After catalyst activation, reactant is reacted continually by the catalyst layer in reactor.The weight hourly space velocity (WHSV) of reactant remains on 3.5h
-1, and the catalytic cracking temperature of C 5 fraction is set as 600 DEG C.By gas chromatography, the product obtained after reaction is analyzed.The conversion ratio of C 5 fraction and the selective and productive rate of light olefin (ethene+propylene) is shown in Figure 22 A and 22B.At this, calculated the productive rate of the conversion ratio of C 5 fraction, the selective of light olefin and light olefin (ethene+propylene) by equation 1 to 4.
See Figure 22 A and 22B, use carbon even better more active than pure catalyst (comparing embodiment) as activity (embodiment 3) display of the ZSM-5 catalyst of template.When compared with the pure ZSM-5 catalyst produced according to comparing embodiment, because comprise as the catalyst that template is produced well develop mesoporous by using carbon according to these embodiments, the reactivity of catalyst creates difference.The mesoporous catalyst comprising the good development of producing according to these embodiments can relax in catalytic cracking C 5 fraction by using the diffusion restriction of the pure ZSM-5 catalyst that only comprises below 1nm micropore and issuable reactant, product and intermediate.Therefore, when use comprises mesoporous catalyst, even better reactivity can be obtained.
In addition, during the reaction time of about 40 hours, pure ZSM-5 catalyst shows catalysqt deactivation fast.This inactivation is caused by Carbon deposition between the stage of reaction.The immediate cause of Carbon deposition is as the polymerisation between the carbonium ion of accessory substance generation during catalytic cracking C 5 fraction.When to produce Carbon deposition in the micropore porch of pure ZSM-5 catalyst due to the polymerisation between carbonium ion, the avtive spot that the avtive spot that micropore inside exists may not be re-used as cracking C 5 fraction works.Therefore, along with Carbon deposition increases, catalytic activity can reduce fast.
On the contrary, passing through to use carbon as in the ZSM-5 catalyst of Template preparation, inactivation trend shows consistent with the reaction time slightly, but this inactivation trend is lower than pure ZSM-5 catalyst.Because by using carbon as the mesoporous character of the ZSM-5 catalyst of Template preparation, this character can be obtained.In this case, even if form Carbon deposition in the porch in hole, block completely mesoporous before C 5 fraction can infiltrate in the inside in hole fully, and can to react.But along with the reaction time extends, Carbon deposition can little by little increase, and finally may block this some holes, and may reduce reactivity.Therefore, may need to show mesoporous characteristic and minimum ZSM-5 catalyst is down in catalysqt deactivation effect, and introduce phosphorus using by use carbon as the ZSM-5 catalyst of Template preparation.
For the ZSM-5 catalyst (embodiment 6 to 10) by being incorporated into by phosphorus by using carbon to prepare in the ZSM-5 catalyst of Template preparation, during the reaction time of 40 hours, show metastable activity.Only when the amount introducing phosphorus is low a little (embodiment 6), according to the passage in reaction time, observe the trend of inactivation.But when the amount introducing phosphorus increases (embodiment 7 to 10), period in the reaction time ZSM-5 catalyst at 40 hours shows stable reactivity.
In order to study the acidity of ZSM-5 catalyst, particularly in order to study the acidity of the highly acid position of ZSM-5 catalyst as shown in table 5 to the impact of reactivity, arrange in Figure 23 A and 23B and relation between the productive rate describing the acidity of highly acid position of ZSM-5 catalyst, the conversion ratio of C 5 fraction and light olefin (ethene+propylene).
See Figure 23 A and 23B, relative to the acidity of highly acid position, react the conversion ratio of C 5 fraction and the productive rate display volcano type distribution of light olefin afterwards in 40 hours.At this, as shown in Figure 22 A and 22B, initial activity is good, but for the ZSM-5 catalyst in highly acid position according to embodiment 3 to 6 with larger acidity, after reaction 40 hours, activity reduces a little.For the ZSM-5 catalyst according to embodiment 8 to 10, when the amount of the phosphorus introduced is larger, stable reactivity can be shown, but the acidity of highly acid position reduces a bit and reactivity reduces a little.Therefore, passing through for according to the ZSM-5 catalyst of embodiment 7 phosphorus introducing appropriate amount, by controlling the acidity of highly acid position, can the deactivation of ZSM-5 catalyst is down to minimum, and can by the maximize yield of light olefin (ethene+propylene).
Simultaneously, be incorporated into by using carbon as the amount of phosphorus in the ZSM-5 catalyst of Template preparation to the impact of the deposition of the reaction time carbon according to catalyst to assess, the ZSM-5 catalyst produced after reaction 40 hours according to embodiment 3 and 6 to 10 is analyzed, carry out CHNS(CHNS932, Leco) analyze, and the result of Carbon deposition amount is shown in Table 11.
< shows 11>
| Classification | Carbon deposition amount (wt%) |
| Embodiment 3 | 9.4 |
| Embodiment 6 | 6.8 |
| Embodiment 7 | 3.5 |
| Embodiment 8 | 3.3 |
| Embodiment 9 | 3.4 |
| Embodiment 10 | 2.5 |
See table 11, do not comprise the Carbon deposition amount of the ZSM-5 catalyst (embodiment 3) of phosphorus significantly higher than the ZSM-5 catalyst (embodiment 6 to 10) comprising phosphorus.In addition, for the ZSM-5 catalyst comprising phosphorus, along with phosphorus amount increases, Carbon deposition amount reduces.As can be known from the results, by phosphorus being incorporated into by using carbon can greatly suppress in the ZSM-5 catalyst of Template preparation in catalytic cracking C 5 fraction due to catalysqt deactivation that the Carbon deposition of catalyst causes.The acidity of highly acid position is considered to reduce along with the introducing of phosphorus.As shown in Figure 22 A and 22B, for the ZSM-5 catalyst (for not comprising the ZSM-5 catalyst of phosphorus or comprising the ZSM-5 catalyst of very low amount phosphorus) of highly acid position with highly acidity, the reactivity of reacting after 40 hours reduces a little, but, for the ZSM-5 catalyst (the ZSM-5 catalyst for comprising appropriate amount phosphorus) of highly acid position with Low acid, show stable reactivity.Therefore, easily can produce Carbon deposition by highly acid position instead of faintly acid position, and the catalyst had Carbon deposition tolerance can be prepared when by introducing phosphorus and controlling the acidity of highly acid position.Only when introducing excessive phosphorus, the activity of catalyst can reduce a little, and therefore expects the phosphorus adding appropriate amount.
Figure 24 A to 24F is the photo figure of ZSM-5 catalyst crystal structure after reaction 40 hours obtained by high-resolution transmission electron microscope (JEM-3010, Jeol) according to embodiment 3,7 and 9.In Figure 24 A to 24F, C-ZSM5,0.3P/C-ZSM5 and 1.4P/C-ZSM5, respectively corresponding to embodiment 3, embodiment 7 and embodiment 9.
See Figure 24 A to 24F, around the crystal structure of ZSM-5 catalyst (embodiment 3) not comprising phosphorus, define the strip being different from catalyst crystal lattice structure.This band is considered to be formed by Carbon deposition.This banded structure is not observed for the ZSM-5 catalyst (embodiment 7 to 9) comprising phosphorus.This result is consistent with the CHNS analysis result in table 11, and from this result, for can, by phosphorus being included in the ZSM-5 catalyst comprising carbon and prepare in the ZSM-5 catalyst of template, confirm to inhibit Carbon deposition.
(3) productive rate of rare earth metal on light olefin and the impact of catalytic activity
By what use the 3rd embodiment conceived according to the present invention to produce, there is micropore and mesoporous ZSM-5 catalyst in order to analyze, by the light olefin that catalytic cracking hydrocarbon mixture produces, ethene and propylene particularly, productive rate, be prepared reaction according to preparation feedback embodiment 3.Have as the C 5 fraction of the component ratio of display in table 9 above as the hydrocarbon mixture of reactant.
[preparation feedback embodiment 3]
In order to carry out the catalytic cracking of C 5 fraction, the ZSM-5 catalyst produced according to embodiment 7 and 11 to 14 is put into reactor respectively, and at 600 DEG C, by nitrogen (40ml), catalyst was activated 1 hour before reacting.Catalyst activation after, by reactant continually by the catalyst layer in reactor to react.The weight hourly space velocity (WHSV) of reactant remains on 3.5h
-1, and the catalytic cracking temperature of C 5 fraction is 600 DEG C.By gas chromatography, the product obtained after reaction is analyzed.Calculate the conversion ratio of C 5 fraction and the selective and productive rate of light olefin (ethene+propylene), and in Figure 25 A and 25B, describe acidity and the impact of alkalescence on reactivity of catalyst.At this, show the relation of lanthanum/between phosphorus atoms ratio and light olefins yields in fig. 26.At this, calculated the productive rate of the conversion ratio of C 5 fraction, the selective of light olefin and light olefin (ethene+propylene) by equation 1 to 4.Reaction result in Figure 25 A and 25B is based on the result that reaction obtains for 20 hours afterwards.
First, reactivity reduction was not shown for the reaction time of 20 hours.From this experimental result, find that the phosphorus component introduced prevents dealuminization and suitably achieve inhibit feature in catalysqt deactivation.
See Figure 25 A, the alkalescence of catalyst greatly have impact on the product distribution obtained after reacting.Along with the basicity of catalyst increases, the selective of light olefin greatly increases.But aromatic compound (benzene,toluene,xylene etc.) selective, reduces.These trend are increased by the alkalescence along with catalyst, and hydrogen transfer activity reduces (see Figure 20) of causing.When the hydrogen transfer activity of catalyst reduces, bimolecular cracking can be suppressed, but, can monomolecular cracking be promoted, and therefore, can preferably directly β-cracking be used for cyclisation carbonium ion and isomerization.Therefore, the selective of light olefin can be improved, and the generation of aromatic compound can be suppressed.
See Figure 25 B, introduce lanthanum and be not considered to play positive acting in the conversion ratio improving C 5 fraction.As mentioned above, the introducing of lanthanum can reduce the acidity (see Figure 17) of catalyst, and the acidity reducing catalyst may cause the reduction of cracking activity, thus reduces reactivity.That is, the lanthanum of introducing can be combined the acidity for reducing catalyst with a part of acidic site of catalyst, and can reduce cracking activity.Therefore, along with lanthanum introduction volume increases, the conversion ratio of C 5 fraction can be reduced.
See Figure 26, for the atomic ratio of lanthanum/phosphorus, the productive rate display volcano type distribution of light olefin.The increase of lanthanum can reduce the acidity of catalyst and reduce the conversion ratio of C 5 fraction, but, the basicity of catalyst can be increased and weaken hydrogen transfer activity thus add the selective of light olefin.Therefore, the catalyst having suitable lanthanum/phosphorus atoms ratio by preparation controls the optical states of acidity as the catalyst described in embodiment 12 and alkalescence, the inactivation of catalyst can be down to minimum and can by the maximize yield of light olefin.
(4) productive rate of alkali metal on light olefin and the impact of catalytic activity
According to the 3rd embodiment of the present invention's design, there is micropore and mesoporous by using in order to analyze, and comprise phosphorus and alkali-metal ZSM-5 catalyst, by the light olefin that catalytic cracking hydrocarbon mixture produces, ethene and propylene especially, productive rate, according to preparation feedback embodiment 3, reaction is prepared for the ZSM-5 catalyst produced by embodiment 15 to 17.Result is shown in Table 12.Use and show, for comparing together with the result of the ZSM-5 catalyst of 12 preparations according to embodiment 7.
< shows 12>
See table 12, and introduce the catalyst (embodiment 7) of phosphorus or introduce phosphorus and compare with the catalyst (embodiment 12) of lanthanum, introducing lithium or potassium shows reactivity lower a little as alkali-metal catalyst (embodiment 15 and 16).But catalyst (embodiment 17) display introducing caesium improves the selective of light olefin, even if show the conversion ratio of C 5 fraction low a little, thus display high yield.In addition, compared with introducing the catalyst of phosphorus or rare earth metal, introduce alkali-metal all catalyst and show the selective of lower aromatic compound.As can be known from the results, introduce alkali metal and be considered to the reaction mechanism that inhibit bimolecular cracking, activated the reaction mechanism of monomolecular cracking simultaneously.When specific alkali metal being optionally incorporated in the ZSM-5 catalyst comprising phosphorus, when with introduce the ZSM-5 catalyst of rare earth metal together with phosphorus compared with, by catalytic cracking C 5 fraction prepare that light olefin can carry out more effective.
As mentioned above, according to the present invention's design can prepare comprise as template carbon and there is the ZSM-5 catalyst of micropore character and mesoporous character simultaneously.This catalyst property can improve the diffusion of reactant and intermediate, and can increase the productive rate comprising the light olefin of ethene and propylene of the hydrocarbon mixture from C4 to C7.
In addition, phosphorus introduction volume can be optimized, so that control has the acidity of the highly acid position of micropore and mesoporous ZSM-5 catalyst thus provides the ZSM-5 catalyst with optimum acidity.When use has micropore and the hydrocarbon mixture preparation of mesoporous ZSM-5 catalyst from C4 to C7 comprises the light olefin of ethene and propylene, stable and good activity can be shown for a long time.
In addition, have in the ZSM-5 catalyst of micropore and mesoporous character by phosphorus and rare earth metal or alkali metal are incorporated into, its bronsted lowry acids and bases bronsted lowry can be formed and can easily control and the catalyst with best atomic ratio.When use has micropore and the hydrocarbon mixture preparation of mesoporous ZSM-5 catalyst from C4 to C7 comprises the light olefin of ethene and propylene, the output of light olefin can be improved, and stable and good activity can be kept for a long time.
Although show particularly and illustrate invention has been with reference to its illustrative embodiments, those of ordinary skill in the art should be understood that the change wherein can made in various ways and details, and do not depart from as by claims below the spirit and scope of the present invention that limit.
Claims (27)
1. prepare the method with micropore and mesoporous ZSM-5 catalyst for one kind, the light olefin comprising ethene and propylene prepared by the hydrocarbon mixture that described catalyst is used for being had by catalytic cracking 4 to 7 carbon, described hydrocarbon mixture produces after naphtha cracking processes, and described method comprises:
A () forms gel by the aging mixture solution comprising silica precursor and aluminum precursor;
B () joins in described gel by can be formed mesoporous template by heat treatment, in advance at 100-150 DEG C by dry for template 1-5 hour, and at room temperature mixture is stirred 1-5 hour, and then at room temperature by mixture ageing 1-5 hour to prepare crystallisation step;
C () is by forming solid product by crystalline mixture aging in step (b);
And
D () is heat-treated described solid product thus is removed described template;
Wherein said template is carbon dust or nanometer polymerization composition granule, described carbon dust or nanometer polymerization composition granule have for 2-50nm diameter spherical, rectangle and cylindrical at least one shape; And wherein based on the described silica precursor of 100 parts by weight, the amount of template is by weight 5-80 part.
2. method according to claim 1, wherein by comprising the mixture solution that every method is come in preparation process (a) below:
(a-1) by monovalent metal hydroxide and tetrapropyl ammonium halide dissolves in distilled water;
(a-2) add described silica precursor thus form homogeneous mixture; And
(a-3) the described aluminum precursor of liquid phase is added drop-wise in described homogeneous mixture.
3. method according to claim 2, wherein said silica precursor is cataloid, and described aluminum precursor is selected from by sodium aluminate (NaAlO
2), aluminum nitrate (Al (NO
3)
3), aluminium secondary butylate, tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide composition group at least one.
4. method according to claim 1, wherein said carbon dust or nanometer polymerization composition granule are the square with 2-50nm diameter.
5. method according to claim 1, wherein said nanometer polymer is selected from least one in the group that is made up of Merlon, polystyrene, polyethylene, polypropylene, poly-(oxirane), poly-(expoxy propane), polyactide and polymethyl methacrylate.
6. method according to claim 1, comprises further:
E phosphorus precursor is incorporated in heat treated solid product by dipping method or ion-exchange process by (),
Based on by weight 100 parts there is micropore and mesoporous described ZSM-5 catalyst, the amount of described phosphorus precursor is by weight 0.1-1.5 part.
7. method according to claim 1, the Si/Al atomic ratio wherein with micropore and mesoporous ZSM-5 catalyst is 5-300.
8. method according to claim 1, the heat treatment wherein in step (d) carries out at the temperature of 300-750 DEG C, continues 3-10 hour.
9. method according to claim 1, after being included in completing steps (d) further:
(d-1) cation of heat treated described solid product is replaced; And
(d-2) the described solid product of cation replacement is heat-treated.
10. method according to claim 9, wherein said cationic displacement is selected from by ammonium nitrate (NH by using to comprise
4nO
3), ammonium chloride (NH
4cl), ammonium carbonate ((NH
4)
2cO
3) and ammonium fluoride (NH
4the solution of at least one in the group F) formed realizes.
11. methods according to claim 9, the heat treatment wherein in step (d-2) carries out at the temperature of 400-700 DEG C, continues 3-10 hour.
12. methods according to claim 6, the dipping method of wherein said phosphorus precursor comprises:
(e-1) use water by described phosphorus precursor hydration thus obtain hydration solution;
(e-2) described solid product heat treated in step (d) is joined in described hydration solution to flood with described hydration solution; And
(e-3) drying and heat treatment are carried out to the described solid product of dipping.
13. methods according to claim 12, wherein said phosphorus precursor is selected from by phosphoric acid (H
3pO
4), mono phosphoric acid ester ammonium ((NH
4) H
2pO
4), Diammonium phosphate (DAP) ((NH
4)
2hPO
4) and ammonium phosphate ((NH
4)
3pO
4) at least one in the group that forms.
14. methods according to claim 12, the heat treatment wherein in step (e-3) carries out at the temperature of 500-750 DEG C, continues 1-10 hour.
15. methods according to claim 6, comprise further:
F Rare earth metal precursors or alkali metal precursor, by dipping method or ion-exchange process, are incorporated in the heat treated described solid product comprising described phosphorus precursor by (),
Wherein based on the atomic ratio relative to described phosphorus, described rare earth metal or alkali-metal amount are 0.1-1.5.
16. methods according to claim 15, wherein the dipping method of Rare earth metal precursors described in step (f) or alkali metal precursor comprises:
(f-1) in water, make described Rare earth metal precursors or alkali metal precursor hydration;
(f-2) solid product comprising phosphorus described in step (e) is joined in the Rare earth metal precursors of hydration including stand-by described solution impregnation or the solution of alkali metal precursor; And
(f-3) drying and heat treatment are carried out to the described solid product of dipping.
17. methods according to claim 16, wherein said rare earth metal is selected from least one in the group that is made up of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu).
18. methods according to claim 16, wherein said alkali metal is selected from least one in the group that is made up of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and caesium (Cs).
19. methods according to claim 16, the heat treatment wherein in step (f-3) carries out at the temperature of 500-750 DEG C, continues 1-10 hour.
20. methods according to claim 1, wherein said hydrocarbon mixture comprises C 5 fraction.
21. 1 kinds have micropore and mesoporous ZSM-5 catalyst, the light olefin comprising ethene and propylene prepared by the hydrocarbon mixture that described catalyst is used for being had by catalytic cracking 4 to 7 carbon, described hydrocarbon mixture produces after naphtha cracking processes, described catalyst is prepared as template by using carbon dust or nanometer polymerization composition granule
Wherein said catalyst is prepared by method according to claim 1, and described catalyst has 360-410m
2the specific area of/g, 0.1-0.2cm
3the volume with the micropore of below 1nm diameter of/g, 0.05-0.3cm
3the mesoporous volume with more than 2nm diameter of/g and the temperature programmed desorption 130-145 μm ol-NH according to ammonia
3the acidity of/g-catalyst.
22. 1 kinds have micropore and mesoporous ZSM-5 catalyst, the light olefin comprising ethene and propylene prepared by the hydrocarbon mixture that described catalyst is used for being had by catalytic cracking 4 to 7 carbon, described hydrocarbon mixture produces after naphtha cracking processes, described catalyst is prepared as template by using carbon dust or nanometer polymerization composition granule
Wherein said catalyst is prepared by method according to claim 6, and described catalyst has 340-400m
2the specific area of/g, 0.05-0.2cm
3the volume with the micropore of below 1nm diameter of/g, 0.05-0.2cm
3the mesoporous volume with more than 2nm diameter of/g, according to the temperature programmed desorption of ammonia in faintly acid position 80-95 μm of ol-NH
3the acidity of/g-catalyst and in highly acid position 15-50 μm of ol-NH
3the acidity of/g-catalyst and analyze the Carbon deposition amount of 2-7wt% according to the CHNS after catalyst reaction 40 hours.
23. catalyst according to claim 22, based on the atomic ratio relative to described phosphorus, comprise rare earth metal or the alkali metal of 0.1-1.5 further.
24. catalyst according to claim 23, wherein said catalyst is prepared by method according to claim 16, and described catalyst has 300-400m
2the specific area of/g, 0.05-0.2cm
3the volume with the micropore of below 1nm diameter of/g, 0.05-0.15cm
3the mesoporous volume with more than 2nm diameter of/g, according to the temperature programmed desorption of ammonia in faintly acid position 70-90 μm of ol-NH
3the acidity of/g-catalyst, in highly acid position 20-45 μm of ol-NH
3the acidity of/g-catalyst and 2-30 μm of ol-CO
2the basicity of/g-catalyst.
25. catalyst according to claim 21, wherein said hydrocarbon mixture comprises C 5 fraction.
The method of the light olefin comprising ethene and propylene prepared by 26. 1 kinds of hydrocarbon mixtures having 4 to 7 carbon by catalytic cracking, and described hydrocarbon mixture produces after naphtha cracking processes, and described hydrocarbon mixture is at 1-20h
-1weight hourly space velocity (WHSV) under, under the temperature range of 300-700 DEG C, according to claim 21 there is micropore and mesoporous ZMS-5 catalyst under react.
27. methods according to claim 26, wherein said hydrocarbon mixture comprises C 5 fraction.
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| KR10-2011-0125643 | 2011-11-29 | ||
| KR1020110125643A KR101279691B1 (en) | 2011-11-29 | 2011-11-29 | Zsm-5 catalyst with micropores and mesopores, preparation method thereof and production method of light olefins through catalytic cracking of hydrocarbons using the catalyst |
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| CN106632760B (en) * | 2015-11-04 | 2020-04-07 | 中国石油化工股份有限公司 | Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method |
| CN106698463B (en) * | 2015-11-12 | 2018-10-12 | 中国石油化工股份有限公司 | A method of synthesis nano-ZSM-5 molecular sieve |
| CN106698454B (en) * | 2015-11-12 | 2018-12-18 | 中国石油化工股份有限公司 | A kind of synthetic method of nanometer of EU-1 molecular sieve |
| CN105728019B (en) * | 2016-03-17 | 2018-07-20 | 中国天辰工程有限公司 | A kind of preparation method and application of the ZSM-5 molecular sieve with Jie's micropore |
| WO2020078437A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Phosphorus-containing rare-earth-containing mfi structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| WO2020078434A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| US11975980B2 (en) | 2018-10-18 | 2024-05-07 | China Petroleum & Chemical Corporation | MFI structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
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