CN102001682B - Method for synthesizing heteroatom substituted MeAPO-31 molecular sieve by microwave heating - Google Patents
Method for synthesizing heteroatom substituted MeAPO-31 molecular sieve by microwave heating Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a heteroatom substituted MeAPO-31 molecular sieve by microwave heating, relating to a preparation method of a MeAPO-31 molecular sieve. The invention aims to solve the technical problems that the traditional method for preparing the MeAPO-31 molecular sieve has long crystallization time, easy generation of mixed crystals in products, limited type and quantity of the heteroatom introduced into a frameworkd, the narrow adjustable range of the produced acid sites and the like. The method comprises the following steps of: firstly, preparing gel by using phosphoric acid, water, di-n-butylamine, aluminum isopropoxide (or boehmite) and metal salt; heating with microwaves; and crystallizing, then centrifugally filtering, washing, drying and roasting to obtain the MeAPO-31 molecular sieve. Compared with the traditional hydrothermal process, the method disclosed in the invention obviously shortens the crystallization time of the molecular sieve and does not generate mixed crystals. The MeAPO-31 molecular sieve prepared with the method can be used as catalysts in the fields of petrochemical industry, fine chemical industry and the like.
Description
Technical field
The present invention relates to the preparation method of MeAPO-31 molecular sieve.
Background technology
AlPO-31 is by AlO
4With PO
4The aluminium phosphate molecular sieve with ATO type topological framework that tetrahedron alternately rearranges, the skeleton charge balance does not have acidic site.Metal heteroatoms such as Mg, Co, Zn, Ti, Mn, Fe, V are introduced the aluminium phosphate molecular sieve skeleton replaces Al with part or P processes the substituted MeAPO-31 molecular sieve of heteroatoms; Make the skeleton of aluminium phosphate molecular sieve that tradable electric charge arranged, can be used as and have gentle tart sieve catalyst.(SAPO-31) compares with the silicoaluminophosphamolecular molecular sieves with identical topological framework; The MeAPO-31 molecular sieve of in the AlPO-31 framework of molecular sieve, only introducing heteroatomss formation such as a spot of Mg, Co can produce abundant active sites; Overcome in the SAPO-31 sieve synthesis procedure because of introducing a large amount of Si atoms and could form enough acidic sites and be prone to produce drawbacks such as SAPO-5 and SAPO-11 molecular sieve stray crystal, and can realize meticulous modulation to the acidity of MeAPO-31 molecular sieve easily and flexibly through heteroatoms kind and the quantity that changes introducing.Because the synthesis condition of MeAPO-31 is simple and easy to do; Has milder and acidity that can meticulous modulation than SAPO-31; MeAPO-31 has metal active center and acid site when supporting the precious metal preparation dual-function catalyst has higher selectivity to isoparaffin in the isomerization reaction of normal paraffin shortening, can be used for preparing the catalyzer of eco-friendly gasoline alkylate, low-freezing diesel oil and efficient lubricant oil.The preparation method of existing MeAPO-31 molecular sieve is a synthetic under hydrothermal condition, and adopting di-n-propylamine usually is template, with aluminium source, phosphorus source, metal-salt, water and a little HF or HNO
3Mix Deng mineral acid, join in the autoclave, airtight post-heating to 150 ℃～200 ℃, crystallization is 3～5 days under autogenous pressure.This method crystallization time is long; And because use can cause SAPO-5; The di-n-propylamine that nearly ten kinds of molecular sieves such as SAPO-11 and SAPO-41 form is a template; Be prone to stray crystal in the crystallization product, and limited as the value volume and range of product of the atoms metal on the heteroatoms introducing framework of molecular sieve, limited the synthetic and application of MeAPO-31 molecular sieve.
In sum, technical problems such as being prone to stray crystal in long, the product of the method crystallization time of existing preparation MeAPO-31 molecular sieve, introducing heteroatoms kind and limited amount in the skeleton, the acidic site variable range of generation is narrow.
Summary of the invention
Technical problems such as the present invention will solve that the method crystallization time of existing preparation MeAPO-31 molecular sieve is long, be prone to stray crystal in the product, introduce heteroatoms kind and limited amount in the skeleton, the acidic site variable range of generation is narrow, and provide the synthetic heteroatoms of a kind of microwave heating to replace the method for MeAPO-31 (Me is meant heteroatomss such as Mg, Co, Mn, Fe, Cr, Ti, Cu, Zn, V) molecular sieve.
The method of the synthetic MeAPO-31 molecular sieve of microwave heating is carried out according to the following steps among the present invention: one, SPA is added in the entry, stir 5min～10min, add the Di-n-Butyl Amine continued again and stir 10～30min; Add metal-salt and aluminium salt continued again and stir 1h～8h; Obtain gel, the mass ratio of wherein said SPA and water is 1: 2.5～4, and the mass ratio of SPA and Di-n-Butyl Amine is 1: 0.4～1.2; The mass ratio of SPA and metal-salt is 1: 0.04～1.0; Said aluminium salt is aluminum isopropylate or pseudo-boehmite, and the mass ratio of SPA and aluminum isopropylate is 1.2～2, and the mass ratio of SPA and pseudo-boehmite is 0.2～1.2; Two, the gel that step 1 is obtained places reaction kettle; Use microwave as heating source, the power of said microwave is 500W～700W, crystallization 0.5h～3h under 130～190 ℃ condition; Be cooled to room temperature, obtain the MeAPO-31 molecular sieve after centrifuging then, washing, drying, the roasting; Metal-salt described in the step 1 is magnesium salts, cobalt salt, manganese salt, molysite, chromic salts, titanium salt, mantoquita, zinc salt or vanadic salts.
The present invention adopts microwave to heat, and just obtains the pure phase MeAPO-31 molecular sieve of high-crystallinity during crystallization 0.5h under microwave heating condition～3h, does not have MeAPO-5, stray crystals such as MeAPO-11 and MeAPO-41; Crystallization time shortens dramatically, and is merely 1/20～1/40 of traditional hydrothermal method.Can adopt the Di-n-Butyl Amine and the pseudo-boehmite of industrial level respectively is organic formwork agent and aluminium source, and the cost of synthetic MeAPO-31 molecular sieve is reduced significantly.Adopt this patent method can synthesize Me
XO
Y/ P
2O
5Mol ratio in 0.01～0.1 scope, change, have different tart MeAPO-31 molecular sieves, have broad application prospects in fields such as petrochemical complex, fine chemistry industries as eco-friendly an acidic catalyst.
Description of drawings
Fig. 1 is the XRD spectra of the sieve sample MgAPO-31 (A) of embodiment 17 preparations; Fig. 2 is the SEM photo of the sieve sample MgAPO-31 (A) of embodiment 17 preparations; Fig. 3 is the XRD spectra of the sieve sample MgAPO-31 (N) of embodiment 18 preparations; Fig. 4 is the SEM photo of the sieve sample MgAPO-31 (N) of embodiment 18 preparations; Fig. 5 is the XRD spectra of the sieve sample MgAPO-31 (PA) of embodiment 19 preparations; Fig. 6 is the SEM photo of the sieve sample MgAPO-31 (PA) of embodiment 19 preparations; Fig. 7 is the XRD spectra of the sieve sample CoAPO-31 (S) of embodiment 20 preparations; Fig. 8 is the SEM photo of the sieve sample CoAPO-31 (S) of embodiment 20 preparations.Fig. 9 is the XRD spectra of the sieve sample CoAPO-31 (N) of embodiment 21 preparations; Figure 10 is the SEM photo of the sieve sample CoAPO-31 (N) of embodiment 21 preparations.
Embodiment
Embodiment one: the method for the synthetic MeAPO-31 molecular sieve of microwave heating is carried out according to the following steps in this embodiment: one, SPA is added in the entry; Stir 5min～10min; Add the Di-n-Butyl Amine continued again and stir 10～30min, add metal-salt and aluminium salt continued again and stir 1h～8h, obtain gel; The mass ratio of wherein said SPA and water is 1: 2.5～4; The mass ratio of SPA and Di-n-Butyl Amine is 1: 0.4～1.2, and the mass ratio of SPA and metal-salt is 1: 0.04～1.0, and said aluminium salt is aluminum isopropylate or pseudo-boehmite; The mass ratio of SPA and aluminum isopropylate is 1.2～2, and the mass ratio of SPA and pseudo-boehmite is 0.2～1.2; Two, the gel that step 1 is obtained places reaction kettle; Use microwave as heating source, the power of said microwave is 500W～700W, crystallization 0.5h～3h under 130～190 ℃ condition; Be cooled to room temperature, obtain the MeAPO-31 molecular sieve after centrifuging then, washing, drying, the roasting; Metal-salt described in the step 1 is magnesium salts, cobalt salt, manganese salt, molysite, chromic salts, titanium salt, mantoquita, zinc salt or vanadic salts.
Quality percentage composition >=85% of this embodiment SPA.
The organic formwork agent that this embodiment adopts is a Di-n-Butyl Amine; Adopting microwave to heat can make crystallization time shorten dramatically; Crystallization time is merely 1/20～1/40 of traditional hydrothermal method; Crystallization 0.5h～3h just obtains the pure phase MeAPO-31 molecular sieve of high-crystallinity under microwave heating condition, does not have MeAPO-5 in the product, and stray crystals such as MeAPO-11 and MeAPO-41 occur.
Embodiment two: what this embodiment and embodiment one were different is: the said magnesium salts of step 1 is magnesium acetate or magnesium nitrate, and said cobalt salt is rose vitriol, Xiao Suangu or Cobaltous diacetate, and said manganese salt is manganese acetate or manganous sulfate; Said molysite is iron nitrate or ferric sulfate; Said chromic salts is chromium nitrate or chromium acetate, and said titanium salt is titanium chloride or tetrabutyl titanate, and said mantoquita is cupric nitrate, copper sulfate or cupric chloride; Said zinc salt is zinc acetate or zinc sulfate, and said vanadic salts is an ammonium vanadate.Other step is identical with embodiment one with parameter.
Embodiment three: what this embodiment was different with embodiment one or two is: the described stirring velocity of step 1 is 200r/min.Other step is identical with embodiment one or two with parameter.
Embodiment four: what this embodiment was different with one of embodiment one to three is: the mass ratio of described SPA of step 1 and water is 1: 2.7～3.8.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what this embodiment was different with one of embodiment one to four is: the mass ratio of described SPA of step 1 and Di-n-Butyl Amine is 1: 0.7～0.9.Other step is identical with one of embodiment one to four with parameter.
Embodiment six: what this embodiment was different with one of embodiment one to five is: the mass ratio of described SPA of step 1 and metal-salt is 0.06～0.8.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: the mass ratio of described SPA of step 1 and aluminum isopropylate is 1.6～1.9.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: what this embodiment was different with one of embodiment one to seven is: the mass ratio of described SPA of step 1 and pseudo-boehmite is 0.4～1.0.Other step is identical with one of embodiment one to seven with parameter.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is: the described crystallization temperature of step 2 is 140～180 ℃, and crystallization time is 1h～2.5h.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: what this embodiment was different with one of embodiment one to eight is: the described crystallization temperature of step 2 is 175 ℃, and crystallization time is 2h.Other step is identical with one of embodiment one to eight with parameter.
Embodiment 11: what this embodiment was different with one of embodiment one to ten is: drying temperature described in the step 2 is 100 ℃～120 ℃, and be 12h～24h time of drying.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 12: what this embodiment was different with one of embodiment one to ten is: drying temperature described in the step 2 is 110 ℃, and be 15h time of drying.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 13: what this embodiment was different with one of embodiment one to 12 is: the maturing temperature described in the step 2 is 500～600 ℃, and roasting time is 2h～6h.Other step is identical with one of embodiment one to 12 with parameter.
Embodiment 14: what this embodiment was different with one of embodiment one to 12 is: the maturing temperature described in the step 2 is 550 ℃, and roasting time is 4h.Other step is identical with one of embodiment one to 12 with parameter.
Embodiment 15: what this embodiment was different with one of embodiment one to 14 is: the power of the said microwave of step 2 is 550W～650W.Other step is identical with one of embodiment one to 14 with parameter.
Embodiment 16: what this embodiment was different with one of embodiment one to 14 is: the power of the said microwave of step 2 is 600W.Other step is identical with one of embodiment one to 14 with parameter.
Embodiment 17: the method for the synthetic MgAPO-31 molecular sieve of microwave heating is carried out according to the following steps in this embodiment: one, SPA (mass concentration is 85%) is added in the entry; Stir 10min; Add the Di-n-Butyl Amine continued again and stir 15min, add magnesium acetate and aluminum isopropylate continued again and stir 100min, obtain gel; The mass ratio of wherein said SPA and water is 1: 3; The mass ratio of SPA and Di-n-Butyl Amine is 1: 0.8, and the mass ratio of SPA and aluminum isopropylate is 1: 1.78, and the mass ratio of SPA and magnesium acetate is 1: 0.047; Two, the gel that step 1 is obtained places reaction kettle, uses microwave as heating source, and the power of said microwave is 600W; Crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging; Extremely neutral with deionized water wash; Dry 15h under 110 ℃ obtains the MgAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as MgAPO-31 (A).
XRD figure spectrum and the SEM photo of the sieve sample MgAPO-31 (A) of this embodiment preparation are as depicted in figs. 1 and 2 respectively.Visible from Fig. 1, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework have obtained the pure phase MgAPO-31 molecular sieve of high-crystallinity.Visible by Fig. 2, this embodiment synthetic MgAPO-31 molecular sieve crystal is that diameter is the nanometer rod of 50nm, exists with the pencil aggregate form.
Embodiment 18: the method for the synthetic MgAPO-31 molecular sieve of a kind of microwave heating of this embodiment is carried out according to the following steps: one, SPA (mass concentration is 85%) is added in the entry; Stir 10min; Add the Di-n-Butyl Amine continued again and stir 15min, add magnesium nitrate and aluminum isopropylate continued again and stir 100min, obtain gel; The mass ratio of wherein said SPA and water is 1: 3; The mass ratio of SPA and Di-n-Butyl Amine is 1: 0.8, and the mass ratio of SPA and aluminum isopropylate is 1: 1.78, and the mass ratio of SPA and magnesium nitrate is 1: 0.053; Two, the gel that step 1 is obtained places reaction kettle, uses microwave as heating source, and the power of said microwave is 600W; Crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging; Extremely neutral with deionized water wash; Dry 15h under 110 ℃ obtains the MgAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as MgAPO-31 (N).
The XRD figure spectrum of the sieve sample MgAPO-31 (N) of this embodiment preparation is as shown in Figure 3, and the SEM photo is as shown in Figure 4.As can beappreciated from fig. 3, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal; Can know that by Fig. 4 the MgAPO-31 crystal grain that this embodiment makes exists with cage shape aggregate form.
Embodiment 19: the method for the synthetic MgAPO-31 molecular sieve of a kind of microwave heating of this embodiment is carried out according to the following steps: one, SPA (mass concentration is 85%) is added in the entry; Stir 10min; Add the Di-n-Butyl Amine continued again and stir 15min, add magnesium acetate and pseudo-boehmite continued again and stir 240min, obtain gel; The mass ratio of wherein said SPA and water is 1: 3; The mass ratio of SPA and Di-n-Butyl Amine is 1: 0.8, and the mass ratio of SPA and pseudo-boehmite is 1: 0.6, and the mass ratio of SPA and magnesium acetate is 1: 0.047; Two, the gel that step 1 is obtained places reaction kettle, uses microwave as heating source, and the power of said microwave is 600W; Crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging; Extremely neutral with deionized water wash; Dry 15h under 110 ℃ obtains the MgAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as MgAPO-31 (PA).
The XRD figure spectrum of the sieve sample MgAPO-31 (PA) of this embodiment preparation and SEM photo are respectively like Fig. 5 and shown in Figure 6.As can beappreciated from fig. 5, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal.Can know that by Fig. 6 the MgAPO-31 crystal grain that this embodiment makes is capsule shape.
Embodiment 20: the method for the synthetic CoAPO-31 molecular sieve of a kind of microwave heating of this embodiment is carried out according to the following steps: one, SPA (mass concentration is 85%) is added in the entry; Stir 10min; Add the Di-n-Butyl Amine continued again and stir 15min, add rose vitriol and aluminum isopropylate stone continued again and stir 100min, obtain gel; The mass ratio of wherein said SPA and water is 1: 3; The mass ratio of SPA and Di-n-Butyl Amine is 1: 0.8, and the mass ratio of SPA and aluminum isopropylate is 1: 1.78, and the mass ratio of SPA and rose vitriol is 1: 0.061; Two, the gel that step 1 is obtained places reaction kettle, uses microwave as heating source, and the power of said microwave is 600W; Crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging; Extremely neutral with deionized water wash; Dry 15h under 110 ℃ obtains the CoAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as CoAPO-31 (S).
The XRD figure spectrum of the sieve sample CoAPO-31 (S) of this embodiment preparation is as shown in Figure 7, and the SEM photo is as shown in Figure 8, as can beappreciated from fig. 7; At 2 θ is 8.5 °; 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal; Can know that by Fig. 8 the CoAPO-31 molecular sieve crystal that this embodiment makes is that diameter is the nanometer rod of 50nm, the crystal that exists with the pencil aggregate form.
Embodiment 21: the method for the synthetic CoAPO-31 molecular sieve of a kind of microwave heating of this embodiment is carried out according to the following steps: one, SPA (mass concentration is 85%) is added in the entry; Stir 10min; Add the Di-n-Butyl Amine continued again and stir 15min, add Xiao Suangu and aluminum isopropylate stone continued again and stir 100min, obtain gel; The mass ratio of wherein said SPA and water is 1: 3; The mass ratio of SPA and Di-n-Butyl Amine is 1: 0.8, and the mass ratio of SPA and aluminum isopropylate is 1: 1.78, and the mass ratio of SPA and Xiao Suangu is 1: 127; Two, the gel that step 1 is obtained places reaction kettle, uses microwave as heating source, and the power of said microwave is 600W; Crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging; Extremely neutral with deionized water wash; Dry 15h under 110 ℃ obtains CoAPO-31 (N) molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as CoAPO-31 (N).
The XRD figure spectrum of the sieve sample CoAPO-31 (N) of this embodiment preparation is as shown in Figure 9, and the SEM photo is shown in figure 10.As can beappreciated from fig. 9, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal; Can know that by Figure 10 the CoAPO-31 molecular sieve crystal diameter that this embodiment makes is the nanometer rod of 50nm, exists with the pencil aggregate form.Under microwave heating condition, just obtain the pure phase CoAPO-31 molecular sieve of high-crystallinity during crystallization 2h, crystallization time is merely 1/20 of traditional hydrothermal method, and crystallization time shortens dramatically; The organic formwork agent that adopts is the Di-n-Butyl Amine of industrial level, and the cost of synthetic CoAPO-31 molecular sieve is further reduced.
Claims (7)
1. the method that heteroatoms replaces the MeAPO-31 molecular sieve is synthesized in a microwave heating; The method that it is characterized in that the synthetic MeAPO-31 molecular sieve of microwave heating is carried out according to the following steps: one, SPA is added in the entry; Stir 5min～10min, add the Di-n-Butyl Amine continued again and stir 10～30min; Add metal-salt and aluminum isopropylate again, perhaps add metal-salt and pseudo-boehmite again, continue to stir 1h～8h; Obtain gel; The mass ratio of wherein said SPA and water is 1: 2.5～4, and the mass ratio of SPA and Di-n-Butyl Amine is 1: 0.4～1.2, and the mass ratio of SPA and metal-salt is 1: 0.04～1.0; The mass ratio of SPA and aluminum isopropylate is 1.2～2, and the mass ratio of SPA and pseudo-boehmite is 0.2～1.2; Two, the gel that step 1 is obtained places reaction kettle; Use microwave as heating source, the power of said microwave is 500W～700W, crystallization 0.5h～3h under 130～190 ℃ condition; Be cooled to room temperature, obtain the MeAPO-31 molecular sieve after centrifuging then, washing, drying, the roasting; Metal-salt described in the step 1 is magnesium salts, cobalt salt, manganese salt, molysite, chromic salts, titanium salt, mantoquita, zinc salt or vanadic salts; Drying temperature described in the step 2 is 100 ℃～120 ℃, and be 12h～24h time of drying; Maturing temperature described in the step 2 is 500～600 ℃, and roasting time is 2h～6h.
2. the synthetic heteroatoms of a kind of microwave heating according to claim 1 replaces the method for MeAPO-31 molecular sieve; It is characterized in that the said magnesium salts of step 1 is magnesium acetate or magnesium nitrate, said cobalt salt is rose vitriol, Xiao Suangu or Cobaltous diacetate, and said manganese salt is manganese acetate or manganous sulfate; Said molysite is iron nitrate or ferric sulfate; Said chromic salts is chromium nitrate or chromium acetate, and said titanium salt is a titanium chloride, and said mantoquita is cupric nitrate, copper sulfate or cupric chloride; Said zinc salt is zinc acetate, zinc nitrate or zinc sulfate, and said vanadic salts is an ammonium vanadate.
3. the synthetic heteroatoms of a kind of microwave heating according to claim 2 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described SPA of step 1 and water is 1: 2.7～3.8.
4. the synthetic heteroatoms of a kind of microwave heating according to claim 3 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described SPA of step 1 and Di-n-Butyl Amine is 1: 0.7～0.9.
5. the synthetic heteroatoms of a kind of microwave heating according to claim 4 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described SPA of step 1 and aluminum isopropylate is 1.6～1.9.
6. the synthetic heteroatoms of a kind of microwave heating according to claim 4 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described SPA of step 1 and pseudo-boehmite is 0.4～1.0.
7. according to the method for claim 5 or the synthetic heteroatoms replacement of 6 described a kind of microwave heatings MeAPO-31 molecular sieve, it is characterized in that the described crystallization temperature of step 2 is 140～180 ℃, crystallization time is 1h～2.5h.
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| CN105776238A (en) * | 2014-12-17 | 2016-07-20 | 中国科学院大连化学物理研究所 | Ionothermal synthesis method of LAU type metal aluminum phosphate molecular sieve |
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| CN101679054A (en) * | 2007-03-13 | 2010-03-24 | 道达尔石油化学产品研究弗吕公司 | Method for preparing metalloaluminophosphate (MEAPO) molecular sieve |
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| Natasa Novak Tusar et al..Framework cobalt and manganese in MeAPO-31 (Me = Co，Mn) molecular sieves.《Microporous and Mesoporous Materials》.2002,第55卷203-216. * |
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