CN108855207B - Heteroatom Beta zeolite catalyst containing alkali metal and preparation method and application thereof - Google Patents
Heteroatom Beta zeolite catalyst containing alkali metal and preparation method and application thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention belongs to the technical field of catalytic materials, and particularly relates to an alkali metal-containing heteroatom Beta zeolite catalyst, and a preparation method and application thereof. The method of the invention prepares the heteroatom-containing Beta zeolite by utilizing the defect sites of the Beta zeolite, without using concentrated acid for dealumination treatment and through three steps of liquid phase reflux, roasting and alkali treatment. The zeolite catalyst can be used for hydrogen transfer reduction reaction and shows good catalytic activity and stability. The method provided by the invention has the advantages of simple operation, mild conditions, wide heteroatom application range, no generation of a large amount of acidic wastewater, environmental friendliness and considerable application prospect.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a heteroatom Beta zeolite catalyst containing alkali metal, a preparation method thereof and application thereof in hydrogen transfer reaction.
Background
The zeolite material has become an important catalytic material due to the regular pore channel structure, adjustable acidity and alkalinity and good thermal stability, and is widely applied to the fields of petrochemical industry and fine chemical industry. The heteroatom zeolites, such as TS-1, Ti-MOR, Sn-Beta, Zr-Beta, Sn-MCM-41 and Zr-SBA-15, show superior catalytic performance in selective oxidation, ketooximation, hydrogen transfer, saccharide isomerization, aldol condensation, etherification and ester exchange reactions (J. Catal., 2014, 320, 160-169; Chem. Rev. Soc. 2016, 45, 584-611). Among them, the hydrogen transfer reaction plays an important role in the catalytic conversion of biomass-derived platform compounds, such as glyceraldehyde, furfural, 5-hydroxymethylfurfural, levulinic acid, glycerol and the like ((ACS Catal. 2016, 6, 1420-1436). For example, zeolites such as Sn-Beta and Zr-Beta exhibit good catalytic effects in the hydrogen transfer reduction reaction of furfural and 5-hydroxymethylfurfural.
Taking Sn-Beta and Zr-Beta zeolites as examples, the preparation method of the heteroatom zeolite is mainly divided into two methods (hydrothermal synthesis method and post-modification synthesis method) ((Chem. Rev. Soc. 2015, 44, 7025-7043; Angew. Chem. Int. Ed.2012, 51, 11736 –11739; J. Phys. Chem. C2011, 115, 3663-3670). The hydrothermal synthesis method is to mix silicon species, heteroatom species, template agent and mineralizer to prepare gel, then to carry out hydrothermal crystallization and synthesize heteroatom zeolite. The hydrothermal synthesis method has disadvantages such as the use of a fluorine-containing mineralizer (hydrofluoric acid or ammonium fluoride), a long hydrothermal crystallization time (more than 40 days), a small amount of heteroatom incorporation, a large crystal grain size of the obtained zeolite, a complicated synthesis step, and poor parallelism. The post-modification synthesis method is that on the basis of zeolite with a crystal phase structure, aluminum in the zeolite is removed by acid to form defect sites, and then hetero atoms are introduced into a zeolite framework by means of gas-solid reaction, liquid-solid reaction, solid-phase grinding and the like (Chem. Soc. Rev., 2015, 44, 7025—7043, CN106694027A, CN104310425B, CN104860329B, CN103252252B, CN103920527B). A disadvantage of the post-modification synthesis is that large amounts of concentrated nitric acid are used for the zeoliteDealuminizing, serious corrosion and pollution. On one hand, partial collapse of the zeolite framework is caused, and the hydrothermal stability of the zeolite is reduced; on the other hand, the dealuminized zeolite needs to be washed, and a large amount of acidic waste water is generated, which is not beneficial to the industrial application of the method. However, zeolite Beta is a intergrowth of three polymorphs and contains a large number of stacking defect sites: (CrystEngComm, 2016, 18, 1782-1789). Therefore, the defect sites contained in the Beta zeolite can be utilized for introducing the heteroatoms, and a more green method is provided for preparing the heteroatom zeolite.
Disclosure of Invention
The invention aims to provide an alkali metal-containing heteroatom Beta zeolite catalyst, a preparation method thereof and application thereof in hydrogen transfer reaction.
The invention provides a preparation method of an alkali metal-containing heteroatom Beta zeolite catalyst, which is a post-modification method, takes industrial Beta zeolite as a raw material, does not need to use concentrated acid for dealumination treatment, and is prepared by a three-step method of liquid phase reflux, roasting and alkali treatment, and the specific steps are as follows:
(1) dissolving heteroatom transition metal inorganic salt in an alcohol solvent, then adding industrial Beta zeolite into the alcohol solvent, and placing the alcohol solvent in an oil bath or a microwave heater for refluxing at the reflux temperature of 78-120 ℃ for 10min-5 h;
(2) and (3) carrying out vacuum filtration under reduced pressure to obtain a filter cake, drying the filter cake in a forced air drying oven for 12-24 hours at the temperature of 60-120 ℃, and then placing the filter cake in a muffle furnace for roasting: heating to 250 ℃ at the heating rate of 1-5 ℃/min, keeping the temperature for 4-8h, heating to 650 ℃ at the heating rate of 1-5 ℃/min, keeping the temperature for 4-8h, and obtaining the heteroatom Beta zeolite, wherein the label is M-Beta, and M represents the heteroatom transition metal species in the step (1);
(3) placing the heteroatom Beta zeolite in an alcohol solution of an alkali metal compound, stirring for 5-30min at room temperature, centrifuging, washing for several times by using a corresponding alcohol solvent, and drying at 60-100 ℃ for 12-24h to obtain the heteroatom Beta zeolite containing alkali metal, wherein the label is X-N-M-Beta, and X represents the molar concentration of the alkali metal compound solution; n represents the kind of alkali metal ion, Li, Na, K, Rb or Cs, and M represents the kind of heteroatom transition metal in the step (1).
In the step (1), the heteroatom transition metal inorganic salt is one of nitrates or chlorides of manganese, cobalt, nickel, copper, zinc, zirconium, tin, hafnium, lanthanum and cerium; the introduction amount of the heteroatom transition metal is 0.5-5% of the mass of the industrial Beta zeolite; the alcohol is methanol, ethanol or isopropanol, and the feeding ratio of the industrial Beta zeolite to the alcohol solution is 1: 15-1: 100 (g/mL).
In the step (3), the alkali metal compound is one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium carbonate or potassium carbonate; the alcohol is one of methanol, ethanol or isopropanol; the molar concentration of the alkali metal compound solution is 5-100mmol/L, and the feeding ratio of the heteroatom Beta zeolite to the alkali metal compound solution is 1: 15-1: 60 (g/mL).
In the invention, the heteroatom Beta zeolite catalyst containing alkali metals, which is prepared by the method, is applied to hydrogen transfer reaction, and shows good catalytic activity and stability:
adding the synthesized zeolite catalyst into an isopropanol solution of furfural for hydrogen transfer reduction reaction of furfural, and analyzing the product by gas phase; the molar ratio of the furfural to the isopropanol is 1: 5-1: 100, the reaction temperature is 80-140 ℃, and the reaction time is 10min-5 h. Experiments show that the heteroatom Beta zeolite containing alkali metals has higher furfural conversion rate and product selectivity.
Compared with the prior art, the preparation method of the heteroatom-containing Beta zeolite catalyst provided by the invention has the advantages of simple and easy operation process, mild conditions, wide heteroatom application range and environmental friendliness, and the obtained zeolite catalyst shows good catalytic activity and stability in hydrogen transfer reaction and has a considerable application prospect.
Drawings
FIG. 1 is an XRD spectrum of a Zr-Beta zeolite catalyst prepared in example 1.
FIG. 2 is a UV-vis spectrum of the Zr-Beta zeolite catalyst prepared in example 1.
FIG. 3 is an SEM image of the Zr-Beta zeolite catalyst prepared in example 1.
Detailed Description
The technical solution of the present invention is described below with reference to specific examples, but the scope of the present invention is not limited thereto.
The industrial Beta zeolite is a sample sold in the market, is purchased from Shanghai Xinnian petrochemical additive company Limited, and has a silicon-aluminum molar ratio (Si/Al) of 14.2.
Example 1
The procedure for synthesizing the alkali metal-containing Zr-Beta zeolite catalyst and the evaluation of hydrogen transfer performance provided in this example are as follows:
(1) 0.0716 g Zr (NO)3)4•5H2Dissolving O in 100 mL of absolute ethyl alcohol, and stirring at room temperature for 30 min; then adding 1.0 g of industrial Beta zeolite, and placing the mixture in an oil bath heater to reflux for 5 hours under normal pressure;
(2) and (4) carrying out vacuum filtration to obtain a filter cake, drying at 60 ℃ for 12 h, and roasting to obtain Zr-Beta. The roasting condition is that the temperature is respectively kept constant at 200 ℃ and 550 ℃ for 6 h, and the heating rate is 1 ℃/min;
(3) the alkali metal compound solution is 6.25, 12.5, 25, 50, 100mmol/L of lithium hydroxide, sodium hydroxide or potassium hydroxide methanol solution; putting 0.5 g of Zr-Beta zeolite into 15 mL of the alkali metal compound solution with different concentrations, stirring for 10min at room temperature, washing for 4 times by using methanol, and drying for 12 h at 65 ℃ to obtain an alkali metal-containing Zr-Beta zeolite catalyst which is marked as X-N-Zr-Beta; wherein X = 6.25, 12.5, 25, 50, 100, N is Li, Na or K; the XRD, UV-vis spectra and SEM pictures of the 25-Na-Zr-Beta zeolite are respectively shown in figure 1, figure 2 and figure 3;
(4) hydrogen transfer reduction reaction of furfural: dissolving 0.48 g of furfural in 3.0 g of isopropanol, adding 0.1 g of catalyst, placing in a microwave reactor, and reacting at 120 ℃ for 3 h. The products of this reaction are furfuryl alcohol and the etherification product of furfuryl alcohol with isopropanol (2-isopropoxymethylfuran). The product was analyzed by Shimadzu 2010 plus gas chromatograph on a FFAP capillary column and FID detector. And calculating the conversion rate of the furfural and the selectivity of the product by an internal standard method through a chromatographic workstation. Wherein, the evaluation result of the catalytic performance and the element composition of the X-Li-Zr-Beta zeolite are shown in the table 1.
From the evaluation results of the hydrogen transfer catalytic performance, it can be seen that the furfural conversion rate shows a trend of increasing first and then decreasing with the increase of the lithium hydroxide concentration, and an optimal point exists. The 25-Li-Zr-Beta zeolite shows the highest furfural conversion rate, which is up to 96.2%. From the point of view of product selectivity, the product gradually transits from 2-isopropoxymethylfuran to furfuryl alcohol as the concentration of lithium hydroxide increases. The furfuryl alcohol product selectivity of the 25-Li-Zr-Beta zeolite was 100.0%. Meanwhile, as can be seen from the elemental compositions in table 1, the silicon-aluminum ratio (Si/Al) and the silicon-zirconium ratio (Si/Zr) of different Zr-Beta zeolite samples have no significant change, indicating that highly active alkali-containing Zr-Beta zeolite can be obtained without dealumination. The content of Li element (Li/Al) increased with the increase of the concentration of lithium hydroxide, and the lithium-aluminum ratio (Li/Al) of the 25-Li-Zr-Beta zeolite was 0.74. The treatment of lithium hydroxide methanol solution can modulate the hydrogen transfer reaction catalytic activity and product distribution of the Zr-Beta zeolite sample.
TABLE 1 evaluation results of X-Li-Zr-Beta Zeolite catalytic performances and elemental compositions
The results of the evaluation of the catalytic performance of the X-Na-Zr-Beta zeolite and the elemental composition are shown in Table 2. As can be seen from Table 2, the catalytic activity and elemental composition of the Zr-Beta zeolite treated with NaOH in methanol also exhibited similar laws. When the 25-Na-Zr-Beta zeolite is used as a catalyst, the conversion rate of the furfural is up to 96.1 percent, and the selectivity of the furfuryl alcohol is 100.0 percent. At this time, the sodium-aluminum ratio (Na/Al) of the 25-Na-Zr-Beta zeolite was 0.89.
TABLE 2 evaluation results of X-Na-Zr-Beta Zeolite catalytic performances and elemental compositions
The results of the evaluation of the catalytic performance of X-K-Zr-Beta zeolite and the elemental composition are shown in Table 3. As can be seen from Table 3, the catalytic activity and elemental composition of the potassium hydroxide methanol solution treated Zr-Beta zeolite also exhibited similar laws. When the 25-K-Zr-Beta zeolite is used as a catalyst, the conversion rate of the furfural is up to 91.9%, and the selectivity of the furfuryl alcohol is 100.0%. At this time, the potassium-aluminum ratio (K/Al) of the 25-K-Zr-Beta zeolite was 0.84.
When the reaction time is 0.5 h, the apparent difference in catalytic performance of Zr-Beta zeolite treated with different alkali metal hydroxide methanol solutions at the same concentration can be seen from Table 4. Wherein, the corresponding catalytic activity sequence is Li > Na > K.
TABLE 3 evaluation results of X-K-Zr-Beta Zeolite catalytic performances and elemental compositions
TABLE 425 comparison of catalytic Performance of the N-Zr-Beta zeolites
Example 2
An experiment was carried out in a similar manner to example 1 except that methanol in step (3) of example 1 was changed to ethanol, and the obtained Zr-Beta zeolite had similar catalytic activity and regularity.
Example 3
An experiment was carried out in a similar manner to example 1 except that methanol in step (3) of example 1 was changed to isopropanol, and the obtained Zr-Beta zeolite had similar catalytic activity and regularity.
Example 4
An experiment was conducted in a similar manner to example 1 except that the anhydrous ethanol in step (1) of example 1 was changed to isopropanol to obtain Zr-Beta zeolite having similar catalytic activity and regularity.
Example 5
An experiment was carried out in a similar manner to example 1 except that the calcination conditions in step (1) of example 1 were changed to a constant temperature of 150 ℃ and 600 ℃ for 4 hours, respectively, and the temperature increase rate was 2 ℃/min, and the obtained Zr-Beta zeolite had similar catalytic activity and regularity.
Example 6
An experiment was conducted in a similar manner to example 1 except that Zr (NO) in step (1) of example 1 was used3)4•5H2Changing O into ZrCl4The obtained Zr-Beta zeolite has similar catalytic activity and law.
Example 7
0.0716 g Zr (NO)3)4•5H2Dissolving O in 15 mL of absolute ethyl alcohol, and stirring at room temperature for 30 min; then 1.0 g of industrial Beta zeolite was added and placed in a microwave heater to reflux at 120 ℃ for 10min, the other conditions were the same as in example 1, and after the obtained 25-Na-Zr-Beta zeolite reacted at 120 ℃ for 3 h, the furfural conversion was 96.0% and the furfuryl alcohol selectivity was 100.0%.
Example 8
An experiment was carried out in a similar manner to example 1 except that the alkali metal compound solution in step (3) of example 1 was changed to a 25 mmol/L rubidium carbonate ethanol solution to prepare zeolite 25-Rb-Zr-Beta. After reacting for 3 hours at 120 ℃, the 25-Rb-Zr-Beta zeolite shows that the conversion rate of furfural is 85.0 percent, and the selectivity of furfuryl alcohol is 100.0 percent.
Example 9
An experiment was carried out in a similar manner to example 1 except that the alkali metal compound solution in step (3) of example 1 was changed to a 25 mmol/L cesium carbonate ethanol solution to prepare zeolite 25-Cs-Zr-Beta. After reacting for 3 hours at 120 ℃, the 25-Cs-Zr-Beta zeolite shows that the conversion rate of furfural is 80.0 percent, and the selectivity of furfuryl alcohol is 100.0 percent.
Example 10
This example examined the recycling effect of the 25-Na-Zr-Beta zeolite prepared in example 1 in furfural hydrogen transfer reduction reaction. After the catalyst is circulated for one time, the catalyst is centrifugally separated, and then fresh raw materials are added for the next reaction. The reaction conditions were the same as in example 1, the reaction time was 3 hours, and the catalyst recycling results are shown in Table 5.
TABLE 525 effect of recycling of Na-Zr-Beta Zeolite
As can be seen from Table 5, the furfural conversion rate remained substantially unchanged after the 25-Na-Zr-Beta zeolite was recycled for 5 times, indicating that the 25-Na-Zr-Beta zeolite has a relatively stable catalytic activity.
Example 11
An experiment was carried out in a similar manner to example 1 except that Zr (NO) in example 1 was used3)4•5H2The input amount of O is doubled, and after the obtained 25-Na-Zr-Beta zeolite reacts for 0.5 h at the temperature of 120 ℃, the conversion rate of furfural is 80.0 percent, and the selectivity of furfuryl alcohol is 100.0 percent.
Example 12
This example expands the applicability of the heteroatom zeolite Beta and experiments were performed in a similar manner to example 1, except that 0.0716 g Zr (NO) was added3)4•5H2O is changed into nitrate of manganese, cobalt, nickel, copper, zinc, tin, lanthanum and cerium with the same heteroatom weight, and the obtained 25-Na-M-Beta zeolite has certain catalytic activity in the hydrogen transfer reduction reaction of furfural. The results of the evaluation of the catalytic performance with a reaction time of 3 hours are shown in Table 6.
As can be seen from Table 6, the synthesized heteroatom-containing Beta zeolite has certain catalytic activity in the hydrogen transfer reduction reaction of furfural, which indicates that the preparation method provided by the invention has certain universality.
TABLE 625-Na-M-Beta Zeolite catalytic Performance evaluation results
The invention utilizes the defect sites of the Beta zeolite, does not need to use concentrated acid for dealumination treatment, and synthesizes the heteroatom Beta zeolite containing alkali metal by three-step methods of liquid phase reflux, roasting and alkali treatment. And the prepared heteroatom Beta zeolite containing alkali metals shows good catalytic activity and stability in hydrogen transfer reduction reaction. The method provided by the invention is simple to operate, mild in condition, wide in heteroatom application range, environment-friendly and quite promising in application prospect.
Claims (4)
1. The preparation method of the heteroatom Beta zeolite catalyst containing alkali metal for hydrogen transfer reaction is a post-modification method and is characterized by comprising the following specific steps:
(1) dissolving heteroatom transition metal inorganic salt in an alcohol solvent, then adding industrial Beta zeolite into the alcohol solvent, and placing the alcohol solvent in an oil bath or a microwave heater for refluxing at the reflux temperature of 78-120 ℃ for 10min-5 h;
(2) carrying out vacuum filtration to obtain a filter cake, drying the filter cake in a blast drying oven for 12-24h at the temperature of 60-120 ℃, then placing the filter cake in a muffle furnace for roasting at the heating rate of 1-5 ℃/min, and respectively keeping the temperature at 250 ℃ of 150-;
(3) placing the heteroatom Beta zeolite in an alcohol solution of an alkali metal compound, stirring for 5-30min at room temperature, centrifuging, washing for several times by using a corresponding alcohol solvent, and drying at 60-100 ℃ for 12-24h to obtain the heteroatom Beta zeolite containing the alkali metal, wherein the label is X-N-M-Beta, and X represents the molar concentration of the alcohol solution of the alkali metal compound; n represents the kind of alkali metal ion, Li, Na, K, Rb or Cs, M represents the kind of heteroatom transition metal in the step (1);
the alkali metal compound in the step (3) is one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium carbonate and cesium carbonate, and the alcohol in the step (3) is one of methanol, ethanol or isopropanol; the molar concentration of the alcoholic solution of the alkali metal compound is 5-100mmol/L, and the feeding ratio of the heteroatom Beta zeolite to the alcoholic solution of the alkali metal compound is 1: 15-1: 60 (g/mL).
2. The method according to claim 1, wherein the inorganic salt of a hetero-atom transition metal in the step (1) is one of nitrate or chloride salts of manganese, cobalt, nickel, copper, zinc, zirconium, hafnium, lanthanum and cerium; the introduction amount of the heteroatom transition metal in the step (1) is 0.5-5% of the mass of the industrial Beta zeolite; the alcohol in the step (1) is one of methanol, ethanol or isopropanol, and the feeding ratio of the industrial Beta zeolite to the alcohol solution in the step (1) is 1: 15-1: 100 (g/mL).
3. An alkali metal containing zeolite Beta zeolite catalyst prepared according to the method of any one of claims 1 to 2.
4. Use of the alkali metal-containing heteroatom zeolite Beta catalyst of claim 3 in the hydrogen transfer reduction of furfural.
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| A Scalable Upgrading of Concentrated Furfural in Ethanol: Combining Meerwein–Ponndorf–Verley Reduction with in Situ Cross Aldol Condensation;Li Gang et al.;《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》;20180129;第6卷(第3期);第4316页 摘要、supporting information第1.2节 * |
| Activation of Carbonyl-Containing Molecules with Solid Lewis Acids in Aqueous Media;Roman-Leshkov Yuriy et al.;《ACS CATALYSIS》;20110928;第1卷(第11期);第1568页第1568页第1.3节 * |
| Post-synthesized zirconium-containing Beta zeolite in Meerwein–Ponndorf–Verley reduction: Pros and cons;Wang Jie et al.;《APPLIED CATALYSIS A-GENERAL》;20150110;第493卷;第115页左栏第3段、右栏第1段 * |
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