CN101279284B - Catalyst for preparing ethylene propylene from catalytic pyrolysis - Google Patents
Catalyst for preparing ethylene propylene from catalytic pyrolysis Download PDFInfo
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Abstract
The present invention relates to a catalyst used for preparing ethylene and propylene by catalytic pyrolysis which mainly solves the problems of high reaction temperature and low ethylene and propylene yield of existing catalyst to prepare ethylene and propylene by catalytic pyrolysis. The present invention better solves the problems by adopting the technical proposal of composing a solidsuper acid by selecting at least one from the symbiosis molecular sieves of ZSM-5 and mordenite zeolites, ZSM-5 and Beta zeolites or ZSM-5 and Y zeolites as well as the groups of the VIB group and the IVB group in the periodic table of elements loaded on the molecular sieve. The present invention can be used for the industrial production of ethylene and propyleneby catalytic pyrolysis.
Description
Technical field
The present invention relates to a kind of catalyst of preparing ethylene propylene from catalytic pyrolysis.
Background technology
Ethylene, propylene industry has critical role as the tap of petrochemical industry in the national economic development.Along with the development of society, the market demand of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and downstream product thereof increases year by year, and the home products occupation rate of market is less than half.More than 100,000,000 ton of ethene is produced in the whole world per year at present, is raw material with naphtha (or ethane) mainly, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of total output.But steam cracking needs high reaction temperature, and energy consumption is big, needs expensive high-temperature alloy steel material, and the operation cycle is short, and the boiler tube life-span is low, discharge great amount of carbon dioxide, and the ethylene, propylene yield is lower, has restricted further developing of ethylene industry.
Catalytic pyrolysis also is one of important method of producing ethylene, propylene.It is under the condition that catalyst exists, and petroleum hydrocarbon is carried out the process that catalytic pyrolysis is produced low-carbon alkene.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of equivalent steam cracking reactions, and therefore than steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; CO2 emission also can reduce, and can adjust the product mix flexibly.Compare with steam cracking technology, this new technology can also increase the total recovery of ethene and propylene, produces the used feed naphtha of equal number ethene and can reduce, and production cost of ethylene reduces significantly.Therefore, the preparing ethylene propylene from catalytic pyrolysis technology is as realizing industrialization, is that the petrochemical industry of raw material brings huge economic benefit with giving ethylene, propylene.
The ZSM-5 molecular sieve is applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and heat endurance preferably.
U.S. Pat P6211104 and domestic patent CN1504540A adopt a kind of 10～70 weight % clays that contain, 5～85 weight % inorganic oxides, 1～50 weight % molecular sieve is formed catalyst, various raw materials to traditional steam heat cracking, the activity, the especially ethene that well are converted into light olefin have been demonstrated.With molecular sieve be by 0～25 weight %Y zeolite of high silica alumina ratio or have the ZSM molecular sieve of MFI structure, form by phosphorus/Al, Mg or Ca dipping, but the ethylene, propylene selectivity of catalyst and yield are not high.
Japan Asahi Chemical Industry (patent CN1274342A) has announced that a kind of high silica alumina ratio, the molecular sieve of aperture between 0.5～0.65 nanometer are catalyst, be the feedstock production ethylene, propylene with the light hydrocarbons that contains alkene, but the ethylene, propylene yield is lower.
Exxon Mobil (00816642.0) announces that a kind of aperture of a kind of usefulness contains the hydrocarbon raw material of naphtha less than the zeolite treatment of 0.7 nanometer, produces ethylene, propylene between 550～600 ℃, and conversion of raw material is lower.Mobil Oil Corporation (CN1413244A) has announced that a kind of mesopore phosphate material with modification is that catalyst and elementary catalytic pyrolysis material combine, the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, but the serviceability temperature of catalyst, conversion of raw material and product yield are all lower.
Be in the catalytic cracking reaction of raw material with the naphtha, for make in the naphtha contained just, the isoparaffin cracking generates alkene, and higher energy need be provided.Therefore to select acid strength and the bigger catalysis material of sour density for use.Solid super-strong acid is because acidity is stronger, and preparation is simple, pollutes lessly, and the selectivity height can use in higher scope, has been subjected to learning this extensive concern both at home and abroad.
Patent WO13869 has reported with two-step method and has prepared Cs
2.5H
0.5PW
12O
40/ SiO
2Catalyst is earlier with carrier impregnation CsCO
3, after roasting, flood H again
3PW
12O
40, the catalyst activity component of Zhi Deing becomes elliposoidal to distribute at carrier surface like this, has good catalytic activity.But the carrier specific area is less, and the catalyst granules diameter is less, and bed resistance is too big in fixed bed reactors, is difficult to operation.
(" Journal of Molecular Catalysis ", 2001,15 (3): such as Ji Shan 228～230) with porous, compound with regular structure and high-specific surface area and the SO of molecular sieve
4 2-/ ZrO
2Highly acid combine, made and had SO
4 2-/ Zr-ZSM-11, SO
4 2-The solid super acid catalyst of/Zr-MCM-41 molecular sieve structure feature, catalyst surface contain more B acid and L acid site, but the easy inactivation of catalyst, easily run off in the acid site.
Patent USP5345026 and USP5510309 announced with the tungstate modified zirconia and made solid acid catalyst, is used for hydrogenation/dehydrogenation catalysis to make hydro carbons open loop and the C that contains ring structure
4～C
8Hydrocarbon isomerization, but the report specific surface area of catalyst little, acidity a little less than, serviceability temperature is also lower.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst activity that uses in the existing naphtha catalytic pyrolysis preparing ethylene propylene reaction is lower, and the problem that the yield of ethylene, propylene is low, reaction temperature is high provides a kind of catalyst of new preparing ethylene propylene from catalytic pyrolysis.This catalyst has the catalytic activity height, ethylene propylene yield height, the advantage that reaction temperature is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of preparing ethylene propylene from catalytic pyrolysis is by weight percentage:
A) at least a in the coexisting molecular sieve of the coexisting molecular sieve of 80～99.5% the coexisting molecular sieve that is selected from ZSM-5 and modenite, ZSM-5 and β zeolite or ZSM-5 and Y zeolite; With carry thereon
B) surplus is selected from the super acids that at least a group vib element in the periodic table of elements or its oxide and at least a IVB family's element or its oxide are formed;
Wherein, in the described coexisting molecular sieve, the weight percentage of ZSM-5 molecular sieve is 60～99.5%; The SiO of coexisting molecular sieve
2/ Al
2O
3Mol ratio is 10～300.
In the technique scheme, the weight percentage preferable range of ZSM-5 is 60～99.5% in the used coexisting molecular sieve, and more preferably scope is 80～99%; The SiO of used coexisting molecular sieve
2/ Al
2O
3The excellent preferable range of mol ratio is 12～50; The consumption preferable range of coexisting molecular sieve is 85～99% by weight percentage.Periodic table of elements group vib element preferred version is selected from least a among Cr, Mo or the W, and more preferably scheme is selected from least a among Mo or the W; The consumption preferable range 0.01～20% of group vib element or its oxide by weight percentage, more preferably scope is 0.1～10%.IVB family element preferred version is selected from least a among Ti, Zr or the Hf, and more preferably scheme is selected from least a among Ti or the Zr; The consumption preferable range 0.01～20% of IVB family element or its oxide by weight percentage, more preferably scope is 0.1～10%.
The raw material that the preparation coexisting molecular sieve uses: the silicon source is metasilicate, silicate sodium or Ludox, the aluminium source is aluminium salt or aluminate, the template agent is at least a in 4-propyl bromide, TPAOH, triethylamine, n-butylamine, tetraethyl ammonium hydroxide, ethylenediamine or the ethamine, and the pH value of regulating colloidal sol with diluted acid is 10～14.Prepare acid solution or salting liquid and ammonium salt solution or the aqueous slkali of solid super-strong acid with corresponding active component element.
The synthetic method concrete operations of coexisting molecular sieve are, get the silicon source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring adds one or more template agent of aequum then, stirs after 30 minutes with rare acid for adjusting pH value in 10～13 scopes, supply distilled water again, add the corresponding crystal seed of aequum.Colloidal sol is put into autoclave, control temperature crystallization a period of time of 120～180 ℃ after, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours, can obtain corresponding coexisting molecular sieve.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make the Hydrogen coexisting molecular sieve.
The present invention since adopted acid strong, have multi-stage artery structure, ethylene, propylene selectivity good coexisting molecular sieve be carrier, select for use and have the acid strength height, catalytic capability is strong, the selectivity height, and serviceability temperature is wide, the acid solid super-strong acid that is difficult for running off carries out loaded modified to coexisting molecular sieve, strengthen the hydrothermal stability and the acidity of coexisting molecular sieve, make the catalyst acid density that makes big, the acid strength height, acid stable is difficult for running off, and is suitable for alkane cracking and becomes ethylene, propylene.
In order to check and rate activity of such catalysts, the related catalyst compressing tablet of invention, break into pieces, sieve after, get 20～40 purpose particles with standby.The C that adopts Shanghai Gaoqiao petro-chemical corporation to produce
4～C
10The naphtha of hydrocarbon is a raw material, naphtha physical index such as table 1.With internal diameter is 12 millimeters down examination of fixed bed reactors normal pressure, is 600～650 ℃ in reaction temperature, and reaction pressure is 0.001MPa～0.5MPa, weight space velocity 0.25～4 hour
-1, under the condition of water/feedstock oil weight ratio 1～4: 1, naphtha being carried out catalytic pyrolysis, the ethylene, propylene yield can reach 55%, has obtained better technical effect.
Table 1 feed naphtha index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.18 |
| N-alkane % (weight %) in the alkane | ＞32.5 |
| Cycloalkane % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, after stirring a period of time, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, add the crystal seed that contains ZSM-5 and modenite presoma, stir and after 30 minutes mixed solution is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the coexisting molecular sieve of ZSM-5 and modenite, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 and modenite weight content be respectively 95% and 5%.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5 and mercerization zeolite symbiosis molecular screen, be designated as FH-1.
[embodiment 2]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 16.7 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram ethylenediamines and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring a period of time, regulate the pH value 11 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.05: 0.4: 40, add 2.8 gram β zeolite seed crystals, mixed solution is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ beta zeolite coexisting molecular sieve, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 weight percentage be 94.6%, the β zeolite is 5.4%.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5/ beta zeolite coexisting molecular sieve, be designated as FH-2.
[embodiment 3]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, stir after 20 minutes, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, add 2.8 gram Y zeolite seed crystals, mixed solution is put into autoclave, 130 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/Y zeolite coexisting molecular sieve.Quantitatively contain the ZSM-5 of 94.5% weight and the Y zeolite of 5.5% weight in the coexisting molecular sieve as can be known with the XRD diffraction.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5/Y zeolite coexisting molecular sieve, be designated as FH-3.
[embodiment 4～7]
The Hydrogen ZSM-5/Y zeolite coexisting molecular sieve that the Hydrogen ZSM-5/ mercerization zeolite symbiosis molecular screen that embodiment 1 is made, the Hydrogen ZSM-5/ beta zeolite coexisting molecular sieve that embodiment 2 makes and embodiment 3 make mixes according to a certain percentage, make mechanical impurity, as shown in table 2.
Table 2
[embodiment 8～25]
According to the method for embodiment 1, embodiment 2 and embodiment 3,, make a collection of Hydrogen coexisting molecular sieve respectively by changing the amount of raw material proportioning, pH value and adding crystal seed, as shown in table 3.
Table 3
[embodiment 26]
Get 66 milliliters of the zirconium nitrate solutions of 0.05 mol, 33 milliliters of ammonium tungstate solutions that add 0.05 mol, the powerful stirring 10 minutes, add then and get Hydrogen ZSM-5/ mercerization zeolite symbiosis molecular screen 20 grams that embodiment 1 makes, stir down at 70 ℃, slow evaporate to dryness is put into baking oven then 120 ℃ of dryings 3 hours, put into 650 ℃ of roastings of Muffle furnace 3 hours again, make WO
3/ ZrO
2The ZSM-5/ mercerization zeolite symbiosis molecular screen catalyst of solid super-strong acid load.The catalyst compressing tablet, break into pieces, sieve after, get 20～40 purpose particles and put into fixed bed reactors, be that 650 ℃, reaction pressure are that 0.02MPa, weight space velocity are 1 hour in reaction temperature
-1, check and rate under water/condition of 3: 1 of feedstock oil weight ratio, the results are shown in Table 4.
[embodiment 27～33]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 26.
[embodiment 34]
Get ZSM-5/Y zeolite coexisting molecular sieve 20 grams that embodiment 22 makes, 66 milliliters of zirconium nitrates that add 0.05 mol, stir evaporate to dryness at 70 ℃ then, put into baking oven then 120 ℃ of dryings 3 hours, put into 650 ℃ of roastings of Muffle furnace 3 hours again, take out cooling then after, 33 milliliters of ammonium tungstate solutions that add 0.05 mol again, stir evaporate to dryness at 70 ℃, behind the drying and roasting, make the coexisting molecular sieve catalyst WO of solid super-strong acid load in a manner described
3/ ZrO
2-ZSM-5/Y zeolite.Method examination according to embodiment 26 the results are shown in Table 4.
[embodiment 35～38]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 34.
Table 4
[embodiment 39]
Get ZSM-5/Y zeolite coexisting molecular sieve 20 grams that embodiment 3 makes, make WO by the method for embodiment 26
3/ ZrO
2The ZSM-5/Y zeolite coexisting molecular sieve of load then as carrier, is pressed the method for embodiment 26 again, makes WO
3/ TiO
2The WO of load
3/ ZrO
2-ZSM-5/Y zeolite coexisting molecular sieve catalyst.Method examination according to embodiment 26 the results are shown in Table 5.
[embodiment 40～50]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 5 according to method modification and the examination of embodiment 39.
Table 5
[embodiment 51]
Get Hydrogen ZSM-5/ mercerization zeolite symbiosis molecular screen 20 grams that embodiment 1 makes, 33 milliliters of ammonium tungstate solutions that add 0.05 mol, stir down at 70 ℃, slow evaporate to dryness, put into baking oven then 120 ℃ of dryings 3 hours, put into 650 ℃ of roastings of Muffle furnace 3 hours again, make the ZSM-5/ mercerization zeolite symbiosis molecular screen catalyst of tungsten load.The catalyst compressing tablet, break into pieces, sieve after, get 20～40 purpose particles and put into fixed bed reactors, be that 650 ℃, reaction pressure are that 0.02MPa, weight space velocity are 1 hour in reaction temperature
-1, check and rate under water/condition of 3: 1 of feedstock oil weight ratio, the results are shown in Table 6.
[embodiment 52～53]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 6 according to method modification and the examination of embodiment 51.
[embodiment 54～57]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 6 according to method modification and the examination of embodiment 34.
Table 6
[comparative example 1]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 40 ZSM-5 molecular sieve, and the method modification according to embodiment 40 makes MoO
3/ ZrO
2And MoO
3/ TiO
2The catalyst of solid super-strong acid load is checked and rated result such as table 7 according to the mode of embodiment 40.
[comparative example 2]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 20 modenite, and the method modification according to embodiment 42 makes WO
3/ ZrO
2And MoO
3/ ZrO
2The catalyst of solid super-strong acid load is checked and rated result such as table 7 according to the mode of embodiment 42.
[comparative example 3]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 40 β zeolite, and the method modification according to embodiment 50 makes WO
3/ ZrO
2, WO
3/ TiO
2, MoO
3/ ZrO
2, MoO
3/ TiO
2, CrO
3/ ZrO
2And CrO
3/ TiO
2The catalyst of solid super-strong acid load is checked and rated result such as table 7 according to the mode of embodiment 50.
[comparative example 4]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 20 Y zeolite, and the method modification according to embodiment 48 makes WO
3/ ZrO
2, MoO
3/ ZrO
2, CrO
3/ ZrO
2And CrO
3/ TiO
2The catalyst of solid super-strong acid load is checked and rated result such as table 7 according to the mode of embodiment 48.
[comparative example 5]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 40 ZSM-5 molecular sieve, according to the method modification of embodiment 51, makes the catalyst of tungsten load, checks and rates result such as table 7 according to the mode of embodiment 51.
Table 7
Claims (7)
1. the catalyst of a preparing ethylene propylene from catalytic pyrolysis is by weight percentage:
A) at least a in the coexisting molecular sieve of the coexisting molecular sieve of 80～99.5% the coexisting molecular sieve that is selected from ZSM-5 and modenite, ZSM-5 and β zeolite or ZSM-5 and Y zeolite; With carry thereon
B) surplus is selected from the super acids that at least a VI B family's element in the periodic table of elements or its oxide and at least a IV B family's element or its oxide are formed;
Wherein, in the described coexisting molecular sieve, the weight percentage of ZSM-5 molecular sieve is 60～99.5%; The SiO of coexisting molecular sieve
2/ Al
2O
3Mol ratio is 10～300.
2. according to the catalyst of the described preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that the coexisting molecular sieve consumption is 85～99% by weight percentage.
3. according to the catalyst of the described preparing ethylene propylene from catalytic pyrolysis of claim 2, it is characterized in that the SiO of coexisting molecular sieve
2/ Al
2O
3Mol ratio is 12～50; The weight percentage of ZSM-5 molecular sieve is 80～99%.
4. according to the catalyst of the described preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that periodic table of elements VI B family element is selected from least a among Cr, Mo or the W, by weight percentage, the consumption of VI B family element or its oxide is 0.01～20%.
5. according to the catalyst of the described preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that periodic table of elements IV B family element is selected from least a among Ti, Zr or the Hf, by weight percentage, the consumption of IV B family element or its oxide is 0.01～20%.
6. according to the catalyst of the described preparing ethylene propylene from catalytic pyrolysis of claim 4, it is characterized in that by weight percentage that the consumption that is selected from periodic table of elements VI B family's element or its oxide is 0.1～10%.
7. according to the catalyst of the described preparing ethylene propylene from catalytic pyrolysis of claim 5, it is characterized in that by weight percentage that the consumption that is selected from periodic table of elements IV B family's element or its oxide is 0.1～10%.
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| US9227181B2 (en) | 2011-09-13 | 2016-01-05 | Basf Corporation | Catalyst to increase propylene yields from a fluid catalytic cracking unit |
| CN103071522B (en) * | 2012-12-26 | 2018-01-05 | 宁夏大学 | A kind of catalyst and method of C4 C6 hydrocarbon mixture catalytic pyrolysis propylene enhancings and ethene |
| CN103272635B (en) * | 2013-05-10 | 2015-03-04 | 神华集团有限责任公司 | Catalyst for preparing low-carbon olefin through high-carbon hydrocarbon conversion and preparation method of catalyst |
| CN104549466B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | In-situ synthesized ZSM-5/Beta symbiotic molecular sieve based catalyst and preparation method thereof |
| CN104549467B (en) * | 2013-10-28 | 2017-07-14 | 中国石油化工股份有限公司 | Composite molecular sieve catalyst of fabricated in situ and preparation method thereof |
| CN106629768A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Synthetic method for uniform nanosized ZSM-5 molecular sieve |
| CN106807353B (en) * | 2015-12-01 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of preparation method of active catalytic material |
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| 贾卫 等,.以乙二胺为模板剂合成Y /ZSM- 5复合分子筛.石油化工35 9.2006,35(9),832-836. * |
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