CN103041845B - Catalyst composition containing modified ZSM-11 zeolite and application of catalyst composition - Google Patents
Catalyst composition containing modified ZSM-11 zeolite and application of catalyst composition Download PDFInfo
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a catalyst composition containing modified ZSM-11 zeolite and an application of the catalyst composition. The catalyst composition comprises the following components of: 30-85 percent of ZSM-11 zeolite, 10-60 percent of binding agent, 0.1-10 percent of alkali metal oxide, 1-20 percent of ZSM-11 zeolite modified additive SiO2 and 1-20 percent of ZSM-11 zeolite modified additive alkali metal oxide. The catalyst composition disclosed by the invention is used in a methylbenzene alkylation process for synthesizing p-methyl methylbenzene from methylbenzene and ethylene and is favorable in catalytic reaction effect.
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymeric and application thereof, particularly this catalyst containing modified ZSM-5-11 zeolite synthetic to the application in methyl-ethyl benzene at toluene and ethene.
Background technology
P-methylstyrene can be obtained to methyl-ethyl benzene dehydrogenation, after polymerization, polymethylstyrene novel plastic can be produced.This polymer is at proportion, heat resistance, and the aspects such as transparency and shrinkage factor are all better than existing polystyrene plastics.In addition p-methylstyrene can with other monomer copolymerization, can improve heat resistance and the anti-flammability of some polymer, can be in a large number for engineering plastics, the manufacture of the aspects such as phthalic resin coating, thereby in widespread attention.Also do not obtain for a long time the satisfactory method to methyl-ethyl benzene of high concentration, obtain the product of contraposition, must there is a kind of well behaved shape-selective catalyst, in pore size, grain size and the hole of requirement zeolite catalyst, acid site intensity is suitable, and the acidity of outer surface is inhibited, likely make alkylation of toluene reaction break the thermodynamical equilibrium CONCENTRATION DISTRIBUTION of contraposition methyl-ethyl benzene, a position methyl-ethyl benzene, ortho position methyl-ethyl benzene product, mainly generate contraposition methyl-ethyl benzene.Catalytic theory infers and thinks and can make toluene and ethene vapor phase alkylation break through the restriction of thermodynamical equilibrium through the ZSM-5 molecular sieve of chemical modification, can obtain 90% above concentration to methyl-ethyl benzene, and substantially do not generate neighbour, a position methyl-ethyl benzene.In recent years, the research of this problem causes the broad interest of Liao Ge company and scientific research institution, and obtain certain progress, if can obtain further success, production technology to methyl-ethyl benzene is produced to dramatic change, to saving the energy, simplified apparatus, reduce production costs, the very important meaning of having increased economic efficiency.
US5698756 uses methyl-silicone oil polymer (Dow-550) to carry out modification to the HZSM-5 molecular sieve of Si/Al=26, the silicone oil polymer of each load 7.8%, modification 4 times altogether.Then in sodium nitrate solution, exchange three times, then at 200 DEG C, be dried and catalyst.Evaluating catalyst condition is: 450 DEG C of temperature, toluene air speed 5 h
-1, benzene alkene is than 4, stagnation pressure 0.7MPa; In the situation that toluene conversion is 15.45%, obtains the overall selectivity of methyl-ethyl benzene has been greater than to 77% effect, but also had the methyl-ethyl benzene product at a certain amount of position and ortho position.
CN1103607A provides ethene and toluene reaction in a kind of catalytic cracked dry gas to produce the shape selective catalysis agent to methyl-ethyl benzene.This kind of shape selective catalysis agent is a kind of Pentasil type catalyst containing rare earth, selects suitable chemical modifier to carry out modification: molecular sieve is carried out to the dipping modifications such as aluminium and magnesium, the amount of its oxide modifier is not less than 0.25%.By modified catalyst at 350 DEG C ~ 420 DEG C of temperature, mass space velocity 0.3 ~ 0.5 h
-1, benzene alkene, than 4 ~ 6, is checked and rated catalyst under the reaction condition of reaction pressure 0.1 ~ 1MPa, can obtain more than more than 85% conversion of ethylene and 90% selective to methyl-ethyl benzene.
Above document has all promoted the para-selectivity of product to methyl-ethyl benzene preferably, but the toluene conversion of product overall selectivity is still lower, can't meet the demand of actual production, thereby has limited its industrial applications.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of containing the carbon monoxide-olefin polymeric of modified ZSM-5-11 zeolite and synthetic to the application in methyl-ethyl benzene at toluene and ethene, solve in prior art toluene conversion not high, selectively lower to methyl-ethyl benzene, the problems such as the side reaction such as disproportionated reaction and isomerization reaction is serious, thus the effect of alkylation of toluene reaction improved.
The present invention is containing the carbon monoxide-olefin polymeric of modified ZSM-5-11 zeolite, in catalyst weight percentage, there is following composition: ZSM-11 zeolite 30% ~ 85%, adhesive 10%～60%, alkali metal oxide 0.1%～10%, ZSM-11 Zeolite modifying auxiliary agent silica 1 %～20%, ZSM-11 Zeolite modifying additive alkali soil metal oxide 1% ~ 20%.
In carbon monoxide-olefin polymeric of the present invention, modified additive silica and modified additive alkaline earth oxide load on ZSM-11 zeolite, and order is first loaded modified additive alkali soil metal oxide, then loaded modified auxiliary agent silica.Loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, processes the ZSM-11 zeolite of alkaline earth oxide modification, then drying and roasting with silicon-containing organic compound.
In carbon monoxide-olefin polymeric of the present invention, ZSM-11 zeolite SiO
2/ Al
2o
3mol ratio is 20 ~ 500, is preferably 30 ~ 200, more preferably 50 ~ 100, and by weight percentage, the content of ZSM-11 zeolite in catalyst is preferably 40% ~ 70%, and more preferably 50% ~ 60%.
In carbon monoxide-olefin polymeric of the present invention, the content of ZSM-11 Zeolite modifying auxiliary agent silica is preferably 2% ~ 10%, and more preferably 3% ~ 8%.One or more in the oxide that is selected from beryllium, magnesium, calcium, strontium, barium of ZSM-11 Zeolite modifying additive alkali soil metal oxide, are preferably beryllium or/and magnesium, more preferably magnesium; In catalyst weight percentage, the content of alkaline earth oxide is preferably 2% ~ 15%, and more preferably 5% ~ 12%.
In carbon monoxide-olefin polymeric of the present invention, adhesive is aluminium oxide or silica, is preferably silica; By weight percentage, its content in catalyst is preferably 15% ~ 50%.
In carbon monoxide-olefin polymeric of the present invention, the oxide that alkali metal oxide is sodium is or/and the oxide of potassium, and by weight percentage, its content in catalyst is preferably 0.5% ~ 5%, and more preferably 1% ~ 3%.
The present invention is applied to toluene containing modified ZSM-5-11 zeolite catalyst composition and ethylene selectivity alkylation generates in methyl-ethyl benzene course of reaction, concrete technology condition can adjusted in a big way, for example, volume space velocity 0.5 h when hydrogen partial pressure 0.5MPa ~ 5.0MPa, 360 DEG C ~ 500 DEG C of reaction temperatures, toluene liquid
-1~ 10.0h
-1, toluene/ethylene molar ratio 1:1 ~ 10:1, hydrogen to oil volume ratio 200:1 ~ 1000:1(hydrogen and the volume ratio of toluene under standard conditions), optimum condition is: volume space velocity 2 h when hydrogen partial pressure 1MPa ~ 3MPa, 380 DEG C ~ 460 DEG C of reaction temperatures, toluene liquid
-1~ 5h
-1, toluene/ethylene molar ratio 3:1 ~ 5:1, hydrogen to oil volume ratio 300:1 ~ 500:1.
The present invention selects ZSM-11 zeolite, after alkaline earth oxide modification and liquid-phase silicone deposition surface modification, adds suitable alkali metal compound, has prepared final catalyst.Catalyst of the present invention catalyzes and synthesizes methyl-ethyl benzene carrying out alkylation of toluene taking ethene as raw material, when can obtaining higher toluene conversion, can greatly suppress the side reactions such as transalkylation, has improved in product selective to methyl-ethyl benzene.Can be used for the synthetic production technology to methyl-ethyl benzene, can significantly reduce operation easier and the energy consumption of the separative element of the product to methyl-ethyl benzene.It is not high that carbon monoxide-olefin polymeric containing modified ZSM-5-11 zeolite of the present invention has solved in prior art toluene conversion, selectively lower to methyl-ethyl benzene, the problems such as the side reaction such as disproportionated reaction and isomerization reaction is serious, thus the effect of alkylation of toluene reaction improved.
Detailed description of the invention
The present invention is as follows containing the preparation method of modified ZSM-5-11 zeolite catalyst composition:
(1) alkaline earth metal compound is loaded on ZSM-11 zeolite, through super-dry and roasting, obtain the ZSM-11 zeolite of alkaline earth oxide modification;
(2) with the ZSM-11 zeolite of the alkaline earth oxide modification making containing the solution impregnation step (1) that changes silicon compound, through super-dry and roasting, obtain the ZSM-11 zeolite of silicon-alkaline earth modification;
(3) the abundant kneading of modified ZSM-5-11 zeolite, adhesive, alkali compounds, extrusion aid and water that step (2) makes becomes plastic paste, and extruded moulding, through super-dry and roasting, obtains catalyst of the present invention.
In step (1), alkaline earth metal compound loads to the method on ZSM-11 zeolite, can adopt ion-exchange, infusion process or kneading method, while wherein adopting ion-exchange or infusion process, the solution alkaline including earth metal compound used of preparing alkaline including earth metal compound is selected from one or more in the chloride of solubility, nitrate, sulfate, be preferably and be selected from chloride and/or nitrate, more preferably chloride.While adopting kneading method, that alkaline including earth metal compound is fully mixed with molecular sieve, alkaline including earth metal compound is to be selected from one or more in oxide, chloride, nitrate, sulfate and carbonate, is preferably oxide and/or nitrate, more preferably nitrate.
The described modifier of step (2) is silicon-containing organic compound, is preferably polyphenyl methylsiloxane, solvent can be can solvent modified dose organic matter or inorganic matter, be preferably organic hydrocarbon, such as n-hexane etc.;
The described adhesive of step (3) is the material that can make material forming, and for example aluminium oxide or silica, be preferably silica, is the precursor of aluminium oxide or silica, as aluminium hydroxide, Ludox, white carbon etc. when use.Alkali compounds is that NaOH is or/and potassium hydroxide.Extrusion aid is the material that is conducive to extruded moulding, can be selected from one or more in graphite, starch, cellulose and sesbania powder, is preferably sesbania powder, and by weight percentage, its amount adding is 0.5% ~ 10% of carrier butt, is preferably 1% ~ 5%.
Drying condition described in step (1), (2) and (3) is that normal temperature ~ 300 DEG C keep 1h ~ 48h, and the described drying condition of step (1), step (2) and step (3) can be identical, also can be different.The roasting condition of step (1), (2) and (3) is 400 DEG C ~ 800 DEG C maintenance 0.5h ~ 10.0h, and the described roasting condition of step (1), step (2) and step (3) can be identical, also can be different.
Catalyst of the present invention is to adopt the medium-sized fixed bed reactors of 100ml to evaluate, and loaded catalyst is 100ml, and appreciation condition is: volume space velocity 4.0h when hydrogen partial pressure 1.3MPa, 390 DEG C of reaction temperatures, toluene liquid
-1, toluene/ethylene molar ratio 4:1, hydrogen to oil volume ratio 400.Catalyst runs was carried out constituent analysis to tail gas and product liquid after 8 hours, calculated the selective of the conversion ratio of ethene and p-methyl-ethylbenzene, and concrete computational methods are as follows:
×100%
×100%
Further illustrate the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited in following embodiment.
[embodiment 1](if there is no below special indicating, degree and composition are all taking weight as benchmark)
The preparation process of carbon monoxide-olefin polymeric of the present invention is as follows:
(1) getting silica alumina ratio (silica/alumina molar ratio, lower with) is 300 grams, 80 ZSM-11 zeolite, makes 450 milliliters and counts the magnesium chloride solution of 50 grams with content of magnesia.The solution of above-mentioned magnesium chloride containing and ZSM-11 zeolite are fully mixed, after 110 DEG C of oven dry, 500 DEG C of roastings in 4 hours, obtain consisting of of sample: magnesia/ZSM-11=1/6.
(2) the magnesium-modified ZSM-11 zeolite (350 grams) making by step (1), then flood with 500 milliliters of the hexane solutions taking silica content as the polyphenyl methylsiloxane of 25 grams preparing, after dipping, leave standstill, thorough to solvent evaporates, roasting at 550 DEG C after dry, obtains consisting of of sample: SiO
2/ MgO/ZSM-11=0.5/1/6.
(3) modified ZSM-5-11(400 gram making by step (2)), 117.5 grams of white carbons (binding agent), 7.6 grams of NaOH, 20 grams of sesbania powder become plastic paste with the appropriate abundant kneading of water, extruded moulding (1.5 millimeters of diameters), through 120 DEG C of dry and 550 DEG C of roastings of 3 hours of 8 hours, obtain catalyst of the present invention, it consists of: Na
2o/SiO
2/ MgO/ZSM-11/ binding agent=0.15/0.5/1/6/2.35(catalyst percentage consists of: Na
2o:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%), be numbered E-1, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment2]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the silica alumina ratio of used ZSM-11 zeolite is 38, the consisting of of the catalyst obtaining: Na
2o:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-2, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment3]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that used magnesium-containing compound is for magnesium nitrate, and the binding agent using is Ludox, the consisting of of the catalyst obtaining: Na
2o:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-3, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment4]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is the composition difference of catalyst, the consisting of of the catalyst obtaining: Na
2o:0.5%, SiO
2: 3.5%, MgO:6%, ZSM-11:50%, binding agent: 40%, be numbered E-4, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment5]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is the composition difference of catalyst, the consisting of of the catalyst obtaining: Na
2o:1%, SiO
2: 6%, MgO:9%, ZSM-11:70%, binding agent: 14%, be numbered E-5, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment6]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the silica alumina ratio of used ZSM-11 zeolite is 120, and the alkaline-earth metal using is beryllium and magnesium, and catalyst composition is different, the consisting of of the catalyst obtaining: Na
2o:1%, SiO
2: 4%, BeO:1.8%, MgO:3.2%, ZSM-11:55%, binding agent: 35%, be numbered E-6, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment7]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is the composition difference of catalyst, obtains consisting of of catalyst: Na
2o:5%, SiO
2: 4%, MgO:1%, ZSM-11:35%, binding agent: 55%, be numbered E-7, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment8]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, difference is that used alkaline-earth metal component is for magnesium nitrate, directly mix with molecular sieve, through drying and calcination process obtains modified ZSM-5-11, the consisting of of the catalyst obtaining: Na
2o:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-8, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[embodiment9]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and it is dry different with the temperature and time of roasting that difference is to adopt in preparation process, and actual conditions is: the treatment conditions of (1) step sample be 200 DEG C 2 hours, 380 DEG C 8 hours; (2) treatment conditions of step be 80 DEG C 16 hours, 580 DEG C 3 hours; (3) treatment conditions of step be 50 DEG C 48 hours, 490 DEG C 6 hours.Obtain catalyst of the present invention, it consists of: Na
2o:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-9, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[comparative example 1]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is that molecular sieve is without alkali earth metal and siliceous deposits modification, and composition is different, the consisting of of the catalyst obtaining: Na
2o:2%, ZSM-11:60%, binding agent: 38%, be numbered C-1, its reaction result in the selective alkylation of toluene and ethene is in table 1.
[comparative example 2]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is that molecular sieve is without siliceous deposits modification, and composition is different, the consisting of of the catalyst obtaining: Na
2o:2%, MgO:10%, ZSM-11:60%, binding agent: 28%, be numbered C-2, its reaction result in the selective alkylation of toluene and ethene is in table 1.
the evaluation result of table 1 different catalysts
| Embodiment numbering | Catalyst | Toluene conversion, % | P-methyl-ethylbenzene is selective, % |
| 1 | E-1 | 24.3 | 97.4 |
| 2 | E-2 | 24.7 | 97.1 |
| 3 | E-3 | 23.9 | 97.9 |
| 4 | E-4 | 23.3 | 98.2 |
| 5 | E-5 | 24.8 | 97.0 |
| 6 | E-6 | 23.1 | 98.6 |
| 7 | E-7 | 22.2 | 99.1 |
| 8 | E-8 | 24.3 | 97.5 |
| 9 | E-9 | 24.2 | 97.8 |
| Comparative example numbering | - | - | - |
| 1 | C-1 | 24.7 | 71.3 |
| 2 | C-2 | 24.4 | 76.9 |
Note: evaluating catalyst process conditions are: volume space velocity 4.0h
-1, 390 DEG C of temperature, pressure 1.3MPa, toluene/ethylene ratio 4.0 (mol/mol), hydrogen to oil volume ratio 400,8 hours time.
Claims (9)
1. the carbon monoxide-olefin polymeric containing modified ZSM-5-11 zeolite, it is characterized in that with carbon monoxide-olefin polymeric weight percent meter, there is following composition: ZSM-11 zeolite 30%～85%, adhesive 10%～60%, alkali metal oxide 0.1%～10%, ZSM-11 Zeolite modifying auxiliary agent silica 1 %～20%, ZSM-11 Zeolite modifying additive alkali soil metal oxide 1%～20%; Wherein modified additive silica and modified additive alkaline earth oxide load on ZSM-11 zeolite, and order changes additive alkali soil metal oxide for first load, then loaded modified auxiliary agent silica.
2. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, process the ZSM-11 zeolite of alkaline earth oxide modification with silicon-containing organic compound, then dry and roasting.
3. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: ZSM-11 zeolite SiO
2/ Al
2o
3mol ratio is 20～500, and by weight percentage, the content of ZSM-11 zeolite in catalyst is 40%～70%.
4. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: the content of ZSM-11 Zeolite modifying auxiliary agent silica is 2%～10%.
5. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: ZSM-11 Zeolite modifying additive alkali soil metal oxide is selected from one or more in the oxide of beryllium, magnesium, calcium, strontium, barium, in catalyst weight percentage, the content of alkaline earth oxide is 2%～15%.
6. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: adhesive is aluminium oxide or silica, by weight percentage, the content of adhesive in catalyst is 15%～50%.
7. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: the oxide that alkali metal oxide is sodium is or/and the oxide of potassium, and by weight percentage, the content of alkali metal oxide in catalyst is 0.5%～5%.
8. described in the arbitrary claim of claim 1 to 7, carbon monoxide-olefin polymeric generates the application in methyl-ethyl benzene course of reaction at toluene and ethylene selectivity alkylation.
9. according to application claimed in claim 8, it is characterized in that: toluene and ethylene selectivity alkylation generate that methyl-ethyl benzene is reacted to hydrogen partial pressure is that 0.5MPa～5.0MPa, reaction temperature are 360 DEG C～500 DEG C, volume space velocity is 0.5h when toluene liquid
-1～10.0h
-1, toluene/ethylene molar ratio is 1:1～10:1, hydrogen to oil volume ratio is 200:1～1000:1.
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| CN111054429A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation and application thereof |
| CN114762832B (en) * | 2021-01-12 | 2023-12-08 | 洛阳市科创石化科技开发有限公司 | Preparation method and application of catalyst for producing mixed propylbenzene by alkylation of benzene and carbon tetraolefin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169338A (en) * | 1996-06-24 | 1998-01-07 | 中国石油化工总公司 | Alkyl catalyst and application thereof |
| CN1201717A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN101584991A (en) * | 2008-05-23 | 2009-11-25 | 中国石油化工股份有限公司 | Catalyst for olefin catalytic cracking to produce propylene and ethylene and application thereof |
| CN101940943A (en) * | 2010-09-28 | 2011-01-12 | 同济大学 | Shape-selective alkylation catalyst for synthesizing p-cymene with toluene and propylene as raw materials |
| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
-
2011
- 2011-10-17 CN CN201110313245.6A patent/CN103041845B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169338A (en) * | 1996-06-24 | 1998-01-07 | 中国石油化工总公司 | Alkyl catalyst and application thereof |
| CN1201717A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN101584991A (en) * | 2008-05-23 | 2009-11-25 | 中国石油化工股份有限公司 | Catalyst for olefin catalytic cracking to produce propylene and ethylene and application thereof |
| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
| CN101940943A (en) * | 2010-09-28 | 2011-01-12 | 同济大学 | Shape-selective alkylation catalyst for synthesizing p-cymene with toluene and propylene as raw materials |
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