CN101837990A - Fluorine-containing all-silica MFI zeolite molecular sieve and preparation method thereof - Google Patents
Fluorine-containing all-silica MFI zeolite molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention provides a method for preparing a fluorine-containing all-silica MFI zeolite molecular sieve, which is characterized in that villiaumite (MF) is added into synthetical silica sol to form an SiO2-Na2O-TPAOH-MF-H2O sol system, and mol rates of components are as follows: MF/SiO2=0.05-1.5, NaOH/SiO2=0.1-0.5, TPAOH/SiO2=0.2-0.5 and H2O/SiO2=10-25. The method for preparing the fluorine-containing all-silica MFI zeolite molecular sieve comprises the following steps of: carrying out hydrothermal synthesis on the sol for 24-120 hours at the synthetical temperature of 90-160 DEG C; centrifuging, washing, drying and roasting the sol to obtain the fluorine-containing all-silica MFI zeolite molecular sieve with high crystallinity. The chemical composition is M+x[Si960192Fx]<x->, wherein X=0.01-1, M=Na+ or K<+> or NH<4+>. In the invention, the prepared fluorine-containing all-silica MFI zeolite molecular sieve has the advantages of the high-ratio surface area and the high activity, and can be applied to fields of catalytic cracking, etherification, separation organic steam and the like of hydrocarbon oil raw materials.
Description
Technical field
The present invention relates to the preparation and the application of fluorine-containing zeolite molecular sieve, particularly the technology of preparing of fluorine-containing all-silica MFI zeolite molecular sieve belongs to zeolite molecular sieve material preparation and Application Areas.
Background technology
Zeolite molecular sieve is the important inorganic poromerics of a class, be to connect skeletons by the three-dimensional four that forms by shared summit between silicon-oxy tetrahedron and the aluminum-oxygen tetrahedron, tetrahedron can link to each other according to different array modes and be built into zeolite molecular sieve skeleton structure miscellaneous.The ZSM-5 zeolite molecular sieve be the seventies in last century by U.S. Mobil company synthetic the earliest, its skeleton Si/Al is 10～∞ than scope, the aperture is 0.54 * 0.56nm, and by the Pentasil structure that eight five-rings are formed, specific surface area generally reaches 400～600cm
2/ g has very high selectivity and thermostability, therefore reaches by reactions such as methanol synthesized gasolines to have unique catalytic performance in alkylation, isomerization, disproportionation, selective cracking process, and be the new catalytic agent material that is widely studied at present.
Fluorine-containing zeolite molecular sieve has unique catalytic activity and selectivity.Yet most fluorine-containing zeolite molecular sieves obtain by last handling process at present.Lee etc. (Microporous and Mesoporous Material, 23 (1998) 211) have studied the mordenite molecular sieve that hydrogen fluoride trealment is crossed, and find that the fluorine processing makes fluorine-containing zeolite molecular sieve produce a large amount of meso-hole structures.Patent US4444902, US4427790 and EP0295020A1 disclose under certain reaction conditions, the mixed type zeolite [molecular sieve (zeolite molecular sieve that contains types such as X, Y and ZSM-5) of preparation is soaked in hydrofluoric acid or villiaumite solution for some time, zeolite molecular sieve after the activation treatment has higher Bronsted acidity, ion-exchange equivalent and catalytic activity, and particularly the fluorine-containing ZSM-5 zeolite molecular sieve of handling through fluorine shows higher catalytic activity in petroleum catalytic cracking.Patent CN1037097A and US604178 will contain metal ion villiaumite solution zeolite molecular sieve will be carried out aftertreatment, find framework aluminum by the F-complexing and from zeolite, remove, thereby metallic cation inserts and replaces aluminium to obtain the heteroatomic zeolite molecular sieve of containing metal in the skeleton.Patent CN1552808A discloses a kind of preparation method of fluorine-containing zeolite [molecular sieve, with HY zeolite molecular sieve and aqueous hydrogen fluoride solution uniform mixing, get fluorine-containing HY zeolite behind the filtration drying, zeolite [molecular sieve after experiment is found to handle has higher cracking activity and abrasion resistance, this catalyzer is used for the catalytic cracking reaction of hydrocarbon ils, and the gasoline product octane value that obtains is higher.Li Jixia etc. (the chemistry of fuel journal, 36 (2008): 508) discover: the ZSM-5 catalyst surface after the hydrogen fluoride trealment is etched, and crystal grain is broken, but that the MFI feature structure of catalyst sample does not have is destroyed, and degree of crystallinity does not have considerable change; The pore volume of zeolite molecular sieve and mean pore size all increase than before handling; Variation has taken place in the surface acidity of catalyzer, and strong acid reduces relatively, and weak acid increases relatively.Thereby the fragmentation of zeolite molecular sieve crystal grain, secondary pore increase the diffusion that improves catalyzer after the hydrogen fluoride trealment, and fluorine is handled the defective bit of enriching that produces, and has strengthened the silanol base to alcoholic acid surface adsorption ability, thereby improve the etherification reaction catalytic activity of catalyzer.Wolch etc. (Microporous and Mesporous Material, 62 (2003) 157) discover, through the ZSM-5 zeolite molecular sieve of hydrogen fluoride trealment to the adsorption rate of normal hexane than high two orders of magnitude of untreated sample.
Many studies show that, zeolite molecular sieve make zeolite molecular sieve phenomenons such as dealuminzation, desiliconization occur after handling through fluorine, thereby cause the zeolite molecular sieve skeleton stability to reduce.On the other hand, the fluorine sources such as hydrofluoric acid that last handling process uses have strong corrodibility and toxicity, and process is difficult to control and harm operator health.Directly in resulting solution, add fluorine source synthesis zeolite report is also arranged.Patent CN101353171A has reported the method for synthetic fluorine-containing nanometer beta zeolite molecular sieve, this method is will to mix with silica gel after the acidifying of aluminium source earlier, make the abundant dispersing and mixing of silica gel and aluminium source with ultrasonic wave, dry, grind, mix the back crystallization then with tetraethylammonium cation template, fluorochemical and water and be prepared from.Patent US3839539A and CA976324A1 have reported that directly adding fluorine silicon ammonium in synthetic colloidal sol prepares fluorine-containing high reactivity HX, HY and A type zeolite molecular sieve, the content of fluorine is 0.01%～0.15% in the zeolite molecular sieve of preparation, studies show that this zeolite molecular sieve has higher thermostability and specific surface area.US5338525 has described at SiO
2-Ga
2O
3-Al
2O
3-NaF-H
2Synthetic Ga, Al type ZSM-5 zeolite molecular sieve in the O system, however the product results of elemental analyses shows does not find the F element in the product.
From existing document, directly add fluorine source report of synthesis zeolite in the colloidal sol and also be difficult to fluorine atom is introduced directly in the crystalline framework of zeolite molecular sieve.Also there is not directly to add the report of fluorine source synthetic fluorine-containing all-silica MFI zeolite molecular sieve in the colloidal sol.Enter the key issue that framework of molecular sieve prepares fluorine-containing MFI zeolite molecular sieve in order to solve fluorine, the present invention adopts and is controlling under suitable basicity (the being the pH value) condition, fluorion with colloidal sol under the effect of TPAOH template is incorporated in nucleation process in the nucleus, and fluorine is introduced in the crystalline framework the most at last.
The invention provides a kind of SiO that in synthetic colloidal sol, adds villiaumite
2-Na
2O-TPAOH-MF-H
2The O system, by hydrothermal synthesis method, single stage method directly prepares the method for fluorine-containing all-silica MFI zeolite molecular sieve.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing fluorine-containing all-silica MFI zeolite molecular sieve fast, easily, in the colloidal sol of synthesis zeolite, directly add the SiO in fluorine source
2-Na
2O-TPAOH-MF-H
2The O system by hydrothermal synthesis method, prepares fluorine-containing all-silica MFI zeolite molecular sieve 90～160 ℃ of next step methods of temperature.Specifically, its preparation process is: (1) mixes template tetrapropylammonium hydroxide, sodium hydroxide, silicon sol, fluorine source and suitable quantity of water, and it is 0.5～2ml/min that silicon sol adds speed, and at room temperature mixes and stir the formation stable sol, stirred formed SiO aging 12～36 hours
2-Na
2O-TPAOH-MF-H
2Each component mol ratio is in the O sol system:
MF/SiO
2＝0.05～1.5，
NaOH/SiO
2＝0.1～0.5，
TPAOH/SiO
2＝0.2～0.5，
H
2O/SiO
2＝10～25。
Preferred range is:
MF/SiO
2＝0.1～1，
NaOH/SiO
2＝0.1～0.4，
TPAOH/SiO
2＝0.2～0.4，
H
2O/SiO
2＝12～25。
(2) above-mentioned colloidal sol after aging is inserted in the teflon-lined stainless steel cauldron, then reactor is put into the baking oven crystallization 24～120 hours that is preheated to 90～160 ℃.After reaction finished, reaction solution had tangible layering.Reaction product through centrifugation, clean to neutral, drying, and put into 550 ℃ of retort furnace roastings 6 hours and can obtain fluorine-containing all-silica MFI zeolite molecular sieve to remove template.
The chemical constitution of the fluorine-containing all-silica MFI zeolite molecular sieve of preparation is among the present invention: M
+ x[Si
96O
192F
x]
X-, X=0.01～1 wherein, M=Na
+Or K
+Or NH
4 +
The fluorine-containing all-silica MFI zeolite molecular sieve of preparation is directly to add villiaumite in synthetic colloidal sol among the present invention, and villiaumite has Sodium Fluoride, Neutral ammonium fluoride and Potassium monofluoride, the preferred fluorinated ammonium.
Technical characterstic of the present invention is to control under suitable basicity (the being the pH value) condition, and the fluorion with colloidal sol under the effect of TPAOH template is incorporated in the nucleus in nucleation process, and then directly fluorine is incorporated in the crystalline framework.This patent is described fluorine-containing all-silica MFI zeolite molecular sieve forming process and roughly is described as:
(1) in initial reaction stage, the common dissolve silica of alkali dissolution effect of the mineralization in fluorine source and sodium hydroxide forms SiF respectively
6 2-And Si (OH)
4
(2) SiF
6 2-Can not become the molecular sieve polymer by direct polymerization, in solution, exist
(3) in the hydrolysis generating process, the Si of formation (OH)
4' nutritive ingredient ' is with template TPA
+For the center is gathered into specific ring texture, and because TPA
+Electric charge phase sucking action, F-enters in the ring texture, Si (OH)
4Further polycondensation forms the ad hoc rules structure mutually---and the elementary cell that MFI type zeolite molecular sieve is formed promptly forms nucleus;
(4) Si (OH) of continuous ' absorption ' colloidal sol of nucleus
4' nutritive ingredient ', the more macrocrystal of formation and nucleus same space structure promptly forms MFI type zeolite molecular sieve crystal.
Among the present invention during synthetic fluorine-containing all-silica MFI zeolite molecular sieve the hydro-thermal synthesis temperature be 90～160 ℃, optimum value is 100～150 ℃; Generated time is 24～120 hours, and optimum value is 24～96 hours.
The method of the synthetic fluorine-containing all-silica MFI zeolite molecular sieve of the single stage method that provides among the present invention, its preparation process is simple, mild condition, can save loaded down with trivial details subsequent processes in the zeolite molecular sieve preparation, save preparation process and time, reduced the pollution of fluorine to environment, and the fluorine-containing all-silica MFI zeolite molecular sieve of preparation has the mesoporous and bigger specific surface area of a greater number, be more suitable for preparing metal heteroatom MFI zeolite molecular sieve material, can be applicable to the catalytic cracking of hydrocarbon oil crude material, etherification reaction, absorption and separating organic steam and other gas, liquid mixture separates, in the field such as ion-exchange and membrane reactor.
Description of drawings
Fig. 1 prepares the synthetic schemes of fluorine-containing all-silica MFI zeolite molecular sieve for single stage method.
Fig. 2 makes x ray diffraction (XRD) figure of the fluorine-containing all-silica MFI zeolite molecular sieve of fluorine source synthetic for Sodium Fluoride.
Fig. 3 makes the XRD figure of the fluorine-containing all-silica MFI zeolite molecular sieve of fluorine source synthetic for Neutral ammonium fluoride.
Embodiment
In order to further describe the present invention, provided several concrete case study on implementation below, but the patent right authority is not limited to these examples.
Embodiment 1
The flow process that single stage method prepares fluorine-containing all-silica MFI zeolite molecular sieve as shown in Figure 1, (1) with template tetrapropylammonium hydroxide, sodium hydroxide silicon sol, Sodium Fluoride and suitable quantity of water mixed dissolution, the adding speed of silicon sol is 0.5～2ml/min, and at room temperature mix and stir the formation stable sol, stirred the SiO that forms aging 24 hours
2-Na
2O-TPAOH-MF-H
2Each component mol ratio is in the O sol system: MF/SiO
2=0.15, NaOH/SiO
2=0.25, TPAOH/SiO
2=0.3, H
2O/SiO
2=20; (2) above-mentioned colloidal sol after aging is inserted in the teflon-lined stainless steel cauldron, then reactor is put into the baking oven crystallization 30 hours that is preheated to 120 ℃.After reaction finished, reaction solution had tangible layering.Reaction product through centrifugation, clean to neutral, drying, and put into 550 ℃ of retort furnace roastings 6 hours and can obtain fluorine-containing all-silica MFI zeolite molecular sieve to remove template.
Sample characterizes through XRD, and Fig. 2 is the XRD diffractogram of synthetic zeolite molecular sieve, and Zhi Bei zeolite molecular sieve is 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 ° typical diffraction peaks of locating to show the MFI zeolite molecular sieve at diffraction angle 2 θ as seen from the figure.The molecular sieve warp
19F solid state nmr analysis revealed, F enters into skeleton, and in conjunction with ultimate analysis test shows such as XRD, atomic emission spectrum (ICP) and fluoride electrodes, the chemical constitution of the fluorine-containing all-silica MFI zeolite molecular sieve of synthetic is: Na
0.1[Si
96O
192F
0.1]
0.1-
Embodiment 2
Building-up process is as described in the embodiment 1, and different is with MF/SiO
2=0.6, generated time extends to 72 hours.After reaction finished, reaction solution had tangible layering.Reaction product through centrifugation, clean to neutral, drying, and put into 550 ℃ of retort furnace roastings 6 hours and can obtain fluorine-containing all-silica MFI zeolite molecular sieve to remove template.
Sample is characterized by the MFI zeolite molecular sieve through XRD.The molecular sieve warp
19F solid state nmr analysis revealed, F enters into skeleton, and in conjunction with ultimate analysis test shows such as XRD, ICP and fluoride electrodes, the chemical constitution of the fluorine-containing all-silica MFI zeolite molecular sieve of synthetic is: Na[Si
96O
192F]
-
Embodiment 3
Building-up process is as described in the embodiment 1, and different is that Sodium Fluoride is replaced to Neutral ammonium fluoride as the fluorine source.Synthetic product can obtain fluorine-containing all-silica MFI zeolite molecular sieve crystal after centrifugation, cleaning-drying and roasting.Sample characterizes through XRD, and Fig. 3 is fluorine-containing all-silica MFI zeolite molecular sieve XRD diffractogram, and Zhi Bei zeolite molecular sieve is 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 ° typical diffraction peaks of locating to show the MFI zeolite molecular sieve at diffraction angle 2 θ as seen from the figure.
Embodiment 4
Building-up process is as described in the embodiment 1, and different is that colloidal sol is formed NaOH/SiO
2=0.35, the reaction times foreshortens to 24 hours.After reaction finished, reaction solution had tangible layering.Reaction product through centrifugation, clean to neutral, drying, and put into 550 ℃ of retort furnace roastings 6 hours and can obtain fluorine-containing all-silica MFI zeolite molecular sieve to remove template.Sample is characterized by the MFI zeolite molecular sieve through XRD.The molecular sieve warp
19F solid state nmr analysis revealed, F enters into skeleton.
Building-up process is as described in the embodiment 1, and different is that temperature of reaction is risen to 150 ℃, and the reaction times foreshortens to 20 hours.After reaction finished, reaction solution had tangible layering.Reaction product through centrifugation, clean to neutral, drying, and put into 550 ℃ of retort furnace roastings 6 hours and can obtain fluorine-containing all-silica MFI zeolite molecular sieve to remove template.Sample is characterized by the MFI zeolite molecular sieve through XRD.The molecular sieve warp
19F solid state nmr analysis revealed, F enters into skeleton.
Claims (6)
1. fluorine-containing all-silica MFI zeolite molecular sieve, its chemical constitution is:
M
+ x[Si
96O
192F
x]
X-, X=0.01～1 wherein, M=Na
+Or K
+Or NH
4 +
2. the preparation method of a fluorine-containing all-silica MFI zeolite molecular sieve, it is characterized in that in synthetic colloidal sol, adding villiaumite, directly hydrothermal preparation goes out fluorine-containing all-silica MFI zeolite molecular sieve, its concrete steps are: (1) mixes template tetrapropylammonium hydroxide, sodium hydroxide, silicon sol, fluorine source and suitable quantity of water, it is 0.5～2ml/min that silicon sol adds speed, and at room temperature mix and stir the formation stable sol, stirred formed SiO aging 12～36 hours
2-Na
2O-TPAOH-MF-H
2Each component mol ratio is in the O sol system: MF/SiO
2=0.05～1.5, NaOH/SiO
2=0.1～0.5, TPAOH/SiO
2=0.2～0.5, H
2O/SiO
2=10～25; (2) colloidal sol hydro-thermal Synthetic 2 4～120 hours under 90～160 ℃ of synthesis temperatures obtains fluorine-containing all-silica MFI zeolite molecular sieve after centrifugal, cleaning, drying and roasting.
3. the preparation method of fluorine-containing all-silica MFI zeolite molecular sieve according to claim 2 is characterized in that villiaumite is Neutral ammonium fluoride or Sodium Fluoride or Potassium monofluoride, and the addition mol ratio of villiaumite is MF/SiO
2=0.1～1.
4. the preparation method of fluorine-containing all-silica MFI type zeolite molecular sieve according to claim 2, the addition mol ratio that it is characterized in that template is TPAOH/SiO
2=0.2～0.4.
5. the preparation method of fluorine-containing all-silica MFI type zeolite molecular sieve according to claim 2, alkali addition mol ratio is NaOH/SiO
2=0.1～0.4.
6. the preparation method of fluorine-containing all-silica MFI type zeolite molecular sieve according to claim 2 is characterized in that the hydro-thermal synthesis temperature is 100～150 ℃; Generated time is 24～96 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126731A (en) * | 2011-01-31 | 2011-07-20 | 浙江大学 | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal |
| CN103933871A (en) * | 2014-04-15 | 2014-07-23 | 南京工业大学 | Preparation method of all-silicon MFI type molecular sieve membrane with high stability |
| CN105540606A (en) * | 2016-01-14 | 2016-05-04 | 南京工业大学 | Method for synthesizing MFI zeolite with clay mineral as raw material in solvent-free mode |
| CN108751222A (en) * | 2018-06-25 | 2018-11-06 | 天津理工大学 | A kind of preparation method and its acoustic applications of the MFI molecular sieves with interaction twin pattern |
| CN109279621A (en) * | 2018-09-13 | 2019-01-29 | 浙江大学 | A method of using general ion thermal method synthesis of silica-base zeolite molecular sieve |
| US10843181B2 (en) | 2018-05-31 | 2020-11-24 | King Fahd University Of Petroleum And Minerals | Method of making a fluoride functionalized zeolite catalyst and method of use |
| CN112939003A (en) * | 2021-02-11 | 2021-06-11 | 贵州大学 | Method for preparing SBA-15 molecular sieve by using fluorine-containing silicon slag and recovering fluorine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0292363A2 (en) * | 1987-05-22 | 1988-11-23 | Rhone-Poulenc Chimie | Zeolites having an MFI-structure, based on silica and titanium oxide, and method for their synthesis |
| CN101182004A (en) * | 2006-11-14 | 2008-05-21 | 中国石油化工股份有限公司 | Method for preparing nano molecular sieve |
| CN101327934A (en) * | 2008-07-17 | 2008-12-24 | 连云港三吉利化学工业有限公司 | Preparation method of titanium-silicon molecular sieve with MFI structure |
| FR2936791A1 (en) * | 2008-10-07 | 2010-04-09 | Inst Francais Du Petrole | Preparing MFI structural type zeolite, useful e.g. as catalyst support, adsorbent or separation agent, comprises mixing source of tetravalent element and quaternary amine compound in aqueous medium and hydrothermal treatment of mixture |
-
2010
- 2010-05-24 CN CN2010101811710A patent/CN101837990B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0292363A2 (en) * | 1987-05-22 | 1988-11-23 | Rhone-Poulenc Chimie | Zeolites having an MFI-structure, based on silica and titanium oxide, and method for their synthesis |
| CN101182004A (en) * | 2006-11-14 | 2008-05-21 | 中国石油化工股份有限公司 | Method for preparing nano molecular sieve |
| CN101327934A (en) * | 2008-07-17 | 2008-12-24 | 连云港三吉利化学工业有限公司 | Preparation method of titanium-silicon molecular sieve with MFI structure |
| FR2936791A1 (en) * | 2008-10-07 | 2010-04-09 | Inst Francais Du Petrole | Preparing MFI structural type zeolite, useful e.g. as catalyst support, adsorbent or separation agent, comprises mixing source of tetravalent element and quaternary amine compound in aqueous medium and hydrothermal treatment of mixture |
Non-Patent Citations (1)
| Title |
|---|
| 《催化学报》 20081231 童伟益等 ZSM-5/Silicalite-1核壳分子筛含氟水热体系的合成及表征 1247-1252 1-6 第29卷, 第12期 2 * |
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|---|---|---|---|---|
| CN102126731A (en) * | 2011-01-31 | 2011-07-20 | 浙江大学 | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal |
| CN103933871A (en) * | 2014-04-15 | 2014-07-23 | 南京工业大学 | Preparation method of all-silicon MFI type molecular sieve membrane with high stability |
| CN103933871B (en) * | 2014-04-15 | 2016-02-10 | 南京工业大学 | A kind of preparation method of high stability all-silica MFI type molecular screen membrane |
| CN105540606A (en) * | 2016-01-14 | 2016-05-04 | 南京工业大学 | Method for synthesizing MFI zeolite with clay mineral as raw material in solvent-free mode |
| CN105540606B (en) * | 2016-01-14 | 2018-05-29 | 南京工业大学 | It is a kind of using clay mineral as the method for raw material uninanned platform MFI type zeolite |
| US10843181B2 (en) | 2018-05-31 | 2020-11-24 | King Fahd University Of Petroleum And Minerals | Method of making a fluoride functionalized zeolite catalyst and method of use |
| US11123727B2 (en) | 2018-05-31 | 2021-09-21 | King Fahd University Of Petroleum And Minerals | Method for converting a C4-C6 olefin into ethylene, propylene and/or butylene |
| CN108751222A (en) * | 2018-06-25 | 2018-11-06 | 天津理工大学 | A kind of preparation method and its acoustic applications of the MFI molecular sieves with interaction twin pattern |
| CN109279621A (en) * | 2018-09-13 | 2019-01-29 | 浙江大学 | A method of using general ion thermal method synthesis of silica-base zeolite molecular sieve |
| CN112939003A (en) * | 2021-02-11 | 2021-06-11 | 贵州大学 | Method for preparing SBA-15 molecular sieve by using fluorine-containing silicon slag and recovering fluorine |
| CN112939003B (en) * | 2021-02-11 | 2022-10-14 | 贵州大学 | Method for preparing SBA-15 molecular sieve by using fluorine-containing silicon slag and recovering fluorine |
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