CN111939966B - Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide - Google Patents

Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide Download PDF

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CN111939966B
CN111939966B CN202010854450.2A CN202010854450A CN111939966B CN 111939966 B CN111939966 B CN 111939966B CN 202010854450 A CN202010854450 A CN 202010854450A CN 111939966 B CN111939966 B CN 111939966B
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molecular sieve
methylmorpholine
sieve catalyst
basic
methylmorpholine oxide
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CN111939966A (en
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邢波
宋翔
杨郭
刘兴勇
王斌
罗文�
叶宇玲
莫莎
兰勇
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SICHUAN INSTITUTE OF FINE CHEMICAL INDUSTRY RESEARCH AND DESIGN
Sichuan University of Science and Engineering
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/24—Oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a basic molecular sieve, a preparation method thereof and application thereof in synthesizing N-methylmorpholine oxide. When the basic molecular sieve catalyst is prepared, the molecular sieve carrier is firstly put into an alkali metal salt solution for dipping, then dried and calcined in a nitrogen atmosphere, thus obtaining the basic molecular sieve catalyst. When preparing N-methylmorpholine oxide, mixing the prepared basic molecular sieve catalyst with N-methylmorpholine, then introducing ozone into the mixture, controlling the reaction temperature to be 30-90 ℃, and reacting for 3-9 h to obtain the N-methylmorpholine oxide. The invention provides a basic molecular sieve, a preparation method thereof and application thereof in preparing N-methylmorpholine oxide (NMMO), wherein ozone is used for replacing H 2 O 2 The alkaline molecular sieve catalyst provided by the invention effectively improves the conversion rate and selectivity of the NMMO synthesized by ozone catalytic oxidation.

Description

Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide
Technical Field
The invention belongs to the technical field of catalytic oxidation synthesis, and particularly relates to an alkaline molecular sieve, a preparation method thereof and application thereof in synthesizing N-methylmorpholine oxide.
Background
N-methyl oxygenMorpholine Oxide (NMMO) is a solvent for preparing Lyocell fiber in common use, the yield of the Lyocell fiber exceeds that of the terylene of the current chemical fiber with the largest variety, the economic benefit is obvious, and the further development of the NMMO is inevitably driven. NMMO is a tertiary amine oxide, and H is used as the main process for industrially synthesizing NMMO 2 O 2 As an oxidant, N-methylmorpholine (NMM) is catalytically oxidized under the action of a basic catalyst to synthesize NMMO. Most of the traditional base catalysis reaction adopts NaOH, KOH or Na 2 CO 3 The solution is used as a catalyst to carry out catalytic reaction. However, the process has major problems: (1) H 2 O 2 Easy decomposition and difficult storage, obtains high-quality NMMO, needs to add excessive oxidant into a reaction system, and increases the risk of cost and production safety; (2) H adopted in the reaction 2 O 2 A certain amount of water is brought into the reaction, so that the pressure of the subsequent rectification is increased; (3) The liquid catalyst is difficult to separate from the product, and has great industrial limitation. Therefore, the development of the efficient synthesis process of the NMMO has important practical significance on the development of the textile industry, and meanwhile, the efficient synthesis process of the NMMO provides raw material support for the rapid development of Lyocell fibers in China.
Disclosure of Invention
Aiming at the prior art, the invention provides a basic molecular sieve, a preparation method thereof and application thereof in synthesizing N-methylmorpholine oxide (NMMO), wherein ozone is used for replacing H 2 O 2 And the introduction of moisture is avoided. The alkaline molecular sieve catalyst provided by the invention effectively improves the conversion rate and selectivity of the NMMO synthesized by ozone catalytic oxidation.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a basic molecular sieve catalyst is provided, which comprises the following steps:
s1: putting the molecular sieve carrier into an alkali metal salt solution with the concentration of 0.1-1 mol/L for soaking for 0.5-3 h, filtering, and drying at the temperature of 75-85 ℃ for 10-15 h to obtain an alkaline molecular sieve precursor; the mass ratio of the molecular sieve carrier to the solute of the alkali metal salt solution is 100;
at N 2 Under the protection, the precursor of the basic molecular sieve is put inCalcining for 2-4 h at 400-650 ℃ to obtain the basic molecular sieve catalyst.
On the basis of the technical scheme, the invention can be further improved as follows.
Furthermore, the molecular sieve carrier is MCM-41 mesoporous molecular sieve or SBA-15 mesoporous molecular sieve.
Further, the solute of the alkali metal salt solution is MgCl 2 、CaCl 2 、Ca(NO 3 ) 2 、SrCl 2 、Sr(NO 3 ) 2 、RbCl、RbNO 3 、AlCl 3 、Al(NO 3 ) 3 、TiCl 4 、Cs 2 CO 3 Or Ti (NO) 3 ) 4 。
The method of the invention can obtain the basic molecular sieve catalyst with excellent catalytic performance. The basic metal salt exhibits excellent catalytic activity in olefin epoxidation, alcohol oxidation, aniline oxidation, and a process for synthesizing a tertiary amine oxide, and is used as a main active component to be loaded on a mesoporous molecular sieve in the present invention. The mesoporous molecular sieve material not only has excellent properties of large specific surface area, developed pore structure, easy-to-regulate surface property, hydrothermal resistance and the like, but also has larger pore diameter compared with the traditional microporous molecular sieve, thereby being more beneficial to the mass transfer of reactants and products. Therefore, after the mesoporous molecular sieve is loaded with the alkaline metal salt, the dispersion degree of the alkaline metal salt on the mesoporous molecular sieve can be improved, the number of catalytic active sites of the mesoporous molecular sieve is increased, and the catalytic activity is obviously improved.
The basic molecular sieve catalyst prepared by the invention can be used for olefin epoxidation, alcohol oxidation, aniline oxidation and a process for synthesizing tertiary amine oxide. Particularly for the synthesis of N-methylmorpholine oxide, the method has higher yield and the quality of the obtained product can be well ensured. The method for synthesizing N-methylmorpholine oxide by adopting the basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 0.1-5;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 20-50 mL/min, controlling the reaction temperature to be 30-90 ℃, and reacting for 3-9 h to obtain the N-methylmorpholine oxide.
The preparation of the N-methylmorpholine oxide can be improved as follows on the basis of the technical scheme.
Further, the mass ratio of the basic molecular sieve catalyst to the N-methylmorpholine in the reaction substrate is 1.
Further, the introduction rate of ozone in the S2 is 40mL/min; the reaction temperature was 60 ℃.
In the invention, alkaline molecular sieve is adopted to catalyze ozone to replace homogeneous catalyst to catalyze H 2 O 2 Can effectively solve the problems existing in the prior art. Alkaline molecular sieve catalyzed ozone compared with homogeneous catalyst for catalyzing H 2 O 2 Has the advantages that: (1) Ozone is a gaseous substance, and does not bring moisture into the reaction; (2) Ozone oxidation ratio H 2 O 2 The method has the advantages that the use cost of the oxidant is saved and the reaction time is shortened under the same reaction condition, so that the generation of side reactions of the NMMO is further reduced, and the quality of the NMMO is improved; (3) The alkaline molecular sieve is a heterogeneous catalyst integrating the characteristics of strong alkalinity, a high-surface-area molecular sieve, shape selectivity and the like, and compared with a liquid alkali homogeneous catalyst, the alkaline molecular sieve has the advantages of strong alkalinity, easiness in separation after reaction, high catalytic selectivity, small corrosion to equipment and recyclability.
The beneficial effects of the invention are:
1. the invention adopts the basic molecular sieve catalyst, and since the basic metal salt is used as a basic catalyst, the basic molecular sieve catalyst is commonly used for the base catalytic reaction (olefin epoxidation, alcohol oxidation, aniline oxidation, synthesis of tertiary amine oxide and the like); meanwhile, the molecular sieve carrier has rich pore structure and large specific surface area, thereby effectively easing reaction conditions and improving the activity of synthesizing N-methylmorpholine oxide by catalytic oxidation of ozone.
2. The invention adopts ozone to replace H 2 O 2 Catalytic oxidation synthesis of N-methyl morpholine oxide, ozone being compared with H 2 O 2 The oxidizing property is stronger, the subsequent separation and purification are easy, and the generated wastewater is less.
3. The method for synthesizing N-methylmorpholine oxide by catalyzing ozone oxidation based on the alkaline molecular sieve is simple, easy to operate and suitable for industrial production.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
Example 1
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. The synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: placing a molecular sieve carrier MCM-41 mesoporous molecular sieve into Cs with the concentration of 0.25mol/L 2 CO 3 Soaking the solution for 0.5h, filtering, and drying at 80 ℃ for 12h to obtain an alkaline molecular sieve precursor; MCM-41 mesoporous molecular sieve and Cs 2 CO 3 Cs in solution 2 CO 3 The ratio of the mass of (a) to (b) is shown in table 1;
s2: in N 2 And under protection, calcining the basic molecular sieve precursor at 500 ℃ for 3 hours to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 1;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 50mL/min, controlling the reaction temperature to be 30 ℃, and reacting for 4 hours to obtain the N-methylmorpholine oxide.
TABLE 1 influence of basic molecular sieve catalysts on N-methylmorpholine conversion and N-methylmorpholine oxide selectivity
MCM-41 and Cs 2 CO 3 Mass ratio of Conversion of N-methylmorpholine (%) N-methylmorpholine oxide selectivity (%)
100:0 54.8 72.6
100:5 69.2 81.3
100:10 78.1 84.2
100:15 87.1 94.6
100:20 82.3 91.7
The high performance liquid chromatography analysis of the conversion rate of N-methylmorpholine (NMM) and the selectivity of N-methylmorpholine oxide (NMMO) in the presence of 5 basic molecular sieve catalysts shows that (table 1 above), when NMMO is prepared by simply using a molecular sieve (100) which is not loaded with an alkali metal, the conversion rate of NMM and the selectivity of NMMO are both low, because the molecular sieve has few catalytic active sites and cannot promote the reaction between NMM and ozone. When MCM-41 and Cs 2 CO 3 When the mass ratio of (1) to (5) to (15) is 100. When MCM-41 and Cs 2 CO 3 When the mass ratio of (2) exceeds 100.
Example 2
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. Wherein, the synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: putting molecular sieve carrier SBA-15 mesoporous molecular sieve into RbNO with the concentration of 0.5mol/L 3 Soaking the solution for 1h, filtering, and drying at 80 ℃ for 12h to obtain an alkaline molecular sieve precursor; SBA-15 mesoporous molecular sieve and RbNO 3 RbNO in solution 3 The mass ratio of (A) to (B) is 100;
s2: at N 2 And under protection, calcining the basic molecular sieve precursor at the temperature shown in the table 2 for 3 hours to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 5;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 40mL/min, controlling the reaction temperature to be 40 ℃, and reacting for 5 hours to obtain the N-methylmorpholine oxide.
TABLE 2 influence of temperature on the conversion of N-methylmorpholine and the selectivity of N-methylmorpholine oxide
Figure BDA0002645893760000051
Figure BDA0002645893760000061
The high performance liquid chromatography analysis on the conversion rate of N-methylmorpholine and the selectivity of N-methylmorpholine oxide under 5 basic molecular sieve catalysts (Table 2 above) shows that the conversion rate of NMM and the selectivity of NMMO are low at a calcination temperature of 300 ℃, because the temperature is low, stable catalytic active sites are not sufficiently formed on the surface of the molecular sieve during calcination, and the catalytic efficiency is low during the reaction process. When the calcination temperature is 400-600 ℃, the conversion rate of the N-methylmorpholine and the selectivity of the N-methylmorpholine are increased along with the increase of the calcination temperature, which shows that the increase of the calcination temperature is beneficial to improving the activity of the alkaline molecular sieve for catalyzing the ozone oxidation to synthesize the N-methylmorpholine. After the calcination temperature exceeds 600 ℃, the structure of the molecular sieve can be damaged in the calcination process, and meanwhile, the adhesion state of alkali metal on the molecular sieve is changed, so that the catalytic activity of the basic molecular sieve catalyst is reduced, and further the conversion rate of NMM and the selectivity of NMMO are influenced.
Example 3
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. Wherein, the synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: putting a molecular sieve carrier SBA-15 mesoporous molecular sieve into SrCl with the concentration of 1mol/L 2 Soaking the solution for 0.5h, filtering, and drying at 75 ℃ for 15h to obtain an alkaline molecular sieve precursor; SBA-15 mesoporous molecular sieve and SrCl 2 SrCl in solution 2 The mass ratio of (A) to (B) is 100;
s2: at N 2 And under protection, calcining the precursor of the basic molecular sieve at 500 ℃ for 4h to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to the mass ratio shown in table 3 to obtain a reaction substrate;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 45mL/min, controlling the reaction temperature at 50 ℃, and reacting for 4 hours to obtain the N-methylmorpholine oxide.
TABLE 3 influence of the mass ratio of basic molecular sieves to N-methylmorpholine on the N-methylmorpholine conversion and N-methylmorpholine oxide selectivity
Mass ratio of basic molecular sieve to N-methylmorpholine Conversion of N-methylmorpholine (%) N-methylmorpholine oxide selectivity (%)
0.1:100 47.2 66.4
1:100 69.8 78.3
2:100 77.6 84.1
3.5:100 82.5 95.12
5:100 88.2 98.7
The high performance liquid chromatography is used for analyzing the N-methylmorpholine conversion rate and the N-methylmorpholine oxide selectivity under the mass ratio of 5 basic molecular sieve catalysts to N-methylmorpholine (table 3 above), wherein the mass ratio is in the range of 0.1-5, and more basic molecular sieve catalysts are added to facilitate the increase of the N-methylmorpholine conversion rate and the N-methylmorpholine oxide selectivity, which shows that the improvement of the addition of the basic molecular sieves is beneficial to the improvement of the activity of the basic molecular sieves for catalyzing the ozone oxidation to synthesize the N-methylmorpholine oxide.
Example 4
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. Wherein, the synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: putting a molecular sieve carrier MCM-41 mesoporous molecular sieve into CaCl with the concentration of 0.1mol/L 2 Soaking the solution for 3 hours, filtering and drying the solution for 10 hours at 85 ℃ to obtain an alkaline molecular sieve precursor; SBA-15 mesoporous molecular sieve and CaCl 2 CaCl in solution 2 The mass ratio of (A) to (B) is 100;
s2: in N 2 And under protection, calcining the precursor of the basic molecular sieve at 400 ℃ for 4h to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 3;
s2: under normal pressure, continuously introducing ozone into the reaction substrate at the speed of 35mL/min, controlling the reaction temperature to be 80 ℃, and reacting under the reaction time shown in the table 4 to obtain the N-methylmorpholine oxide.
TABLE 4 influence of reaction time on N-methylmorpholine conversion and N-methylmorpholine oxide selectivity
Reaction time (hours) Conversion of N-methylmorpholine (%) N-methylmorpholine oxide Selectivity (%)
3 49.4 65.7
5 89.2 94.3
7 92.6 98.5
9 84.5 93.8
The conversion rate of N-methylmorpholine (NMM) and the selectivity of N-methylmorpholine oxide (NMMO) in 4 reaction times are analyzed by high performance liquid chromatography, and the results show that when the reaction time is 3-7 hours, the conversion rate of N-methylmorpholine and the selectivity of N-methylmorpholine oxide increase with the increase of the reaction time, which indicates that the increase of the reaction time is beneficial to improving the activity of N-methylmorpholine oxide synthesized by ozone oxidation under the catalysis of an alkaline molecular sieve. When the reaction time exceeds 7 hours, side reactions increase, which not only does not improve the reaction efficiency, but also reduces the conversion rate of NMM and the selectivity of NMMO.
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.

Claims (4)

1. The application of the basic molecular sieve catalyst in synthesizing N-methylmorpholine oxide is characterized by comprising the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 0.1-5; the basic molecular sieve catalyst is prepared by the following steps:
and (4) SS1: putting the molecular sieve carrier into an alkali metal salt solution with the concentration of 0.1-1 mol/L for soaking for 0.5-3 h, filtering, and drying at 75-85 ℃ for 10-15 h to obtain an alkaline molecular sieve precursor; the mass ratio of the molecular sieve carrier to the solute of the alkali metal salt solution is 100; the molecular sieve carrier is an MCM-41 mesoporous molecular sieve or an SBA-15 mesoporous molecular sieve;
and (4) SS2: in N 2 Calcining the precursor of the basic molecular sieve at 400-650 ℃ for 2-4 h under protection to obtain a basic molecular sieve catalyst;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 20-50 mL/min, controlling the reaction temperature to be 30-90 ℃, and reacting for 3-9 h to obtain the N-methylmorpholine oxide.
2. Use according to claim 1, characterized in that: the mass ratio of the basic molecular sieve catalyst to the N-methylmorpholine in the reaction substrate is 1.
3. Use according to claim 1, characterized in that: the ozone introducing speed in the S2 is 40mL/min; the reaction temperature was 60 ℃.
4. Use according to claim 1, characterized in that: the solute of the alkali metal salt solution is MgCl 2 、CaCl 2 、Ca(NO 3 ) 2 、SrCl 2 、Sr(NO 3 ) 2 、RbCl、RbNO 3 、AlCl 3 、Al(NO 3 ) 3 、TiCl 4 、Cs 2 CO 3 Or Ti (NO) 3 ) 4 。
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