CN111482177A - Catalyst for preparing hydrogenated terphenyl and preparation method and application thereof - Google Patents

Catalyst for preparing hydrogenated terphenyl and preparation method and application thereof Download PDF

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CN111482177A
CN111482177A CN202010377323.8A CN202010377323A CN111482177A CN 111482177 A CN111482177 A CN 111482177A CN 202010377323 A CN202010377323 A CN 202010377323A CN 111482177 A CN111482177 A CN 111482177A
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catalyst
nib
mgo
washing
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王海波
徐宁
王晴
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Jiangsu Xinhe Agricultural Chemical Co ltd
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Jiangsu Xinhe Agricultural Chemical Co ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B01J35/40—
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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Abstract

The invention relates to a catalyst for preparing hydrogenated terphenyl, a preparation method and application thereof, wherein the catalyst comprises a carrier and an active component, the carrier comprises MgO, the active component comprises a NiB compound, the molar ratio of Ni to B in the NiB compound is 1 (0.34-0.4), the catalyst is used for catalyzing the hydrogenation of mixed terphenyl to prepare the hydrogenated terphenyl, and has the advantages of good selectivity, high conversion rate and more application times.

Description

Catalyst for preparing hydrogenated terphenyl and preparation method and application thereof
Technical Field
The invention belongs to the field of organic synthesis, and relates to a catalyst for preparing hydrogenated terphenyl, a preparation method and application thereof.
Background
Hydrogenated terphenyl is heat conducting oil with excellent performance, and the main component of the hydrogenated terphenyl is a mixture of partially hydrogenated terphenyl isomers, and the hydrogenated terphenyl is obtained by partially hydrogenating a mixture of ortho-terphenyl, meta-terphenyl and para-terphenyl in different proportions (the saturation is 39%). Hydrogenated terphenyl has the characteristics of excellent thermal stability, oxidation resistance, low vapor pressure and the like, is widely applied to fine chemical industries such as petrochemical industry, synthetic fibers, synthetic resins, medicines, printing and dyeing, organic silicon monomer synthesis and the like, and is an important fine petrochemical product which needs to be developed at home.
The synthetic route of hydrogenated terphenyl at home and abroad is mainly prepared by adopting the catalytic hydrogenation of mixed terphenyl. The synthesis technology for preparing hydrogenated terphenyl by catalytic hydrogenation of mixed terphenyl has the characteristics of mild reaction conditions, simple production process, low cost and easily obtained raw materials, and the core technology of the method is a catalyst.
The process of preparing hydrogenated terphenyl by catalytic hydrogenation of mixed terphenyl is analyzed from an organic synthesis mechanism, and is subjected to a link of generating an intermediate through partial hydrogenation, so that the intermediate is easy to further react with a reaction intermediate product and a target product, a plurality of byproducts are generated through reaction, the reaction conversion rate, the selectivity and the yield are reduced, meanwhile, the byproducts are easy to coke at the reaction temperature and are adsorbed on the surface of a catalyst, the catalyst poisoning is caused, the number of times of applying the catalyst is seriously reduced, the product quality is reduced, and the production cost is increased. Therefore, the development of the catalyst with high selectivity and high activity is strengthened as the key of catalytic hydrogenation, and manufacturers at home and abroad carry out a great deal of research on the catalyst.
Generally, platinum oxide or modified noble metal catalysts are mainly used for preparing hydrogenated terphenyl by catalytic hydrogenation, but the series of catalysts have the disadvantages of poor activity, poor selectivity, low conversion rate, easy poisoning and inactivation and high preparation cost, so that the preparation cost of the hydrogenated terphenyl is high.
CN103804114A discloses a process for preparing hydrogenated terphenyls, comprising the steps of: (1) synthesizing biphenyl; (2) performing primary rectification; (3) performing secondary rectification; (4) hydrogenation; the scheme does not give which catalyst is adopted for the hydrogenation reaction, and does not give the conditions of the hydrogenation reaction;
CN107032942A discloses a method for using rectified organic solid residue in the production of biphenol to conduct thermal oil, which comprises the following steps: (1) adding coupling rectification residues containing 2-methyl-3-chlorobiphenyl, 1, 3-diphenyl toluene, 1-phenyl-3- (2 '-methyl-3' -chlorine) phenyl toluene and 1,3- (2 '-methyl-3' -chlorine) diphenyl toluene into a solvent for dissolving; (2) adding activated carbon for decolorization, filtering, distilling to remove a solvent, transferring into a high-pressure kettle, adding a catalyst and an acid-binding agent, performing nitrogen replacement for three times, performing hydrogen replacement for three times, heating to 200-350 ℃, starting stirring, introducing hydrogen, reacting, filtering to remove the catalyst, transferring into a rectifying kettle, performing reduced pressure rectification, and collecting to obtain mixed hydrogenated terphenyl, wherein the adopted catalyst is activated carbon loaded with 5% of ruthenium and 0.3% of palladium; the method of the scheme has the problems of high preparation process cost, low catalytic activity of the catalyst, poor selectivity on the generated hydrogenated terphenyl and short catalytic life.
Therefore, the development of a catalyst with high catalytic efficiency, high selectivity and long catalytic life and a preparation method of hydrogenated terphenyl are still significant.
Disclosure of Invention
The invention aims to provide a catalyst for preparing hydrogenated terphenyl, a preparation method and application thereof, wherein the catalyst comprises a carrier and an active component, the carrier comprises MgO, the active component comprises a NiB compound, the molar ratio of Ni to B in the NiB compound is 1 (0.34-0.4), the catalyst is used for catalyzing the hydrogenation of mixed terphenyl to prepare the hydrogenated terphenyl, and has the advantages of good selectivity, high conversion rate and multiple application times.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst for the production of hydrogenated terphenyls, the catalyst comprising a support comprising MgO and an active component comprising a NiB compound in which Ni and B are present in a molar ratio of 1 (0.34-0.4), such as 1:0.35, 1:0.36, 1:0.37, 1:0.38 or 1:0.39, etc.
The carrier in the catalyst comprises MgO, the active component comprises a NiB compound with the molar ratio of Ni to B being 1 (0.34-0.4), and when the NiB compound is used for preparing hydrogenated terphenyl by using mixed terphenyl of the catalyst, the selectivity of the product hydrogenated terphenyl is high, the selectivity of the product hydrogenated terphenyl can reach 96 percent, the conversion rate of the mixed terphenyl is high, the conversion rate can reach 98 percent, the stability of the catalyst is good, and the application frequency can reach 8 times; further solves the problems of poor catalyst activity, poor selectivity, low conversion rate and high production cost in the traditional hydrogenated terphenyl preparation process.
Because the mixed terphenyl belongs to petrochemical products, trace impurities in the mixed terphenyl easily cause poisoning of a noble metal catalyst, the catalyst is not easy to be poisoned and inactivated in the process of preparing hydrogenated terphenyl by using the mixed terphenyl, and has high stability.
Preferably, the mass percentage of the NiB compound in the catalyst is 5-18%, for example 6%, 8%, 10%, 12%, 14% or 16% and the like, based on 100% by mass of the catalyst.
Preferably, the particle size of the support is 250-300nm, such as 260nm, 270nm, 280nm, 290nm, and the like.
The particle size of the magnesium oxide used as the carrier in the catalyst is 250-300nm, and when the magnesium oxide is used as the carrier to load a NiB compound as an active component, the obtained catalyst has high stability, the activity of the catalyst is reduced slightly after repeated application, the catalyst has high conversion rate, and the catalyst has high selectivity on the product hydrogenated terphenyl.
Preferably, the active component is present in amorphous form.
In a second aspect, the present invention provides a process for the preparation of a catalyst as described in the first aspect, the process comprising the steps of:
(1) soaking magnesium oxide powder in silver source solution to obtain Ag2O/MgO；
(2) Ag obtained in the step (1)2O/MgO is dispersed in the NiB plating solution,and carrying out reaction to obtain the catalyst.
In the preparation process of the catalyst, Ag is used as an inducer to prepare Ag2O/MgO, and then completing chemical plating reaction in NiB plating solution to obtain the catalyst; the preparation process is simple and the cost is low.
Preferably, the silver source of step (1) comprises silver nitrate.
Preferably, Ag in step (1)2The amount of Ag element supported in O/MgO is 0.11 to 0.15 wt%, for example, 0.12 wt%, 0.13 wt%, or 0.14 wt%, etc.
Preferably, the impregnation process of step (1) is accompanied by stirring.
Preferably, the temperature of the impregnation is 35-45 ℃, such as 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃ or 44 ℃ and the like.
Preferably, the time of the impregnation is 3-5h, such as 3.5h, 4h or 4.5h, etc.
Preferably, the impregnation in step (1) further comprises solid-liquid separation and drying.
Preferably, the method of solid-liquid separation comprises suction filtration.
Preferably, the drying is air drying.
Preferably, the drying time is 20-28h, such as 21h, 22h, 23h, 24h, 25h, 26h or 27h, etc.
Preferably, the NiB plating solution in the step (2) contains nickel salt and KBH4Ethylenediamine, NaOH and a solvent.
Preferably, the solvent comprises water.
Preferably, the nickel salt comprises nickel sulfate.
Preferably, Ni is contained in the NiB plating solution in the step (2)2+、KBH4The molar ratio of ethylenediamine to NaOH is 1 (0.8-2.1) to (4.3-5.9) to (12-19.2), for example 1:2.03:4.37:12.04, 1:1.5:5:14 or 1:0.82:5.83:19.16, preferably 1 (2-2.05) to (4.3-4.5) to (12-12.1).
Preferably, in the NiB plating solution in the step (2), the Ni content in the Ni salt is 2-3 g/L, such as 2.1 g/L, 2.2 g/L, 2.3 g/L, 2.4 g/L, 2.5 g/L, 2.6 g/L, 2.7 g/L, 2.8 g/L or 2.9 g/L.
Preferably, in the NiB plating solution in the step (2), KBH4The content of (b) is 2-5 g/L, for example 2.5 g/L, 3 g/L, 3.5 g/L, 4 g/L or 4.5 g/L.
Preferably, the content of the ethylenediamine in the NiB plating solution in the step (2) is 12-16 g/L, such as 12.5 g/L, 13 g/L, 13.5 g/L, 14 g/L, 14.5 g/L, 15 g/L or 15.5 g/L, and the like.
Preferably, in the NiB plating solution in the step (2), the content of NaOH is 22-35 g/L, such as 23 g/L, 24 g/L0, 25 g/L1, 26 g/L2, 27 g/L, 28 g/L, 29 g/L, 30 g/L, 31 g/L, 32 g/L, 33 g/L or 34 g/L, and the like.
Preferably, Ag in step (2)2The ratio of the mass of O/MgO to the volume of the NiB plating solution is 8-12 g/L, such as 8.5 g/L, 9 g/L, 9.5 g/L, 10 g/L, 10.5 g/L, 11 g/L or 11.5 g/L.
Ag control in the preparation process of the catalyst2The ratio of the mass of O/MgO to the volume of the NiB plating solution is in the range, which is beneficial to increasing the number of active sites on the surface of the prepared catalyst, further improving the activity of the catalyst and the selectivity of the product hydrogenated terphenyl, and simultaneously being beneficial to prolonging the service life of the catalyst.
Preferably, the reaction in step (2) is carried out at a temperature of 40-50 deg.C, such as 42 deg.C, 44 deg.C, 46 deg.C or 48 deg.C.
The temperature for reaction is controlled within the range in the preparation process of the catalyst, so that the service life of the catalyst is favorably optimized, and the catalytic activity and the selectivity of the product hydrogenated terphenyl are improved; when the temperature is lower than 40 ℃, the reaction speed is lower, and when the temperature is higher than 50 ℃, the product is easy to polymerize when the obtained catalyst is used for catalysis, and the number of hydrogenation reaction byproducts is increased.
Preferably, the reaction in step (2) is carried out with stirring.
Preferably, the heating mode in the process of carrying out the reaction in the step (2) is water bath heating.
Preferably, the reaction in step (2) is carried out for a time of 0.3 to 2h, such as 0.5h, 0.8h, 1h, 1.2h, 1.5h or 1.8h, etc.
Preferably, the reaction in the step (2) also comprises solid-liquid separation and washing after the reaction is finished.
Preferably, the washing agent used for washing is water and anhydrous methanol.
Preferably, the washing method is to wash the mixture to be neutral by water and then wash the mixture by anhydrous methanol.
Preferably, the washing with anhydrous methanol further comprises storing the catalyst in anhydrous methanol.
The catalyst is washed by the absolute methanol solution and stored in the absolute methanol, which is beneficial to the storage of the catalyst, and the methanol has the characteristics of lower cost and convenient recovery compared with ethanol, thereby reducing the industrial application cost.
As a preferred technical scheme of the invention, the preparation method of the catalyst comprises the following steps:
(1) soaking magnesium oxide powder in silver nitrate solution, stirring at 35-45 deg.C for 3-5 hr, vacuum filtering, separating, and air drying to obtain Ag with Ag loading of 0.11-0.15 wt%2O/MgO；
(2) Ag obtained in the step (1)2Dispersing O/MgO in NiB plating solution, heating and stirring for 0.3-2h in water bath at 40-50 ℃, carrying out solid-liquid separation, washing with water to neutrality, and washing with anhydrous methanol to obtain the catalyst.
In a third aspect, the present invention provides the use of a catalyst as described in the first aspect for the catalytic hydrogenation of mixed terphenyls to produce hydrogenated terphenyls.
Preferably, the method for catalyzing the hydrogenation of the mixed terphenyl comprises the steps of mixing the catalyst, the mixed terphenyl and methanol, introducing hydrogen, and reacting to obtain the hydrogenated terphenyl.
Preferably, the reaction is carried out in a stainless steel autoclave.
Preferably, the reaction is carried out at a temperature of 85-95 deg.C, such as 86 deg.C, 87 deg.C, 88 deg.C, 89 deg.C, 90 deg.C, 91 deg.C, 92 deg.C, 93 deg.C or 94 deg.C.
Preferably, the pressure of the hydrogen during the reaction is 5-8MPa, such as 5.5MPa, 6MPa, 6.5MPa, 7MPa or 7.5MPa, etc.
Preferably, the mass ratio of the catalyst, the mixed terphenyl and the methanol is 1 (100-180) to (100-180), such as 1:150:150, 1:166.6:166.6 or 1:175:175, etc., preferably 1 (160-170) to (160-170).
Compared with the prior art, the invention has the following beneficial effects:
(1) the carrier of the catalyst comprises MgO, the active component comprises a NiB compound with the molar ratio of Ni to B being 1 (0.34-0.4), and the NiB compound is used in the process of preparing hydrogenated terphenyl by catalyzing hydrogenation of mixed terphenyl, has high catalytic activity on the mixed terphenyl, has high selectivity on the product hydrogenated terphenyl, has small catalyst dosage and high hydrogenated terphenyl yield, further reduces the production cost, and has good popularization and application values;
(2) the catalyst has high stability in the process of catalyzing hydrogenation of mixed terphenyl, the application frequency can reach 8 times, and the service life of the catalyst is long;
(3) the catalyst has the advantages of simple preparation process, wide raw material source, small occupied area and small equipment investment by adopting a powder chemical plating method.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In the catalyst of this embodiment, MgO is used as a carrier, a NiB compound is used as an active component, the molar ratio of Ni to B is 2.5, and the mass percentage content of the NiB compound in the catalyst is 14.79%; the active component exists in an amorphous state, and the particle size of the carrier is 270 nm; the preparation method of the catalyst comprises the following steps:
(1) 50g of MgO powder are added to 100m L of AgNO3Stirring the solution (the mass fraction of the loaded Ag is controlled to be 0.12%) for 4h at 313K, then carrying out suction filtration on the sample, and airing the sample in the air for 24h to obtain the Ag2O/MgO for standby;
(2) will be provided with1.6g of Ag in step (1)2O/MgO powder was added to a NiB bath of 150m L (bath composition: 5 g/L KBH)4、12g/L NiSO4·6H2O, 12 g/L ethylenediamine and 22 g/L NaOH), then heating and stirring in 318K water bath for 30min to obtain black NiB/MgO amorphous catalyst, washing the catalyst with deionized water to neutrality, washing with anhydrous methanol for 3 times, and storing in anhydrous methanol.
The catalyst obtained in this example was tested for catalytic activity, and the test conditions for hydrogenation of mixed terphenyls to produce hydrogenated terphenyls are as follows:
0.6g of the catalyst prepared in the embodiment, 100g of mixed terphenyl and 100g of methanol are added into a stainless steel autoclave with the thickness of 500m L, hydrogen is introduced, the temperature is increased to 363K, the hydrogen is introduced to 5MPa until the reaction is finished, the saturation rate of the hydrogenated terphenyl is 39 percent, the catalyst is filtered and reused, the number of times of use reaches 8, and the activity is not reduced.
Example 2
In the catalyst of this embodiment, MgO is used as a carrier, a NiB compound is used as an active component, the molar ratio of Ni to B is 2.5, and the mass percentage content of the NiB compound in the catalyst is 14.79%; the active component exists in an amorphous state, and the particle size of the carrier is 280 nm; the preparation method of the catalyst comprises the following steps:
(1) 50g of MgO powder are added to 100m L of AgNO3Stirring the solution (the mass fraction of the loaded Ag is controlled to be 0.12%) for 4h at 313K, then carrying out suction filtration on the sample, and airing the sample in the air for 24h to obtain the Ag2O/MgO for standby;
(2) mixing 1.6g of Ag in the step (1)2O/MgO powder was added to a NiB bath of 150m L (bath composition 5 g/L KBH)4、12g/L NiSO4·6H2O, 16 g/L ethylenediamine and 35 g/L NaOH), then heating and stirring in 318K water bath for 30min to obtain black NiB/MgO amorphous catalyst, washing the catalyst with deionized water to neutrality, washing with anhydrous methanol for 3 times, and storing in anhydrous methanol.
The activity test method of the catalyst in the embodiment is the same as that in the embodiment 1, the saturation rate of the hydrogenated terphenyl obtained by testing is 35%, and the catalyst can be filtered and reused for 5 times.
Example 3
In the catalyst of this embodiment, MgO is used as a carrier, a NiB compound is used as an active component, the molar ratio of Ni to B is 2.82, and the mass percentage content of the NiB compound in the catalyst is 12.31%; the active component exists in an amorphous state, and the particle size of the carrier is 290 nm; the preparation method of the catalyst comprises the following steps:
(1) 50g of MgO powder are added to 100m L of AgNO3Stirring the solution (the mass fraction of the loaded Ag is controlled to be 0.12%) for 4h at 313K, then carrying out suction filtration on the sample, and airing the sample in the air for 24h to obtain the Ag2O/MgO for standby;
(2) mixing 1.6g of Ag in the step (1)2O/MgO powder was added to a NiB bath of 150m L (bath composition 2 g/L KBH)4、12g/L NiSO4·6H2O, 16 g/L ethylenediamine and 35 g/L NaOH), then heating and stirring in 318K water bath for 30min to obtain black NiB/MgO amorphous catalyst, washing the catalyst to be neutral by deionized water, washing 3 times by anhydrous methanol, and storing in the anhydrous methanol.
The method for testing the catalytic activity of the catalyst in the embodiment is the same as that in the embodiment 1, the saturation rate of the hydrogenated terphenyl obtained by testing is 35%, and the catalyst can be filtered and reused for 5 times.
Example 4
This example differs from example 1 in that the silver nitrate solution in step (1) was replaced with 50m L silver nitrate solution at an equal concentration to obtain Ag2The mass fraction of Ag supported on O/MgO was 0.09%, and other conditions and parameters were exactly the same as those in example 1.
The catalyst obtained in this example was tested for catalytic activity, and the test conditions for hydrogenation of mixed terphenyls to produce hydrogenated terphenyls are as follows:
1g of the catalyst prepared in the embodiment, 100g of mixed terphenyl and 100g of methanol are added into a stainless steel autoclave with the thickness of 500m L, hydrogen is introduced, the temperature is raised to 363K, the hydrogen is introduced to 8MPa until the reaction is finished, the saturation rate of the hydrogenated terphenyl is 35 percent, and the catalyst is filtered and reused for 3 times.
Example 5
This example differs from example 1 in that the silver nitrate solution of equal concentration in step (1) was replaced with 200m L silver nitrate solution to obtain Ag2The mass fraction of Ag supported on O/MgO was 0.16 wt%, and other conditions and parameters were exactly the same as those in example 1.
The method for testing the catalytic activity of the catalyst in the embodiment is the same as that in the embodiment 1, the saturation rate of the hydrogenated terphenyl obtained by testing is 35%, and the catalyst can be filtered and reused for 3 times.
Example 6
This example is different from example 1 in that the particle diameter of the carrier MgO is 150nm, and other parameters and conditions are completely the same as those in example 1.
The method for testing the catalytic activity of the catalyst in the embodiment is the same as that in the embodiment 1, the saturation rate of the hydrogenated terphenyl obtained by testing is 32%, and the catalyst can be filtered and reused for 4 times.
Example 7
This example is different from example 1 in that the particle diameter of the carrier MgO is 400nm, and other parameters and conditions are completely the same as those in example 1.
The method for testing the catalytic activity of the catalyst in the embodiment is the same as that in the embodiment 1, the saturation rate of the hydrogenated terphenyl obtained by testing is 33%, and the catalyst can be filtered and reused for 3 times.
Comparative example 1
The comparative example is different from example 1 in that the particle size of the carrier is replaced by alumina, and other parameters and conditions are the same as those of example 1.
The method for testing the catalytic activity of the catalyst in the comparative example is the same as that in example 1, the saturation rate of the hydrogenated terphenyl obtained by testing is 30%, the effect is poor, and no application experiment is carried out.
The test method comprises the following steps: adopting a gas chromatography analysis and area normalization method;
the results of the tests for selectivity to mixed terphenyls and selectivity to hydrogenated terphenyls in examples 1-7 and comparative example 1 are shown in table 1;
TABLE 1
Figure BDA0002480457120000111
As can be seen from the table above, when the catalyst is used in the process of preparing hydrogenated terphenyl by hydrogenating mixed terphenyl, the mixed terphenyl has high conversion rate which can reach 98 percent, and the catalyst has high selectivity to the product hydrogenated terphenyl, and the selectivity can reach 96 percent; clearly superior to the catalyst in comparative example 1.
As can be seen from comparison of examples 1, 4 and 5, the catalyst of the present invention was prepared using Ag as an inducing agent2When the mass fraction of Ag loaded in O/MgO is 0.011-0.15%, the obtained catalyst has better catalytic activity and stability; as can be seen from comparison of examples 1, 6 and 7, the catalyst of the present invention preferably has a MgO support particle size of 250-300nm for use in the preparation of hydrogenated terphenyl, and if the support particle size is too large or too small, the stability and catalytic activity of the obtained catalyst are reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A catalyst for preparing hydrogenated terphenyl is characterized by comprising a carrier and an active component, wherein the carrier comprises MgO, the active component comprises a NiB compound, and the molar ratio of Ni to B in the NiB compound is 1 (0.34-0.4).
2. The catalyst according to claim 1, wherein the mass percent of the NiB compound in the catalyst is 5-18% based on 100% of the mass of the catalyst;
preferably, the particle size of the carrier is 250-300 nm;
preferably, the active component is present in amorphous form.
3. A process for the preparation of a catalyst according to claim 1 or 2, characterized in that it comprises the following steps:
(1) soaking magnesium oxide powder in silver source solution to obtain Ag2O/MgO；
(2) Ag obtained in the step (1)2And dispersing O/MgO in the NiB plating solution to react to obtain the catalyst.
4. The method of claim 3, wherein the silver source of step (1) comprises silver nitrate;
preferably, Ag in step (1)2The load amount of Ag element in O/MgO is 0.11-0.15 wt%;
preferably, the impregnation process of step (1) is accompanied by stirring;
preferably, the temperature of the impregnation is 35-45 ℃;
preferably, the time for the impregnation is 3-5 h;
preferably, the impregnation in the step (1) further comprises solid-liquid separation and drying;
preferably, the solid-liquid separation method comprises suction filtration;
preferably, the drying is air drying;
preferably, the drying time is 20-28 h.
5. The method of claim 3 or 4, wherein the NiB plating solution of step (2) comprises a nickel salt, KBH4Ethylenediamine, NaOH and a solvent;
preferably, the solvent comprises water;
preferably, the nickel salt comprises nickel sulfate;
preferably, Ni is contained in the NiB plating solution in the step (2)2+、KBH4Molar ratio of ethylenediamine to NaOHIs 1 (0.8-2.1): (4.3-5.9): 12-19.2);
preferably, in the NiB plating solution in the step (2), the content of Ni in the Ni salt is 2-3 g/L;
preferably, in the NiB plating solution in the step (2), KBH4The content of (A) is 2-5 g/L;
preferably, in the NiB plating solution in the step (2), the content of the ethylenediamine is 12-16 g/L;
preferably, the content of NaOH in the NiB plating solution in the step (2) is 22-35 g/L.
6. The method of any one of claims 3-5, wherein Ag in step (2)2The ratio of the mass of O/MgO to the volume of the NiB plating solution is 8-12 g/L;
preferably, the temperature for carrying out the reaction in step (2) is 40-50 ℃;
preferably, the reaction in step (2) is carried out with stirring;
preferably, the heating mode in the reaction process in the step (2) is water bath heating;
preferably, the reaction in step (2) is carried out for a time of 0.3 to 2 h.
7. The method according to any one of claims 3 to 6, wherein the reaction in step (2) further comprises solid-liquid separation and washing after the reaction is finished;
preferably, the washing agent used for washing is water and anhydrous methanol;
preferably, the washing method comprises the steps of firstly washing the mixture to be neutral by water, and then washing the mixture by using anhydrous methanol;
preferably, the washing with anhydrous methanol further comprises storing the catalyst in anhydrous methanol.
8. A method according to any of claims 3-7, characterized in that the method comprises the steps of:
(1) soaking magnesium oxide powder in silver nitrate solution, stirring at 35-45 deg.C for 3-5 hr, vacuum filtering, separating, and air drying to obtain Ag with Ag loading of 0.11-0.15 wt%2O/MgO；
(2) Ag obtained in the step (1)2Dispersing O/MgO in NiB plating solution, heating and stirring for 0.3-2h in water bath at 40-50 ℃, carrying out solid-liquid separation, washing with water to neutrality, and washing with anhydrous methanol to obtain the catalyst.
9. Use of a catalyst according to claim 1 or 2 for the catalytic hydrogenation of mixed terphenyls to produce hydrogenated terphenyls.
10. The use according to claim 9, wherein the process for the catalytic hydrogenation of mixed terphenyls comprises mixing a catalyst, mixed terphenyl and methanol, feeding hydrogen gas, and reacting to obtain hydrogenated terphenyl;
preferably, the temperature for carrying out the reaction is 85-95 ℃;
preferably, the pressure of hydrogen in the reaction process is 5-8 MPa;
preferably, the mass ratio of the catalyst, the mixed terphenyl and the methanol is 1 (100- > 180): 100- > 180), and preferably 1 (160- > 170): 160- > 170.
CN202010377323.8A 2020-05-07 2020-05-07 Catalyst for preparing hydrogenated terphenyl and preparation method and application thereof Pending CN111482177A (en)

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