CN115970707A - Preparation method and application method of hydrogenation catalyst - Google Patents
Preparation method and application method of hydrogenation catalyst Download PDFInfo
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Abstract
The invention relates to the field of catalyst hydrogenation, in particular to the field of catalyst hydrogenation, and specifically relates to a preparation method of a hydrogenation catalystA preparation method and an application method thereof. The technical points are as follows: composite carrier Ni-Ce-Al prepared by adopting ion coprecipitation method 2 O 3 Then adopting an isometric impregnation method to load Ru on the composite carrier Ni-Ce-Al 2 O 3 C, removing; the composite carrier Ni-Ce-Al 2 O 3 The specific surface area of (A) is 150 to 200m 2 (iv) a pore volume of 0.6 to 0.8cm 2 (iii) a mean pore diameter of 8.5 to 9.5nm. The invention selects proper carrier and catalyst to carry out catalytic hydrogenation process, has simple preparation process and is suitable for continuous production. The modification of the carrier enables the catalyst to have a proper pore channel so that raw material molecules pass through, and the catalyst has higher activity under the synergistic effect of the active component and the composite carrier.
Description
Technical Field
The invention relates to the field of catalyst hydrogenation, in particular to a preparation method and an application method of a hydrogenation catalyst.
Background
The technological process of synthesizing hydrogenated bisphenol product with bisphenol compound may be continuous or intermittent hydrogenation, and the selected catalyst includes noble metal supported catalyst, metal skeleton catalyst and alkali earth metal catalyst.
The existing hydrogenated bisphenol A synthesis process mostly adopts a supported noble metal catalyst and adopts a high-pressure reaction kettle to carry out intermittent hydrogenation or tubular fixed bed continuous hydrogenation. The hydrogenation process of the reaction kettle belongs to intermittent discontinuous reaction, and products obtained by intermittent reaction generally have poor technical quality index stability and cannot ensure industrial mass production along with the defects of high production cost and the like.
The tubular fixed bed catalytic hydrogenation process belongs to continuous hydrogenation, and the obtained product has the advantages of stable quality, low energy consumption and the like, but the bisphenol A hydrogenation process belongs to a strong exothermic reaction, the temperature rise of a catalyst bed layer can not be avoided under the condition of high load reaction, and the side reaction is aggravated due to overhigh temperature, so that in the current production technology, the proportion of most trans-isomers is usually 40-50%, and the hydrogenated bisphenol product has three isomers, wherein the trans-isomer has wider application value, and can generate synergistic effect and better mechanical property in a polymer, such as the improvement of the softening point of the polymer.
Therefore, there is a need in the art to develop a method for preparing a hydrogenation catalyst that can simultaneously hydrogenate bisphenols products with a high trans ratio at a relatively low cost.
In view of the defects of the existing hydrogenation catalytic reaction, the inventor develops a preparation method and an application method of a hydrogenation catalyst based on years of abundant experience and professional knowledge of the materials and by matching theoretical analysis and research innovation.
Disclosure of Invention
The invention aims to provide a preparation method of a hydrogenation catalyst, which selects a proper carrier and a catalyst to carry out a catalytic hydrogenation process, has a simple preparation process and is suitable for continuous production. The modification of the carrier enables the catalyst to have a proper pore channel so that raw material molecules pass through, and the catalyst has higher activity under the synergistic effect of the active component and the composite carrier.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a hydrogenation catalyst, which adopts an ion coprecipitation method to prepare a composite carrier Ni-Ce-Al 2 O 3 Then adopting an isometric impregnation method to load Ru on the composite carrier Ni-Ce-Al 2 O 3 The above step (1); composite carrier Ni-Ce-Al 2 O 3 The specific surface area of (A) is 150 to 200m 2 (iii) a pore volume of 0.6 to 0.8 cm/g 2 (iv) g, the average pore diameter is 8.5 to 9.5nm.
The invention uses the coprecipitation method to modify the carrier to prepare the composite carrier, is beneficial to better structural design of the catalyst during preparation of the catalyst, can generate a certain pore channel by roasting and decomposing while increasing the strength of the carrier, effectively reduces the agglomeration of particles, further improves the pore volume and the pore diameter of the carrier, ensures that the surface of the catalyst has no obvious accumulation phenomenon, and has larger specific surface area of the molded catalyst.
The invention prepares the composite carrier by modifying the carrier, changes the pore structure of the catalyst, enables the catalyst to have a proper pore channel to allow the raw material bisphenol A to pass through, changes the activity of the catalyst, simultaneously has high load, and can obtain the hydrogenated bisphenol product with high trans-proportion by using the catalyst.
Further, composite carrier Ni-Ce-Al 2 O 3 And (3) modifying.
Further, composite carrier Ni-Ce-Al 2 O 3 The content of Ni in the alloy is 0.2 to 0.5wt%, the content of Ce is 0.2 to 0.5wt%, and the load of Ru is 0.2 to 1wt%.
Further, the composite carrier Ni-Ce-Al is prepared by adopting an ion coprecipitation method 2 O 3 The specific operation is as follows: mixing Ni (NO) 3 ) 2 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 Dissolving O in water, and stirring uniformly to obtain powder Al 2 O 3 The carrier is stirred evenly and Na is added 2 CO 3 Adjusting the pH value of the aqueous solution to 7~8 to obtain a suspension, placing the suspension in a water bath kettle, heating, stirring, crystallizing, filtering, washing and drying to obtain solid powder; drying the solid powder, grinding, sieving, tabletting and roasting to obtain the composite carrier Ni-Ce-Al 2 O 3 。
Further, porous Al 2 O 3 The carrier is prepared by mixing pseudoboehmite, citric acid, sesbania powder and water, and the particle size of the carrier is 40 meshes.
Further, the temperature of the water bath kettle is 60 to 80 ℃.
Further, the pellet was a cylinder of 3X 3mm in diameter.
Further, the baking is carried out in a muffle furnace, and the baking temperature is 600 to 800 ℃.
Further, ru is loaded on the composite carrier Ni-Ce-Al by adopting an isometric impregnation method 2 O 3 The method comprises the following specific operations:
adding the aqueous solution of ruthenium source into the composite carrier Ni-Ce-Al 2 O 3 Continuously stirring until the mixture is fully mixed and impregnated, and drying and roasting the impregnated mixture to obtain a hydrogenation catalyst precursor;
and reducing the hydrogenation catalyst precursor by using hydrogen to obtain the hydrogenation catalyst.
Further, the baking temperature is 200 to 400 ℃.
Further, the specific operation of reducing the hydrogenation catalyst precursor by using hydrogen is as follows: and (3) placing the catalyst in a reduction furnace, continuously introducing hydrogen, and carrying out programmed temperature reduction at the reduction temperature of 100-300 ℃ for 1-3 h.
Further, the ruthenium source is ruthenium chloride.
The second purpose of the invention is to provide a method for applying a hydrogenation catalyst, which has the same technical effect.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a method for applying a plurality of hydrogenation catalysts, which is to dissolve bisphenol compounds in an organic solvent and continuously introduce hydrogen, and continuously prepare high trans-ratio hydrogenated bisphenol products under the action of the hydrogenation catalysts by adopting a fixed bed reactor.
Further, the bisphenol compound is bisphenol A, bisphenol S or bisphenol F.
Further, the process conditions of the hydrogenation catalytic reaction are as follows: the reaction temperature is 110 to 160 ℃, and the liquid space velocity is 0.18 to 0.36h -1 The reaction pressure is 4 to 6MPa.
In conclusion, the invention has the following beneficial effects:
the addition of nickel in the composite carrier has an inhibiting effect on hydrogenation of upper C = O in the raw material, so that the generation of a bisphenol compound deep hydrogenation product is reduced, and the generation of a polymer is reduced; the addition of cerium inhibits the aggregation of the ruthenium component, so that the active component is more uniformly dispersed on the surface of the carrier, the activity of the product is improved by the synergistic effect of the active component and the ruthenium component, the proportion of the trans-isomer of the hydrogenated bisphenol product is further improved by roasting the composite carrier at high temperature, the active component ruthenium content is reduced, the higher activity is still maintained, and the production cost is reduced to a certain extent. This is due to the higher energy content of the cis isomer, which tends to be converted to the trans isomer upon heating, i.e., at high temperatures, sufficient energy is supplied to effect isomerization due to thermodynamic equilibrium.
Drawings
FIG. 1 shows Ru/Al 2 O 3 And Ru/Ni-Ce-Al 2 O 3 SEM picture of (1);
FIG. 2 shows Ru/Al 2 O 3 And Ru/Ni-Ce-Al 2 O 3 XRD pattern of (A) was 0.5% Ru/Al 2 O 3 (B) 0.5% Ru/0.2% Ni-Al 2 O 3 ，(C) 0.5 % Ru/0.2%Ce-Al 2 O 3 ，(D) 0.5% Ru/0.2%Ni-0.2%Ce-Al 2 O 3 ，(E) 0.2 %Ru /0.2%Ni-0.2%Ce-Al 2 O 3 ，(F) 0.5 %Ru/0.5 %Ni-0.5%Ce- Al 2 O 3 。
Detailed Description
To further illustrate the technical means and effects adopted by the present invention to achieve the predetermined objects, the detailed description of the preparation method and the application method of the hydrogenation catalyst according to the present invention will be provided below.
Example 1
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.73g of porous powder alumina carrier, placing solid powder in a 90 ℃ oven for drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 x 3mm, and placing the cylindrical composite carrier in a muffle furnace for roasting at 700 ℃ for 3 hours;
s2, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed;
and S3, soaking for 2 hours at room temperature, stirring with a glass rod during the soaking, drying in a 105 ℃ oven overnight after the soaking to obtain a solid compound, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3 hours, tabletting and forming after the solid compound is finished, reducing for 2 hours in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen continuously during the period to obtain the hydrogenation catalyst.
(2) The catalyst is adopted to carry out hydrogenation catalytic reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 On the contraryAnd continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A, the bisphenol S and the bisphenol F.
Example 2
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.73g of powdered alumina carrier for later use, and then weighing 0.20g of Ni (NO) 3 ) 2 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing and drying, placing solid powder in a drying oven at 90 ℃, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at 700 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2h, stirring by using a glass rod during the soaking, drying in a 105 ℃ oven overnight after the soaking to obtain a solid compound, placing the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, then reducing for 2h in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen continuously during the period to obtain the hydrogenation catalyst.
(2) The catalyst is adopted to carry out hydrogenation catalytic reaction:
20mL of the solid catalyst is loaded into a fixed bed, and the reaction temperature is set to be 130 ℃, the reaction pressure is 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 3
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.61g of powdered alumina carrier for later use, and then weighing 0.12g of Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Stirring the carrier uniformly, and placing the carrier in a water bath kettleHeating and stirring at the medium temperature of 70 ℃, filtering, washing, drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at the temperature of 700 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2h while stirring with a glass rod, and drying in an oven at 105 deg.C overnight to obtain solid compound;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, and then reducing for 2h in a reduction furnace at the temperature of 140 ℃, wherein hydrogen is continuously introduced during the reduction process to prepare the solid catalyst.
(2) The catalyst is adopted to carry out hydrogenation catalytic reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 4
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.41g of powdered alumina carrier for later use, and then weighing 0.20g of Ni (NO) 3 ) 2 ·6H 2 O and 0.12g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing, drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at 700 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2 hr while stirring with a glass rod, drying in an oven at 105 deg.C overnight to obtain solidA bulk complex;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, then reducing for 2h in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen all the time to prepare the solid catalyst.
(2) Hydrogenation reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 5
(1) Preparation of hydrogenation catalyst:
the same as in example 4.
(2) Hydrogenation of styrene-butadiene-styrene block polymers:
20mL of the solid catalyst is loaded into a fixed bed, and the reaction temperature is set to be 110 ℃, the reaction pressure is 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 6
(1) Preparation of hydrogenation catalyst:
the same as in example 4.
(2) Hydrogenation of styrene-butadiene-styrene block polymers:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 110 ℃, the reaction pressure is set to be 4Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 7
(1) Preparation of hydrogenation catalyst:
the same as in example 4.
(2) Hydrogenation of styrene-butadiene-styrene block polymers:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 110 ℃, the reaction pressure is set to be 4Mpa, and the space velocity is set to be 0.18h -1 Hydrogen is continuously introduced in the reaction process, and bisphenol A is doubly addedPhenol S and bisphenol F are catalytically reacted.
Example 8
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 18.92g of powdered alumina carrier for later use, and then weighing 0.50g of Ni (NO) 3 ) 2 ·6H 2 O and 0.31g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing, drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at 700 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, continuously stirring until the mixture is fully mixed, soaking the mixture at room temperature for 2 hours, stirring the mixture by using a glass rod during the soaking, and drying the soaked mixture in a 105 ℃ oven overnight to obtain a solid composite;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, then reducing for 2h in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen all the time to prepare the solid catalyst.
(2) Hydrogenation reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 9
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.14g of powdered alumina carrier for later use, and then weighing 0.20g of Ni (NO) 3 ) 2 ·6H 2 O and 0.12g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Stirring of the supportUniformly placing the mixture in a water bath kettle, heating and stirring the mixture at 70 ℃, filtering, washing and drying the mixture, grinding the mixture by using a mortar, tabletting the mixture to obtain a cylindrical composite carrier with the diameter of 3 x 3mm, and roasting the cylindrical composite carrier for 3 hours at 700 ℃ to obtain the composite carrier;
s3, weighing 0.54g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2h while stirring with a glass rod, and drying in an oven at 105 deg.C overnight to obtain solid compound;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, then reducing for 2h in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen all the time to prepare the solid catalyst.
(2) Hydrogenation of styrene-butadiene-styrene block polymers:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 10
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.57g of powdered alumina carrier for later use, and then weighing 0.20g of Ni (NO) 3 ) 2 ·6H 2 O and 0.12g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing, drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at 700 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.11g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL deionized water, adding into the composite carrier while stirring, stirring continuously until mixing thoroughly, soaking at room temperature for 2h while stirring with a glass rod, placing in a containerDrying in an oven at 105 ℃ overnight to obtain a solid compound;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, then reducing for 2h in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen all the time to prepare the solid catalyst.
(2) Hydrogenation reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 11
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.41g of powdered alumina carrier for later use, and then weighing 0.20g of Ni (NO) 3 ) 2 ·6H 2 O and 0.12g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing, drying, grinding by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 x 3mm, and roasting at 600 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2h while stirring with a glass rod, and drying in an oven at 105 deg.C overnight to obtain solid compound;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, then reducing for 2h in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen all the time to prepare the solid catalyst.
(2) Hydrogenation reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 12
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.41g of powdered alumina carrier for later use, and then weighing 0.20g of Ni (NO) 3 ) 2 ·6H 2 O and 0.12g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing, drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at 800 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2h while stirring with a glass rod, and drying in an oven at 105 deg.C overnight to obtain solid compound;
and S3, putting the solid compound into a muffle furnace, heating the muffle furnace to 300 ℃ at the speed of 2 ℃/min, roasting for 3h, then reducing for 2h in a reduction furnace at the temperature of 140 ℃, and introducing hydrogen all the time to prepare the solid catalyst.
(2) Hydrogenation reaction:
20mL of the solid catalyst is loaded into a fixed bed, and the reaction temperature is set to be 130 ℃, the reaction pressure is 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 13
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.41g of powdered alumina carrier for later use, and then weighing 0.20g of Ni (NO) 3 ) 2 ·6H 2 O and 0.12g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding and dryingTreated powdered Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing, drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at 700 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2h while stirring with a glass rod, and drying in an oven at 105 deg.C overnight to obtain solid compound;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 200 ℃ at the speed of 2 ℃/min, roasting for 3h, and then reducing for 2h in a reduction furnace at the temperature of 140 ℃, wherein hydrogen is continuously introduced during the reduction process to prepare the solid catalyst.
(2) Hydrogenation reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Example 14
(1) Preparation of hydrogenation catalyst:
s1, firstly weighing 19.41g of powdered alumina carrier for later use, and then weighing 0.20gNi (NO) 3 ) 2 ·6H 2 O and 0.12g Ce (NO) 3 ) 3 ·6H 2 Adding 15mL of deionized water into a beaker, and stirring for dissolving;
s2, adding dried powder Al 2 O 3 Uniformly stirring the carrier, placing the carrier in a water bath kettle, heating and stirring at 70 ℃, filtering, washing, drying, crushing by using a mortar, tabletting to obtain a cylindrical composite carrier with the diameter of 3 multiplied by 3mm, and roasting at 700 ℃ for 3 hours to obtain the composite carrier;
s3, weighing 0.27g RuCl at room temperature 3 ·3H 2 Dissolving O in 15mL of deionized water, adding the mixture into the composite carrier while stirring, and continuously stirring until the mixture is fully mixed; soaking at room temperature for 2 hr while stirring with glass rodDrying in a 105 ℃ oven overnight to obtain a solid compound;
and S4, putting the solid compound into a muffle furnace, heating the muffle furnace to 400 ℃ at the speed of 2 ℃/min, roasting for 3h, and then reducing for 2h in a reduction furnace at the temperature of 140 ℃, wherein hydrogen is continuously introduced during the reduction process to prepare the solid catalyst.
(2) Hydrogenation reaction:
20mL of the solid catalyst is loaded into a fixed bed, the reaction temperature is set to be 130 ℃, the reaction pressure is set to be 6Mpa, and the space velocity is set to be 0.3h -1 And continuously introducing hydrogen in the reaction process to perform catalytic reaction on the bisphenol A bisphenol S and the bisphenol F.
Test results
Table 1 shows the degrees of hydrogenation and the selectivities of bisphenol A bisphenol S and bisphenol F in examples 1 to 15.
TABLE 1 degree of hydrogenation and selectivity for bisphenol A bisphenol S and bisphenol F
By comparison of the data in table 1, the following conclusions are drawn:
adding 0.2% of Ni and 0.2% of Ce simultaneously based on macroporous alumina by ion coprecipitation method to form Ni-Ce-Al 2 O 3 The composite carrier is calcined at high temperature of 700 ℃, 0.5 percent of Ru is loaded by an isometric impregnation method on the basis of the high temperature, the calcination is continued for 200 ℃, the catalyst prepared by the method has higher activity for hydrogenating the bisphenol compounds, the proportion of the trans-isomer of the hydrogenated bisphenol A can reach 76 percent at most, and the proportions of the trans-isomers of the hydrogenated bisphenol F and the hydrogenated bisphenol S also reach higher proportions.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the hydrogenation catalyst is characterized in that the composite carrier Ni-Ce-Al is prepared by adopting an ion coprecipitation method 2 O 3 Then adopting an isometric impregnation method to load Ru on the composite carrier Ni-Ce-Al 2 O 3 The above step (1); the composite carrier Ni-Ce-Al 2 O 3 The specific surface area of (A) is 150 to 200m 2 (iii) a pore volume of 0.6 to 0.8 cm/g 2 (iv) g, the average pore diameter is 8.5 to 9.5nm.
2. The preparation method of the hydrogenation catalyst according to claim 1, wherein the composite carrier is prepared by a coprecipitation method, bimetallic Ni and Ce are added for modification, and the composite carrier is calcined at a high temperature of 600 to 800 ℃.
3. The method for preparing a hydrogenation catalyst according to claim 1 or 2, wherein the composite carrier is Ni-Ce-Al 2 O 3 The content of Ni in the alloy is 0.2-0.5 wt%, the content of Ce in the alloy is 0.2-0.5 wt%, and the load of Ru is 0.2-1wt%.
4. The method for preparing a hydrogenation catalyst according to claims 1-2, wherein the composite carrier Ni-Ce-Al is prepared by the ion coprecipitation method 2 O 3 The specific operation is as follows: mixing Ni (NO) 3 ) 2 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 Dissolving O in water, and stirring uniformly to obtain powder Al 2 O 3 The carrier is stirred uniformly and Na is added 2 CO 3 Adjusting the pH value of the aqueous solution to 7~8 to obtain a suspension, placing the suspension in a water bath kettle, heating, stirring, crystallizing, filtering, washing and drying to obtain solid powder; drying, crushing, sieving, tabletting and roasting the solid powder to obtain the composite carrier Ni-Ce-Al 2 O 3 。
5. The preparation method of the hydrogenation catalyst according to claim 1, wherein the equal volume impregnation method is adopted to load Ru on the composite carrier Ni-Ce-Al 2 O 3 The method comprises the following specific operations:
adding the aqueous solution of ruthenium source into the composite carrier Ni-Ce-Al 2 O 3 Continuously stirring until the mixture is fully mixed and impregnated, and drying and roasting the impregnated mixture to obtain a hydrogenation catalyst precursor;
and reducing the hydrogenation catalyst precursor by using hydrogen to obtain the hydrogenation catalyst.
6. The method of claim 5, wherein the ruthenium source is ruthenium chloride.
7. The method for producing a hydrogen catalyst according to claim 5, wherein the hydrogen reduction temperature is 200 to 400 ℃ and the reduction time is 1 to 3 hours.
8. The application method of the hydrogenation catalyst obtained by the preparation method of 1~7, which is characterized in that bisphenol compound is dissolved in organic solvent, and hydrogen is continuously introduced, and a fixed bed reactor is adopted to continuously prepare high trans-ratio hydrogenated bisphenol product under the action of the hydrogenation catalyst.
9. The method for using a hydrogenation catalyst according to claim 8, wherein the bisphenol compound is bisphenol A, bisphenol S or bisphenol F.
10. The method for using a hydrogen catalyst according to claim 8, characterized in that the process conditions are: the reaction temperature is 110 to 160 ℃, and the liquid space velocity is 0.18 to 0.36h -1 The reaction pressure is 4 to 6MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114192142A (en) * | 2021-11-22 | 2022-03-18 | 泰兴市凌飞化学科技有限公司 | Catalyst for hydrogenating dinonylphenol and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114192142A (en) * | 2021-11-22 | 2022-03-18 | 泰兴市凌飞化学科技有限公司 | Catalyst for hydrogenating dinonylphenol and preparation method thereof |
| CN114192142B (en) * | 2021-11-22 | 2024-03-22 | 泰兴市凌飞化学科技有限公司 | Catalyst for dinonyl phenol hydrogenation and preparation method thereof |
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