CN114602464A - Hydrocatalyst for C-V petroleum resin and its preparing process - Google Patents

Hydrocatalyst for C-V petroleum resin and its preparing process Download PDF

Info

Publication number
CN114602464A
CN114602464A CN202210436456.7A CN202210436456A CN114602464A CN 114602464 A CN114602464 A CN 114602464A CN 202210436456 A CN202210436456 A CN 202210436456A CN 114602464 A CN114602464 A CN 114602464A
Authority
CN
China
Prior art keywords
carbon
hours
activated carbon
petroleum resin
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210436456.7A
Other languages
Chinese (zh)
Inventor
翟庆阁
黄明志
黄闽岳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinochem Quanzhou Energy Technology Co Ltd
Original Assignee
Sinochem Quanzhou Energy Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinochem Quanzhou Energy Technology Co Ltd filed Critical Sinochem Quanzhou Energy Technology Co Ltd
Priority to CN202210436456.7A priority Critical patent/CN114602464A/en
Publication of CN114602464A publication Critical patent/CN114602464A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a C-V petroleum resin hydrogenation catalyst and a preparation method thereof, and mainly solves the problems that chromophoric groups in the C-V petroleum resin are not easy to adsorb on the catalyst and the hydrogenation activity of the catalyst is low. The invention relates to a carbon five petroleum resin hydrogenation catalyst which comprises the following components: (a) the carrier is active carbon modified by alkaline earth ions; (b) the active metal is a transition metal. Under the action of the catalyst, the adsorption of carbon five petroleum resin molecules is facilitated, so that the chroma of hydrogenated carbon five resin is reduced, and the active carbon modified by alkaline earth ions is used as a carrier, so that the dispersing capacity of active metal is improved, and the surface acidity and alkalinity can be improved.

Description

Hydrocatalyst for C-V petroleum resin and its preparing process
Technical Field
The invention relates to a catalyst for preparing hydrogenated carbon five petroleum resin with low chroma and high softening point, which can reduce the chroma of the hydrogenated carbon five petroleum resin and improve the softening point.
Background
The main chain of the carbon five petroleum resin is an aliphatic structure, and has the characteristics of low acid value, good miscibility, water resistance, ethanol resistance, chemical corrosion resistance and the like. However, the carbon five petroleum resin has the defects of high brittleness, dark color, odor, lack of polar groups on the structure and the like due to the unsaturated chemical bond of the carbon five petroleum resin. Unsaturated carbon-carbon double bonds in the resin are subjected to hydrogenation saturation in a catalytic hydrogenation mode, and the unsaturation degree is reduced, so that the performances of the resin such as stability, oxidation resistance and the like are improved. The hydrogenated carbon five petroleum resin is colorless, tasteless, high in light oxygen stability, and is an upgrade of common yellow resin additives used in specific fields, especially furniture binder, printing ink, high-grade paper, paint and other fields. With the requirement of human on health and environmental protection, the hydrogenated carbon five resin gradually replaces the carbon five petroleum resin to produce energy, and the hydrogenated carbon five petroleum resin can be applied to more fields.
At present, the catalyst system for efficient hydrogenation of carbon five petroleum resin is mainly a noble metal Pt/Pd-based catalyst and a Ni-based catalyst. Patent CN107876056A adopts a multiple-time slurry dipping method to obtain Al2O3The film-coated activated carbon carrier is loaded with nickel oxide and one of the additives Fe, Co and Cu to form the petroleum resin hydrogenation catalyst, so that the product quality of the hydrogenated carbon five resin can be effectively improved. The patent CN102935370A adopts a catalyst formed by nickel oxide loaded on an alumina-titanium oxide composite carrier and auxiliary agent magnesium oxide or copper oxide, and has low-temperature hydrogenation activity and good stability. In patent CN102453217B, it is reported that a catalyst in which an alumina/silica supported active metal nickel and an auxiliary agent are one of Zn, K, Ba, Ca, Fe, and Cu can meet the requirement of petroleum resin hydrogenation decolorization. Patent CN109999820B reports a preparation method of a nickel-based catalyst, which uses quaternary hydrotalcite NiMgAl-M-LDH (M = La, Cu) as a carrier, and can effectively improve the chroma of carbon penta resin and maintain a higher softening point.
In the research results of the prior patents and the literature, the formula of the carbon-five petroleum resin hydrogenation catalyst formed by using the alkaline earth metal modified activated carbon material as a carrier to support noble metal is not mentioned. The existing catalyst takes inorganic matters and inorganic minerals as carriers, surface groups have stronger hydrophilicity and poor action force with non-polar petroleum resin molecules, and the adsorption of carbon five petroleum resin molecules is reduced. The invention uses the active carbon as the hydrophobic carrier, and the adsorption of the nonpolar petroleum resin molecules on the surface of the catalyst can be increased due to the nonpolar graphite crystal structure; the alkaline earth ions modify the surface hydroxyl and carboxylic acid groups, so that the surface acidity of the activated carbon can be reduced, the rearrangement reaction in the hydrogenation of the carbon five resin is weakened, and the softening point of the hydrogenated carbon five resin is still higher. The acid sites formed on the surface easily cause rearrangement of petroleum resin molecules in the hydrogenation process, so that the softening point of the hydrogenated resin is reduced. Proper amount of alkaline earth metal modifies the surface acidity site, thus reducing the surface acidity and maintaining the softening point. Alkali metal modification can also reduce surface acidity, but alkali metals tend to passivate active metal lattice oxygen, thereby reducing the hydrogenation performance of active metals.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a catalyst to solve the problems of poor adsorption and poor decolorization efficiency of carbon-five petroleum resin.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst described in the first technical problem.
The invention aims to solve the technical problem and provides a method for applying the catalyst to the hydrofining reaction of the carbon five petroleum resin.
In order to solve one of the technical problems, the invention provides a catalyst for preparing hydrogenated carbon five petroleum resin with low chroma and high softening point, and the technical scheme of the invention is as follows: a carbon five petroleum resin hydrogenation catalyst comprises the following components:
(a) the carrier is active carbon modified by alkaline earth ions;
(b) the active metal is a transition metal; wherein the loading amount of the active metal is 0.1-5% of the mass of the carrier.
In the above technical scheme, the carrier is activated carbon modified by alkaline earth ions, and the activated carbon is one of wood chip activated carbon and shell activated carbon.
In the technical scheme, the carrier is alkaline earth ion modified activated carbon, and the activated carbon is treated by 0.5 mol/L concentrated hydrochloric acid.
In the above technical scheme, the carrier is modified by alkaline earth ionsDecorated activated carbon, the specific surface area of the activated carbon is 800-1600 m2/g。
In the technical scheme, the carrier is alkaline earth ion modified activated carbon, and the benzene adsorption value of the activated carbon is 40-60 wt%.
In the above technical scheme, the carrier is activated carbon modified by alkaline earth ions, and the alkaline earth ions are Ca2+，Mg2 +，Ba2+One or more of (a). Wherein the magnesium ion precursor is one or more of magnesium nitrate, magnesium chloride and magnesium acetate.
In the above technical scheme, the alkaline earth metal precursor compound is not particularly limited, and may be reasonably selected by a person skilled in the art, for example, the alkaline earth ion-containing precursor may be, but is not limited to, magnesium nitrate, magnesium chloride, magnesium acetate, and calcium chloride.
In the technical scheme, the carrier is activated carbon modified by alkaline earth ions, and the mass fraction of the alkaline earth ions is 0.5-10%.
In the technical scheme, the transition metal is one or more of Pt, Pd, Ir, Ru and Rh.
In the above technical solutions, the precursor compound of the active metal is not particularly limited, and may be reasonably selected by a person skilled in the art, for example, the Pt-group-containing precursor may be, but is not limited to, chloroplatinic acid, palladium chloride, iridium chloride, and platinum tetraammine nitrate.
The invention also aims to provide a catalyst for preparing hydrogenated carbon-five petroleum resin with low chroma and high softening point, the method uses active carbon modified by alkaline-earth ions as a carrier in the catalyst, the hydrophobicity of the carbon material is favorable for the adsorption of the carbon-five petroleum resin, and the surface acidity site can be reduced after the modification by the alkaline-earth ions, thereby avoiding the reduction of the softening point.
Another object of the present invention is to provide a catalyst for preparing a hydrogenated carbon pentapetroleum resin with low color and high softening point, which comprises the treatment of activated carbon and the efficient loading of active metal in the activated carbon.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a carbon five petroleum resin hydrogenation catalyst comprises the following steps:
(1) preparing a hydrochloric acid solution with the concentration of 0.5 mol/L, immersing activated carbon in the hydrochloric acid solution, treating at the water temperature of 90 ℃ for 12 hours, carrying out suction filtration and washing to be neutral, and drying at the temperature of 100 ℃ for 12 hours;
(2) weighing salt containing alkaline earth ions, dissolving in deionized water, adding activated carbon treated by hydrochloric acid solution, aging at room temperature for 6 hours, drying at 110 ℃ for 4 hours, and roasting at 350 ℃ for 6 hours in nitrogen atmosphere to obtain the alkaline earth ion modified activated carbon.
(3) Dissolving a salt containing transition metal in deionized water, adding activated carbon modified by alkaline earth ions, aging at room temperature for 12 hours, drying at 110 ℃ for 6 hours, and reducing at 300 ℃ for 4 hours in a hydrogen atmosphere to obtain the carbon five petroleum resin hydrogenation catalyst.
(4) Adding silica sol (30% SiO) into the above C-V petroleum resin hydrogenation catalyst2) After compaction and forming, the catalyst particles are crushed and sieved to 40 meshes for testing the catalytic performance.
The invention aims to solve the technical problem of providing an application method of the catalyst for carrying out the hydrofining reaction of the hydrocarbon-modified petroleum resin.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention takes the cyclohexane solution of carbon five resin as a reactant, and carries out performance evaluation on the catalyst in any one of the technical schemes on a high-pressure fixed bed reactor. The catalyst loading volume was 20.0 ml. Reducing the catalyst before feeding by using hydrogen to ensure that the loaded active component exists in an elementary substance form, wherein the reduction conditions are as follows: the temperature is 200-450 ℃, the pressure is 0.5-7.0 MPa, the hydrogen flow rate is 10-200 ml/min, and the time is 0.5-5.0 h; reaction conditions are as follows: the temperature is 180-400 ℃, the pressure is 1.0-15.0 MPa, and the volume airspeed is 0.5-4.5 h-1The volume ratio of hydrogen to oil is 200-1000. The carbon five resin used for the hydrogenation reaction is 5# resin, the softening point of the resin is 100 ℃, the color number is 5#, and the bromine value is 5.93 gBr/100 g.
The softening point is analyzed by a ring and sphere method GB/2294, bromine value analysis is carried out by an iodometry method (SWB 2301-62), and the hydrogenation reaction conversion rate of the petroleum resin is calculated. Color numbers were tested using the Gardener method.
Figure 673718DEST_PATH_IMAGE002
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1% Pt/Mg (1%) -AC
1. Catalyst preparation
300 ml of hydrochloric acid solution with the concentration of 0.5 mol/L is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 1.24g of magnesium nitrate is weighed and dissolved in 3g of deionized water, 20g of activated carbon treated by hydrochloric acid solution is added, after aging for 6 hours at room temperature, drying is carried out for 4 hours at 110 ℃, and roasting is carried out for 6 hours at 350 ℃ under nitrogen atmosphere, and the product is recorded as Mg (1%) -AC. Weighing 10g of Mg (1%) -AC carrier of the magnesium ion modified activated carbon, and measuring the water absorption of the carrier to be 28%; 0.27g of chloroplatinic acid (Pt content: 37%) was weighed out and dissolved in deionized water, added to the above 10g of Mg (1%) -AC support, aged at room temperature for 12 hours, dried at 110 ℃ for 6 hours, and reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst was recorded as 1% Pt/Mg (1%) -AC.
To the above 1% Pt/Mg (1%) -AC catalyst was added 2g of silica sol (30% SiO2) After compaction and forming, the catalyst particles are crushed and sieved to 40 meshes for testing the catalytic performance.
2. Catalyst evaluation
The hydrogenation reaction of the carbon five resin is carried out on a high-pressure fixed bed reactor, and the filling volume of the catalyst is 10.0 ml. Before reaction, the catalyst needs to be reduced for 2 hours at the temperature of 450 ℃ under normal pressure, and after the temperature is reduced to the reaction temperature, a solution containing 20 wt% of carbon penta resin-cyclohexane is introduced to react with hydrogen. Reaction stripThe parts are as follows: the reaction temperature is 250 ℃, the reaction pressure is 8.0 MPa, and the mass space velocity of the raw material is 1.0 h-1The volume ratio of hydrogen to resin-cyclohexane solution was 600: 1. The reaction results are shown in Table 1.
Comparative example 1% Pt/AC
1. Catalyst preparation
300 ml of hydrochloric acid solution with the concentration of 0.5 mol/L is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 0.27g of chloroplatinic acid (Pt content: 37%) was weighed out and dissolved in deionized water, and added to the above 10g of AC support, and after aging at room temperature for 12 hours, the mixture was dried at 110 ℃ for 6 hours and reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst was recorded as 1% Pt/AC.
To the above 1% Pt/AC catalyst was added 2g of silica sol (30% SiO)2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Comparative example 2 1% Pt/Mg (1%) -Al2O3
1. Catalyst preparation
1.24g of magnesium nitrate was weighed out and dissolved in 20ml of deionized water, after which 20g of Al was added2O3Stirring the powder for 6 hours, evaporating the powder to dryness in a water bath at 90 ℃, drying the powder for 12 hours, roasting the powder for 4 hours in a muffle furnace at 450 ℃, and recording the carrier as Mg (1%) -Al2O3. 0.27g of chloroplatinic acid (Pt content: 37%) was weighed out and dissolved in 20ml of deionized water, and 10g of the above-mentioned Mg (1%) -Al carrier powder was added2O3Stirring for 6 hours, evaporating to dryness in a water bath at 90 ℃, drying for 12 hours, and then roasting in a muffle furnace at 450 ℃ for 4 hours in an air atmosphere, wherein the catalyst is recorded as 1% Pt/Mg (1%) -Al2O3。
To the above 1% Pt/Mg (1%) -Al2O32g of silica sol (30% SiO) was added to the catalyst2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Comparative example 3 1% Pt/Mg (1%) -SiO2
1.24g of magnesium nitrate was weighed out and dissolved in 20ml of deionized water, after which 20g of SiO were added2Stirring the powder for 6 hours, evaporating the powder to dryness in a water bath at 90 ℃, drying the powder for 12 hours, roasting the powder for 4 hours in a muffle furnace at 450 ℃, and recording the carrier as Mg (1%) -SiO2. 0.27g of chloroplatinic acid (Pt content: 37%) was weighed out and dissolved in 20ml of deionized water, and 10g of the above-mentioned support powder Mg (1%) -SiO was added2Stirring for 6 hours, evaporating to dryness in a water bath at 90 ℃, drying for 12 hours, and then roasting in a muffle furnace at 450 ℃ for 4 hours in an air atmosphere, wherein the catalyst is recorded as 1% Pt/Mg (1%) -SiO2。
To the above 1% Pt/Mg (1%) -SiO22g of silica sol (30% SiO) was added to the catalyst2) After compaction and forming, the catalyst particles are crushed and sieved to 40 meshes for testing the catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Comparative example 4 1% Pt/Na (1%) -AC
1. Catalyst preparation
300 ml of hydrochloric acid solution with the concentration of 0.5 mol/L is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 0.74g of sodium nitrate is weighed and dissolved in 3g of deionized water, 20g of activated carbon treated by hydrochloric acid solution is added, after aging for 6 hours at room temperature, drying is carried out for 4 hours at 110 ℃, and roasting is carried out for 6 hours at 350 ℃ under nitrogen atmosphere, and the product is recorded as Na (1%) -AC. Weighing 10g of Na (1%) -AC carrier modified by sodium ions, and measuring the water absorption rate to be 28%; 0.27g of chloroplatinic acid (Pt content 37%) was weighed out, dissolved in deionized water, added to the above 10g of Na (1%) -AC support, aged at room temperature for 12 hours, dried at 110 ℃ for 6 hours, and reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst was recorded as 1% Pt/Na (1%) -AC.
To the above 1% Pt/Na (1%) -AC catalyst was added 2g of silica sol (30% SiO2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Comparative example 5 1% Pt/B (1%) -AC
1. Catalyst preparation
300 ml of 0.5 mol/L hydrochloric acid solution is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 1.14g of boric acid is weighed and dissolved in 3g of deionized water, 20g of activated carbon treated by hydrochloric acid solution is added, after aging for 6 hours at room temperature, the mixture is dried for 4 hours at 110 ℃ and roasted for 6 hours at 350 ℃ under nitrogen atmosphere, and the product is recorded as B (1%) -AC. Weighing 10g of boron ion modified activated carbon B (1%) -AC carrier, and measuring the water absorption rate to be 28%; 0.27g of chloroplatinic acid (Pt content 37%) was weighed out, dissolved in deionized water, added to the above-mentioned 10g B (1%) -AC support, aged at room temperature for 12 hours, dried at 110 ℃ for 6 hours, and reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst was recorded as 1% Pt/B (1%) -AC.
To the above 1% Pt/B (1%) -AC catalyst was added 2g of silica sol (30% SiO2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 2 1% Pt/Ca (1%) -AC
1. Catalyst preparation
300 ml of 0.5 mol/L hydrochloric acid solution is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 0.82g of calcium nitrate is weighed and dissolved in 3g of deionized water, 20g of activated carbon treated by hydrochloric acid solution is added, after aging for 6 hours at room temperature, drying is carried out for 4 hours at 110 ℃, and roasting is carried out for 6 hours at 350 ℃ under nitrogen atmosphere, and the product is marked as Ca (1%) -AC. Weighing 10g of Ca (1%) -AC carrier modified by calcium ions, and measuring the water absorption of the carrier to be 28%; 0.27g of chloroplatinic acid (Pt content: 37%) was weighed out, dissolved in deionized water, added to the above 10g of Ca (1%) -AC support, aged at room temperature for 12 hours, dried at 110 ℃ for 6 hours, and reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst was recorded as 1% Pt/Ca (1%) -AC.
To the above 1% Pt/Ca (1%) -AC catalyst was added 2g of silica sol (30% SiO2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 3 1% Pt/Ba (1%) -AC
1. Catalyst preparation
300 ml of hydrochloric acid solution with the concentration of 0.5 mol/L is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 0.30g of barium chloride is weighed and dissolved in 3g of deionized water, 20g of activated carbon treated by hydrochloric acid solution is added, after aging for 6 hours at room temperature, drying is carried out for 4 hours at 110 ℃, and roasting is carried out for 6 hours at 350 ℃ under nitrogen atmosphere, and the product is recorded as Ba (1%) -AC. Weighing 10g of barium ion modified active carbon Ba (1%) -AC carrier, and measuring the water absorption rate to be 28%; 0.27g of chloroplatinic acid (Pt content: 37%) was weighed out, dissolved in deionized water, added to the above 10g of Ba (1%) -AC support, aged at room temperature for 12 hours, dried at 110 ℃ for 6 hours, and reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst was recorded as 1% Pt/Ba (1%) -AC.
To the above 1% Pt/Ba (1%) -AC catalyst was added 2g of silica sol (30% SiO2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 4 1% Pd/Mg (1%) -AC
300 ml of 0.5 mol/L hydrochloric acid solution is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 1.24g of magnesium nitrate is weighed and dissolved in 3g of deionized water, 20g of activated carbon treated by hydrochloric acid solution is added, after aging for 6 hours at room temperature, drying is carried out for 4 hours at 110 ℃, and roasting is carried out for 6 hours at 350 ℃ under nitrogen atmosphere, and the product is recorded as Mg (1%) -AC. Weighing 10g of Mg (1%) -AC carrier of the magnesium ion modified activated carbon, and measuring the water absorption of the carrier to be 28%; 0.17g of palladium chloride (Pt content 59.5%) was weighed out, dissolved in deionized water, added to the above 10g of Mg (1%) -AC support, aged at room temperature for 12 hours, dried at 110 ℃ for 6 hours, reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst was recorded as 1% Pd/Mg (1%) -AC.
To the above 1% Pd/Mg (1%) -AC catalyst was added 2g of silica sol (30% SiO2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 5 1% Ir/Mg (1%) -AC
1. Catalyst preparation
300 ml of hydrochloric acid solution with the concentration of 0.5 mol/L is prepared and placed in a three-neck flask, 40g of coconut shell activated carbon is weighed and placed in the solution, and the solution is treated for 12 hours at the water temperature of 90 ℃. The activated carbon after hydrochloric acid treatment is filtered, washed to be neutral and dried for 12 hours at 100 ℃. Weighing 10g of activated carbon treated by hydrochloric acid solution, and measuring the water absorption rate to be about 30%; 0.2g of magnesium nitrate is weighed and dissolved in 3g of deionized water, 20g of activated carbon treated by hydrochloric acid solution is added, after aging for 6 hours at room temperature, drying is carried out for 4 hours at 110 ℃, and roasting is carried out for 6 hours at 350 ℃ under nitrogen atmosphere, and the product is recorded as Mg (1%) -AC. Weighing 10g of Mg (1%) -AC carrier of the magnesium ion modified activated carbon, and measuring the water absorption of the carrier to be 28%; 0.17g of iridium chloride (with an Ir content of 60%) is weighed out, dissolved in deionized water, added to the above 10g of Mg (1%) -AC support, aged at room temperature for 12 hours, dried at 110 ℃ for 6 hours, reduced at 300 ℃ for 4 hours under a hydrogen atmosphere, and the catalyst is recorded as 1% Ir/Mg (1%) -AC.
To the above 1% Ir/Mg (1%) -AC catalyst was added 2g of silica sol (30% SiO2) After compaction and forming, the catalyst is crushed and sieved into 40-mesh particles for testing catalytic performance.
2. Catalyst evaluation
The catalytic performance of the catalyst in the carbon five resin hydrofinishing reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
TABLE 1
Figure DEST_PATH_IMAGE004
It is understood from a comparison between example 1 and comparative example 1 that the alkaline earth ions modify the activated carbon to improve the acidity of the catalyst surface and maintain a good softening point.
Comparing example 1 with comparative example 2 and comparative example 3, it can be seen that the activated carbon as a carrier of a petroleum resin hydrogenation catalyst can improve the hydrogenation conversion rate by adsorbing organic macromolecules, thereby reducing the chroma of the hydrogenated resin.
As is clear from comparison between example 1 and comparative example 4, the alkaline earth metal can maintain the hydrogenation activity of the active metal more than the modification with the alkali metal.
It is understood from comparison between example 1 and comparative example 5 that the modification of activated carbon by B does not improve the surface acidity to an alkaline earth metal, resulting in an excessive reduction in the softening point.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (10)

1. The carbon five petroleum resin hydrogenation catalyst is characterized by comprising the following components:
(a) the carrier is active carbon modified by alkaline earth ions;
(b) the active metal is a transition metal;
wherein the loading amount of the active metal is 0.1-5% of the mass of the carrier.
2. The carbon-five petroleum resin hydrogenation catalyst as claimed in claim 1, wherein the activated carbon is one of wood chip activated carbon and shell activated carbon.
3. The carbon-five petroleum resin hydrogenation catalyst as defined in claim 2, wherein the specific surface area of the activated carbon is 800-1600 m2/g。
4. The carbon five petroleum resin hydrogenation catalyst as claimed in claim 2, wherein the benzene adsorption value of the activated carbon is 40-60 wt%.
5. The carbon-five petroleum resin hydrogenation catalyst as defined in claim 1, wherein the alkaline earth ion is Ca2+，Mg2+，Ba2+One or more of (a).
6. The carbon-five petroleum resin hydrogenation catalyst as claimed in claim 1, wherein the mass fraction of alkaline earth ions in the alkaline earth ion-modified activated carbon is 0.5-10%.
7. The carbon five petroleum resin hydrogenation catalyst according to claim 1, wherein the preparation method of the alkaline earth ion modified activated carbon comprises the following steps:
(1) preparing a hydrochloric acid solution with the concentration of 0.5 mol/L, immersing activated carbon in the hydrochloric acid solution, treating at the water temperature of 90 ℃ for 12 hours, performing suction filtration and washing to be neutral, and drying at the temperature of 100 ℃ for 12 hours;
(2) weighing salt containing alkaline earth ions, dissolving in deionized water, adding activated carbon treated by hydrochloric acid solution, aging at room temperature for 6 hours, drying at 110 ℃ for 4 hours, and roasting at 350 ℃ for 6 hours in nitrogen atmosphere to obtain the alkaline earth ion modified activated carbon.
8. The carbon five petroleum resin hydrogenation catalyst according to claim 1, wherein the transition metal is one or more of Pt, Pd, Ir, Ru, Rh.
9. The method for preparing the hydrocarbon-penta petroleum resin hydrogenation catalyst according to claim 1, characterized by comprising the steps of: dissolving a salt containing transition metal in deionized water, adding activated carbon modified by alkaline earth ions, aging at room temperature for 12 hours, drying at 110 ℃ for 6 hours, and reducing at 300 ℃ for 4 hours in a hydrogen atmosphere to obtain the carbon five petroleum resin hydrogenation catalyst.
10. Use of the hydrogenation catalyst of claim 1 in the hydrofinishing of carbon five petroleum resins.
CN202210436456.7A 2022-04-25 2022-04-25 Hydrocatalyst for C-V petroleum resin and its preparing process Pending CN114602464A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210436456.7A CN114602464A (en) 2022-04-25 2022-04-25 Hydrocatalyst for C-V petroleum resin and its preparing process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210436456.7A CN114602464A (en) 2022-04-25 2022-04-25 Hydrocatalyst for C-V petroleum resin and its preparing process

Publications (1)

Publication Number Publication Date
CN114602464A true CN114602464A (en) 2022-06-10

Family

ID=81869532

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210436456.7A Pending CN114602464A (en) 2022-04-25 2022-04-25 Hydrocatalyst for C-V petroleum resin and its preparing process

Country Status (1)

Country Link
CN (1) CN114602464A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115814787A (en) * 2023-01-03 2023-03-21 中化泉州能源科技有限责任公司 Metal loss resistant carbon five petroleum resin hydrogenation catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008033324A1 (en) * 2007-07-18 2009-02-19 China Petroleum & Chemical Corp., Chaoyang Pd / C hydrogenation catalyst, preparation and use thereof
CN103357423A (en) * 2013-07-29 2013-10-23 西安凯立化工有限公司 Preparation method of modified palladium-carbon catalyst for aromatic amine preparation, and application of catalyst
CN103386308A (en) * 2013-07-27 2013-11-13 西安凯立化工有限公司 Nickel catalyst for C5 petroleum resin hydrogenation as well as preparation method and application thereof
CN104043484A (en) * 2013-03-13 2014-09-17 中国石油天然气股份有限公司 Catalyst for preparing ethanol by catalytic hydrogenation of acetic acid and preparation and application thereof
CN104941649A (en) * 2015-04-14 2015-09-30 大连理工大学 Hydrogenation catalyst for petroleum resin and preparation method and application thereof
CN111375413A (en) * 2018-12-29 2020-07-07 中国石油化工股份有限公司 Reduced hydrogenation catalyst and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008033324A1 (en) * 2007-07-18 2009-02-19 China Petroleum & Chemical Corp., Chaoyang Pd / C hydrogenation catalyst, preparation and use thereof
CN104043484A (en) * 2013-03-13 2014-09-17 中国石油天然气股份有限公司 Catalyst for preparing ethanol by catalytic hydrogenation of acetic acid and preparation and application thereof
CN103386308A (en) * 2013-07-27 2013-11-13 西安凯立化工有限公司 Nickel catalyst for C5 petroleum resin hydrogenation as well as preparation method and application thereof
CN103357423A (en) * 2013-07-29 2013-10-23 西安凯立化工有限公司 Preparation method of modified palladium-carbon catalyst for aromatic amine preparation, and application of catalyst
CN104941649A (en) * 2015-04-14 2015-09-30 大连理工大学 Hydrogenation catalyst for petroleum resin and preparation method and application thereof
CN111375413A (en) * 2018-12-29 2020-07-07 中国石油化工股份有限公司 Reduced hydrogenation catalyst and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115814787A (en) * 2023-01-03 2023-03-21 中化泉州能源科技有限责任公司 Metal loss resistant carbon five petroleum resin hydrogenation catalyst
CN115814787B (en) * 2023-01-03 2024-05-14 中化泉州能源科技有限责任公司 Anti-metal-loss carbon five petroleum resin hydrogenation catalyst

Similar Documents

Publication Publication Date Title
CN109999902B (en) Packaged platinum group sub-nanometer metal loaded porous titanium-silicon molecular sieve catalyst and preparation and application thereof
US6126914A (en) Hydrogenation catalyst for production of hydrogen peroxide, and method for preparation of same
CN107020147A (en) A kind of MFI structure sheet molecular sieve catalyst, the preparation method and the usage of package metals oxide or metal nanoparticle
WO2007134722A1 (en) Temperature-resistant catalyst for gas phase oxidation
CN113600157B (en) Rare earth doped spherical alumina Pd-based catalyst and preparation method and application thereof
CN107626329B (en) Platinum/alumina catalyst and preparation method and application thereof
EP0690825B1 (en) Catalytic treatment process for effluents containing organic and inorganic compounds, preferably from epichlorhydrine production
CN101157029A (en) A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method
CN112371173B (en) Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof
CN113117671A (en) Hydrogen peroxide catalyst, preparation method and application
CN111686721A (en) Palladium ruthenium alloy catalyst and preparation method and application thereof
CN114602464A (en) Hydrocatalyst for C-V petroleum resin and its preparing process
CN109806861B (en) Preparation of nano-sandwich structure noble metal catalyst and application of nano-sandwich structure noble metal catalyst in hydrogen and oxygen direct synthesis of hydrogen peroxide
CN113171772A (en) Preparation method of noble metal-based catalyst
CN113426475B (en) Alpha, beta-unsaturated aldehyde ketone hydrogenation catalyst and preparation method thereof
CN111250098B (en) Water hydrogenation catalyst for Fischer-Tropsch synthesis reaction and preparation method and application thereof
CN114669294A (en) Composite catalyst for preparing 2, 2-di (2-tetrahydrofuryl) propane by hydrogenating 2, 2-di (2-furyl) propane
CN106964385A (en) Carrier-free copper bismuth catalyst for preparing 1,4 butynediols and preparation method thereof
Toshima et al. Platinum cluster catalysts supported on porous chelate resin-metal complexes: effect of resin porosity on catalytic activity
CN1192819C (en) Catalytic oxidation method of carbon-containing compound
CN111013583A (en) Preparation method of monolithic catalyst for efficiently decomposing carbon monoxide at room temperature
CN1150060C (en) Adsorbent for removing carbonyl metal compound in gas
DE19847792A1 (en) Process for the production of precious metal-containing catalysts on carbon-containing support materials
CN115814787B (en) Anti-metal-loss carbon five petroleum resin hydrogenation catalyst
EP4434619A1 (en) Catalyst for catalytic degradation of ethylene, preparation method therefor and use thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination