Low-color high-transparency carbon five petroleum resin hydrogenation catalyst and preparation method thereof

Abstract

The present application relates to a kind of low chroma high transparent carbon five petroleum resin hydrogenation catalyst and its preparation method, mainly solve the poor activity of this kind of carbon five petroleum resin catalyst, the problem of poor stability.The carbon five petroleum resin hydrogenation catalyst involved in the present application is prepared using colloidal carbon coating method, should include the following components: (a) active metal is one or several of Pt group;(b) adjuvant is boron nitride;(c) carrier is colloidal carbon ball.Under the action of the catalyst of the present application, the carrier carbon ball helps the adsorption of unsaturated bond in petroleum resin molecule, the modification of boron nitride can improve the ability of active metal activation hydrogen, and then improve hydrogenation activity and the chroma of hydrogenated carbon five resin.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of low color high transparent carbon five petroleum resin hydrogenation catalyst. BACKGROUND

[0002] The main chain of carbon five petroleum resin is fatty structure, with low acid value, good miscibility, water resistance, ethanol resistance and chemical corrosion resistance etc.But due to the existence of unsaturated chemical bond in carbon five petroleum resin, carbon five petroleum resin has the defects of large brittleness, deep color, odor and lack of polar groups in structure etc.Through the way of catalytic hydrogenation, the unsaturated carbon-carbon double bond in it is hydrogenated to saturation, thereby reducing its unsaturation, increasing the stability and antioxidant properties of resin etc.Hydrogenated carbon five petroleum resin is colorless, odorless, high light oxygen stability, is the upgrade of ordinary yellow resin used in specific field, especially furniture adhesive, ink, high-grade paper, paint etc.Field used additives.With the improvement of human health and environmental protection requirements, hydrogenated carbon five resin will gradually replace carbon five petroleum resin production capacity, realize application in more fields.

[0003] C5 petroleum resin hydrogenation catalysts are mainly divided into Ni-based and noble metal-based catalysts.Although Ni-based catalysts have cost advantage and are easy to industrialize, their activity is relatively low, and high reaction temperature is needed.In view of the above problems, in recent years, noble metal catalysts are gradually increasing in the application of carbon five petroleum resin hydrogenation, and noble metal catalysts have higher hydrogenation performance and milder reaction conditions, but the dispersion of noble metal on the carrier is poor, and the chlorine element in the resin often causes the loss of active metal in the hydrogenation catalyst.Patent CN104525198B improves the catalytic activity of the catalyst by adding Ag or VB group elements, and at the same time makes it have good resistance to sulfur, halogen, nitrogen and other impurities, so as to have longer service life.CN106268725A uses γ-alumina as carrier and adopts step-by-step method to load 0.5%~1.2% palladium, 0.5%~1.2% molybdenum, 5.0%~10.0% manganese and other metals, so that the catalyst has good hydrogenation activity.CN102935367B provides a C5 petroleum resin hydrogenation catalyst, which comprises an alumina-titanium oxide composite carrier and a metal palladium and an auxiliary agent molybdenum, tungsten loaded on the composite carrier, and the catalyst has not only low hydrogenation activity, but also good impurity resistance and good stability when used in C5 petroleum resin hydrogenation process.

[0004] In the research results of existing patents and documents, there is no mention of using colloidal carbon spheres as carrier to composite platinum group active metal and boron nitride to form petroleum resin hydrogenation catalyst, in order to improve hydrogenation activity and adjust the color and transparency of hydrogenated petroleum resin.The interaction between boron nitride and platinum group metal can improve the ability of active metal to activate hydrogen, and the unsaturated bond in the carrier carbon sphere can improve the adsorption of resin macromolecules on the surface of the catalyst, and the interaction of multiple components can improve the performance of the catalyst. SUMMARY

[0005] One of the technical problems to be solved by the present application is to improve the hydrogenation activity of the catalyst and reduce the color of the hydrogenated resin.

[0006] Another technical problem to be solved by the present application is to provide a preparation method of the catalyst described in one of the above technical problems.

[0007] A third technical problem to be solved by the present application is to provide a method for the hydrorefining reaction of carbon five petroleum resin by using the catalyst described in one of the above technical problems.

[0008] To solve one of the above technical problems, the present application provides a low-color high-transparency carbon five petroleum resin hydrogenation catalyst preparation method, and the technical solution of the present application is as follows: a low-color high-transparency carbon five petroleum resin hydrogenation catalyst preparation method, comprising the following components:

[0009] (a) the active metal is one or more of the Pt group;

[0010] (b) the additive is boron nitride;

[0011] (c) the carrier is colloidal carbon spheres.

[0012] In the above technical solution, the active metal is one or more of the Pt group active metals, which are Pt, Pd, Ir, Ru, and Rh.

[0013] In the above technical solution, the proportion of the active metal in the catalyst is 0.01-5%, and the proportion of the additive boron nitride in the catalyst is 0.5-10%. The rest is colloidal carbon spheres.

[0014] In the above technical solution, the additive boron nitride is one of hexagonal boron nitride (HBN), rhombohedral boron nitride (RBN), cubic boron nitride (CBN), and wurtzite boron nitride (WBN).

[0015] In the above technical solution, the colloidal carbon spheres are obtained by dehydration and crosslinking of polyhydroxy compounds such as glucose, fructose, sucrose, or cyclodextrin, and then calcining under nitrogen.

[0016] Another object of the present application is to provide a low-color high-transparency carbon five petroleum resin hydrogenation catalyst preparation method, which uses colloidal carbon spheres as a carrier to complex platinum group active metals and boron nitride to form a petroleum resin hydrogenation catalyst, so as to improve the hydrogenation activity and adjust the color and transparency of the hydrogenated petroleum resin.

[0017] To achieve this object, the technical solution of the present application is as follows:

[0018] The preparation method of the low-color high-transparency carbon five petroleum resin hydrogenation catalyst is as follows:

[0019] (1) The catalyst proportion of palladium chloride and hexagonal boron nitride is weighed and dispersed in 100 ml of water, stirred for 4 hours, and then the catalyst proportion of glucose is added and dissolved in the above solution until the glucose is completely dissolved.

[0020] (2) The above aqueous solution containing palladium salt, boron nitride powder and glucose is transferred to a high-pressure reaction kettle, hydrothermally reacted at 200°C for 48h, and then filtered, washed and dried to obtain black-brown powder.

[0021] (3) The obtained black-brown powder is transferred to a tube furnace, activated at 650°C for 12 hours under a nitrogen atmosphere, and a carbon five petroleum resin hydrogenation catalyst containing Pd, boron nitride and colloidal carbon spheres is obtained.

[0022] In the above preparation technical solution, the active metal precursor is one or more of soluble salts such as nitrate, chloride, acetate, and preferably chloride.

[0023] In the above preparation technical solution, the hydrothermal temperature is 120-260°C.

[0024] In the above preparation technical solution, the hydrothermal time is 12-72 hours.

[0025] In the above preparation technical solution, the calcination atmosphere is inert gas nitrogen, argon, helium, and preferably nitrogen.

[0026] In the above preparation technical solution, the inert atmosphere activation temperature is 450-800°C.

[0027] In the above preparation technical solution, the inert atmosphere activation time is 6-60 hours.

[0028] The third technical problem to be solved by the present application is to provide an application method of the above catalyst for carbon five petroleum resin hydrofining reaction.

[0029] To solve the above technical problems, the technical solution of the present application is as follows:

[0030] The present application uses a cyclohexane solution of carbon five resin as a reactant to evaluate the performance of the catalyst in any one of the above technical solutions in a high-pressure fixed bed reactor. The catalyst loading mass is 20.0 ml. The catalyst is reduced with hydrogen before feeding to make the supported active component exist in the form of an element. The reduction conditions are: temperature 200-450°C, pressure 0.5-7.0 MPa, hydrogen flow rate 10-200 ml / min, time 0.5-5.0 h; reaction conditions: temperature 180-400°C, pressure 1.0-15.0 MPa, volume space velocity 0.5-4.5 h -1 , hydrogen / oil molar ratio 200-1000. The carbon five resin used for hydrogenation reaction is 5# resin with a bromine value of 5.93 g Br / 100 g.

[0031] Bromine value analysis was performed by iodine method (SWB2301-62) to calculate the conversion of petroleum resin hydrogenation reaction. The active metal content in the catalyst was tested by ICP-MS. The active metal dispersion in the catalyst was tested by H2-O2 titration method.

[0032]

[0033] The application will be further described by examples, but the examples are not intended to limit the scope of the application. DETAILED DESCRIPTION

[0034] Example 1: 0.5Pd-2h-BN@C

[0035] 1. Catalyst preparation

[0036] 0.17 g of palladium chloride and 0.4 g of hexagonal boron nitride (h-BN) were weighed and dispersed in 100 ml of water. After being stirred for 4 hours, 48.8 g of glucose was added to the above solution until the glucose was completely dissolved. The above aqueous solution containing palladium salt, boron nitride powder, and glucose was transferred to a high-pressure reaction kettle, and hydrothermal reaction was carried out at 200℃ for 48 h. Then, the black-brown powder was obtained by filtration, washing, and drying. The obtained black-brown powder was transferred to a tube furnace, and activated at 650℃ for 12 hours under nitrogen atmosphere to obtain a carbon five petroleum resin hydrogenation catalyst containing Pd, boron nitride, and colloidal carbon spheres, which was marked as 0.5Pd-2h-BN@C.

[0037] The above 0.5Pd-2h-BN@C catalyst was compacted and formed, and then crushed and sieved into 40 mesh granular catalyst for catalytic performance test.

[0038] 2. Catalyst evaluation

[0039] The carbon five resin hydrogenation reaction was carried out in a high-pressure fixed bed reactor, and the catalyst loading mass was 10.0 ml. Before the reaction, the catalyst was reduced at 450℃ under normal pressure for 2 hours. After the temperature was reduced to the reaction temperature, 20wt% carbon five resin-cyclohexane solution and hydrogen were introduced for reaction. The reaction conditions were as follows: reaction temperature 250℃, reaction pressure 8.0 MPa, mass space velocity of raw material 1.0 h -1 , and the molar ratio of hydrogen to carbon five resin-cyclohexane solution was 600:1. The reaction results are shown in Table 1.

[0040] Comparative Example 1: 0.5Pd@C

[0041] 1. Catalyst preparation

[0042] Take 0.17 g of palladium chloride dispersed in 100 ml of water, after stirring for 4 hours, add 49.8 g of glucose to dissolve in the above solution, until the glucose is completely dissolved. The above water solution containing palladium salt and glucose is transferred to a high pressure reactor, hydrothermal reaction at 200°C for 48h, then filtered, washed and dried to get black brown powder. The obtained black brown powder is transferred to a tube furnace, activated at 650°C for 12 hours under nitrogen atmosphere, to get carbon five petroleum resin hydrogenation catalyst containing Pd and colloidal carbon balls, the catalyst is marked as 0.5Pd@C.

[0043] The above 0.5Pd@C catalyst is compacted and formed, then crushed and sieved into 40 mesh granular catalyst for catalytic performance test.

[0044] 2. Catalyst evaluation

[0045] The catalyst is evaluated in the same way as in Example 1 for its catalytic performance in carbon five resin hydrogenation refining reaction. The reaction results are shown in Table 1.

[0046]

Comparative Example 2

[0047] 1. Catalyst preparation

[0048] Take 0.4 g of hexagonal boron nitride (h-BN) dispersed in 100 ml of water, after stirring for 4 hours, add 49.0 g of glucose to dissolve in the above solution, until the glucose is completely dissolved. The above water solution containing boron nitride powder and glucose is transferred to a high pressure reactor, hydrothermal reaction at 200°C for 48h, then filtered, washed and dried to get black brown powder. The obtained black brown powder is transferred to a tube furnace, activated at 650°C for 12 hours under nitrogen atmosphere, to get carbon five petroleum resin hydrogenation catalyst containing hexagonal boron nitride (h-BN) and colloidal carbon balls, the catalyst is marked as 2BN@C.

[0049] The above 2BN@C catalyst is compacted and formed, then crushed and sieved into 40 mesh granular catalyst for catalytic performance test.

[0050] 2. Catalyst evaluation

[0051] The catalyst is evaluated in the same way as in Example 1 for its catalytic performance in carbon five resin hydrogenation refining reaction. The reaction results are shown in Table 1.

[0052]

Comparative Example 3

[0053] 0.17 g of palladium chloride and 19.1 g of hexagonal boron nitride (h-BN) were weighed into 100 ml of water, stirred thoroughly for 4 hours, and then evaporated in a water bath at 90°C. After that, they were dried in an oven at 120°C for 12 hours, and then calcined in a muffle furnace at 500°C for 6 hours to obtain a carbon five petroleum resin hydrogenation catalyst containing Pd and hexagonal boron nitride (h-BN), which was marked as 2BN@C.

[0054] After the 2BN@C catalyst was compacted and formed, it was crushed and sieved into a 40-mesh granular catalyst for testing of the catalytic performance.

[0055] 2. Catalyst evaluation

[0056] The catalytic performance of the catalyst in the carbon five resin hydrogenation refining reaction was evaluated in the same manner as in Example 1. The reaction results are shown in Table 1.

[0057]

Example 2

[0058] 1. Catalyst preparation

[0059] 0.21 g of chloroplatinic acid and 0.4 g of hexagonal boron nitride (h-BN) were weighed into 100 ml of water, stirred thoroughly for 4 hours, and then 48.8 g of glucose was added and dissolved in the above solution until the glucose was completely dissolved. The aqueous solution containing the palladium salt, boron nitride powder, and glucose was transferred to a high-pressure reaction kettle and hydrothermally reacted at 200°C for 48 hours. After that, the black-brown powder was obtained by filtration, washing, and drying. The obtained black-brown powder was transferred to a tube calcination furnace and activated at 650°C for 12 hours under a nitrogen atmosphere to obtain a carbon five petroleum resin hydrogenation catalyst containing Pd, boron nitride, and colloidal carbon spheres, which was marked as 0.5Pd-2h-BN@C.

[0060] After the 0.5Pd-2h-BN@C catalyst was compacted and formed, it was crushed and sieved into a 40-mesh granular catalyst for testing of the catalytic performance.

[0061] 2. Catalyst evaluation

[0062] The catalytic performance of the catalyst in the carbon five resin hydrogenation refining reaction was evaluated in the same manner as in Example 1. The reaction results are shown in Table 1.

[0063]

Example 3

[0064] 1. Catalyst preparation

[0065] Take 0.16 g of iridium chloride and 0.4 g of hexagonal boron nitride (h-BN) dispersed in 100 ml of water, after stirring for 4 hours, add 48.8 g of glucose to dissolve in the above solution until the glucose is completely dissolved. The above aqueous solution containing palladium salt, boron nitride powder and glucose is transferred to a high pressure reactor, hydrothermal reaction at 200℃ for 48h, then filtered, washed and dried to obtain black brown powder. The obtained black brown powder is transferred to a tube furnace, activated at 650℃ for 12 hours under nitrogen atmosphere, to obtain a carbon five petroleum resin hydrogenation catalyst containing Pd, boron nitride and colloidal carbon spheres, and the catalyst is marked as 0.5Pd-2h-BN@C.

[0066] The above 0.5Pd-2h-BN@C catalyst is compacted and formed, then broken and sieved into 40 mesh granular catalyst for catalytic performance test.

[0067] 2、Catalyst evaluation

[0068] The catalytic performance of the catalyst in the carbon five resin hydrogenation refining reaction is evaluated by the same method as in Example 1. The reaction results are shown in Table 1.

[0069]

Example 4

[0070] 1、Catalyst preparation

[0071] Take 0.17 g of palladium chloride and 0.4 g of cubic boron nitride (c-BN) dispersed in 100 ml of water, after stirring for 4 hours, add 48.8 g of glucose to dissolve in the above solution until the glucose is completely dissolved. The above aqueous solution containing palladium salt, boron nitride powder and glucose is transferred to a high pressure reactor, hydrothermal reaction at 200℃ for 48h, then filtered, washed and dried to obtain black brown powder. The obtained black brown powder is transferred to a tube furnace, activated at 650℃ for 12 hours under nitrogen atmosphere, to obtain a carbon five petroleum resin hydrogenation catalyst containing Pd, boron nitride and colloidal carbon spheres, and the catalyst is marked as 0.5Pd-2c-BN@C.

[0072] The above 0.5Pd-2c-BN@C catalyst is compacted and formed, then broken and sieved into 40 mesh granular catalyst for catalytic performance test.

[0073] 2、Catalyst evaluation

[0074] The catalytic performance of the catalyst in the carbon five resin hydrogenation refining reaction is evaluated by the same method as in Example 1. The reaction results are shown in Table 1.

[0075]

Example 5

[0076] 1、Catalyst preparation

[0077] 0.17 g of palladium chloride and 0.4 g of r-BN were weighed into 100 ml of water, and after being stirred for 4 hours, 48.8 g of glucose was added to dissolve in the above solution until the glucose was completely dissolved. The above aqueous solution containing the palladium salt, boron nitride powder, and glucose was transferred to a high-pressure reactor, and hydrothermally reacted at 200°C for 48 hours, and then filtered, washed, and dried to obtain a black-brown powder. The obtained black-brown powder was transferred to a tube furnace, activated at 650°C for 12 hours under a nitrogen atmosphere, and a carbon five petroleum resin hydrogenation catalyst containing Pd, boron nitride, and colloidal carbon spheres was obtained, and the catalyst was labeled as 0.5Pd-2r-BN@C.

[0078] The above 0.5Pd-2r-BN@C catalyst was compacted and formed, and then crushed and sieved into a 40-mesh granular catalyst for testing of the catalytic performance.

[0079] 2. Catalyst evaluation

[0080] The catalytic performance of the catalyst in the carbon five resin hydrogenation refining reaction was evaluated by the same method as in Example 1. The reaction results are shown in Table 1.

[0081] From the comparison of Example 1, Example 2, Example 3, and Comparative Example 1, it can be seen that under the dispersion effect of the carbon spheres as the carrier, the active metal is dispersed in a smaller particle size, and the petroleum resin hydrogenation catalyst has higher activity.

[0082] From the comparison of Example 1 and Comparative Example 2, it can be seen that BN itself does not have hydrogenation activity.

[0083] From the comparison of Example 1 and Comparative Example 3, it can be seen that without the carbon spheres as the carrier, the Pd is loaded on the BN carrier, the particle size of the active metal Pd is larger, and the petroleum resin hydrogenation catalyst has lower activity.

[0084] Table 1 Catalyst performance list

[0085] Active metal particle size / nm Hydroconversion rate / % Hydroresin color Example 1 1.4 98 0# Comparative Example 1 1.6 86 1# Comparative Example 2 - - 5# Comparative Example 3 3.1 81 2# Example 2 1.4 96 0# Example 3 1.5 94 0# Example 4 1.3 94 0# Example 5 1.4 95 0#

[0086] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application shall be included in the scope of the present application.

Claims

1. A low color high transparency C5 petroleum resin hydrogenation catalyst, characterized in that, It comprises the following components: (a) active metal, one or more of Pt group; (b) assistant, boron nitride; (c) carrier, colloidal carbon sphere; The proportion of the active metal in the catalyst is 0.01-5%, the proportion of the assistant boron nitride in the catalyst is 0.5-10%, and the rest is colloidal carbon sphere; the colloidal carbon sphere is prepared by dehydration and crosslinking of glucose, fructose, sucrose or cyclodextrin polyhydroxy compound and then calcination under nitrogen.

2. The catalyst according to claim 1, characterized in that, The active metal is one or more of Pt, Pd, Ir, Ru and Rh.

3. The catalyst of claim 1, wherein The assistant is one of hexagonal boron nitride, rhombohedral boron nitride, cubic boron nitride or wurtzite boron nitride.

4. The process for the preparation of a catalyst according to any one of claims 1 to 3, characterized in that, It comprises the following steps: (1) the precursors of the active metal and hexagonal boron nitride in the proportion of the catalyst are dispersed in 100 mL water, stirred for 4 hours, then the glucose in the proportion of the catalyst is added and dissolved in the above solution until the glucose is completely dissolved; (2) the above water solution containing the precursors of the active metal, boron nitride powder and glucose is transferred to a high-pressure reaction kettle for hydrothermal reaction, then filtered, washed and dried to obtain black-brown powder; (3) the obtained black-brown powder is transferred to a tube furnace for activation in an inert gas atmosphere to obtain a carbon five petroleum resin hydrogenation catalyst containing active metal, boron nitride and colloidal carbon sphere.

5. The preparation method according to claim 4, characterized in that, The precursors of the active metal in step (1) include one or more of soluble salts such as nitrate, chloride and acetate.

6. The preparation method according to claim 4, characterized in that, The precursors of the active metal in step (1) are chloride soluble salts.

7. The preparation method according to claim 4, characterized in that, The hydrothermal reaction temperature in step (2) is 120-260℃.

8. The preparation method according to claim 4, characterized in that, The hydrothermal reaction time in step (2) is 12-72 hours.

9. The preparation method according to claim 4, characterized in that, The inert gas in step (3) includes any one of nitrogen, argon and helium.

10. The method of claim 4, wherein, The inert gas in step (3) is nitrogen.

11. The preparation method according to claim 4, characterized in that, The activation temperature in the inert gas atmosphere in step (3) is 450-800℃.

12. The method of claim 4, wherein, The activation time in the inert gas atmosphere in step (3) is 6-60 hours.

13. The catalyst according to any one of claims 1-3 for use in carbon five petroleum resin hydrofining.

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