PREPARATION METHOD OF HIGHLY AROMATIC HYDROCARBON HYDROGENATED RESIN

Abstract

The present invention relates to a preparation method of a highly aromatic hydrocarbon hydrogenated resin, comprising the processes of fraction cutting, pretreatment, catalytic polymerization, two-stage hydrogenation, etc. The highly aromatic hydrocarbon hydrogenated resin obtained by the present invention has excellent compatibility with elastomers such as SBS, SIS and the like, and is suitable for hot melt adhesives, coatings, rubber modification, etc.

Claims

1. A preparation method of a highly aromatic hydrocarbon hydrogenated resin, comprising: step 1, an ethylene tar is rectifying cut to obtain fraction A with a distillation range of 180˜260° C., which is degummed in a packed bed for use; step 2, the fraction A and a C5 monoolefin is mixed at a mass ratio of 1:(0˜0.2) to obtain ingredient B; first 40˜60% of the total material mass of a solvent and 0.2˜2.0% of a Friedel-Crafts catalyst are charged into a stirred reactor, then ingredient B is added dropwisely at −30˜10° C. and the reaction is carried out for 0.5˜3 h to obtain a polymerization solution; step 3, the polymerization solution in the step 2 is alkali-washed, and then washed with water to neutral, the catalyst is removed; then, vacuum distillation is carried out to 200˜250° C. under a vacuum of −0.08˜−0.09 MPa to remove the solvent and oligomers to obtain a resin liquid; step 4, the resin liquid in the step 3 is diluted with a hydrogenated mineral oil at a mass ratio of 1:(2˜10), and then sent to a first-stage hydrogenation reactor, and react with H.sub.2 at a pressure of 10˜18 MPa and a temperature of 280˜350° C. in the presence of Fe—Mo/γ-Al.sub.2O.sub.3 hydrogenation catalyst to obtain a hydrogenated resin liquid A; step 5, the hydrogenated resin liquid A obtained in the step 4 is sent to an activated alumina packed column to remove impurities at 120˜180° C.; then to a second-stage hydrogenation reactor to react with H.sub.2 at a pressure of 12˜15 MPa and a temperature of 240˜300° C. in the presence of a metal modified Pd/γ-Al.sub.2O.sub.3 catalyst to obtain a hydrogenated resin liquid B; and step 6, the hydrogenated resin liquid B obtained in the step 5 is sent to a rectification column, and the rectification is carried out at a vacuum degree of −0.080˜−0.095 MPa and a temperature of 200˜260° C., the solvent is recovered at the top of the column, and the bottom material is granulated to obtain the highly aromatic hydrogenated resin.

2. The preparation method according to claim 1, wherein the composition of the fraction A in the step 1 is: 0.5˜4.0 wt % methylstyrene, 0.5˜2.0 wt % dihydrodicyclopentadiene, 2.0˜5.0 wt % indene, 10.0˜25.0 wt % methylindene, 3.0˜8.0 wt % dimethylindene, 20.0˜35.0 wt % naphthalene, 10.0˜15.0 wt % methylnaphthalene, 3.0˜8.0 wt % dimethylnaphthalene, the rest are inert components.

3. The preparation method according to claim 1, wherein the composition of the C5 monoolefin in the step 2 is: 2.0˜5.0 wt % 1-pentene, 10.0˜20.0 wt % 2-pentene, 8.0˜15.0 wt % 2-methyl-1-butene, 20.0˜30.0 wt % 2-methyl-2-butene, 0˜5.0 wt % cyclopentene, the rest are inert components.

4. The preparation method according to claim 1, wherein the composition of ingredient B in the step 2 is: 0˜0.83 wt % 1-pentene, 0˜3.33 wt % 2-pentene, 0˜2.5 wt % 2-methyl-1-butene, 0˜5.0 wt % 2-methyl-2-butene, 0˜0.83 wt % cyclopentene, 0.42˜4.0 wt % methylstyrene, 0.42˜2.0 wt % dihydrodicyclopentadiene, 1.67˜5.0 wt % indene, 8.33˜25.0 wt % methylindene, 2.5˜8.0 wt % dimethylindene, 16.67˜35.0 wt % naphthalene, 8.33˜15.0 wt % methylnaphthalene, 2.5˜8.0 wt % dimethylnaphthalene, the rest are inert components.

5. The preparation method according to claim 1, wherein the solvent in the step 2 is one or more of toluene, xylene, and trimethy-benzene.

6. The preparation method according to claim 1, wherein the Fe—Mo/γ-Al.sub.2O.sub.3 hydrogenation catalyst in the step 4 has a Fe/Mo molar ratio of (1.5˜2.2):1, and the content of γ-Al.sub.2O.sub.3 is 55˜70 wt %.

7. The preparation method according to claim 1, wherein the activated alumina in the step 5 is obtained by modifying with 0.05˜1.5 wt % iron sulfate or aluminum sulfate, and the average diameter thereof is 13˜25 mm.

8. The preparation method according to claim 1, wherein the metal-modified Pd in the metal-modified Pd/γ-Al.sub.2O.sub.3 catalyst in the step 5 is Mo-modified Pd, wherein the content of Pd is 0.8˜1.1 wt %, the Mo/Pd molar ratio is (0.02˜0.2):1, the rest is γ-Al.sub.2O.sub.3; the metal-modified Pd/γ-Al.sub.2O.sub.3 catalyst has a specific surface area of 130˜180 m.sup.2/g, a pore volume of 0.4˜0.6 cm.sup.3/g, and a particle size of 2˜10 mm.

9. The preparation method according to claim 1, wherein the highly aromatic hydrogenated resin obtained in the step 6 has a softening point of 90˜120° C., a Gardner color number of ≤4.0 #, and an aromaticity of 5˜20%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] FIG. 1 is a schematic diagram of the process flow of the present invention.

DESCRIPTION OF THE EMBODIMENTS

[0033] The present invention will be further explained below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, the skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

[0034] Due to the extremely complex composition of ethylene tar, Table 1 is only its approximate composition.

TABLE-US-00001 TABLE 1 Components Content, wt % Naphthalene  4.0~18.0 Indene and derivatives thereof  0.5~10.0 Methylnaphthalene  2.0~10.0 Dimethylnaphthalene  2.0~10.0 Biphenyl 0.5~2.0 Benzopyrene 0.1~2.0 Aromatic compounds 20.0~60.0 Asphaltene 10.0~40.0

[0035] The typical composition of cut fraction A of the ethylene tar used in the examples is shown in Table 2.

TABLE-US-00002 TABLE 2 Typical composition of fraction A (distillation range: 180~260° C.) No. Compound name Content, % 1 Methylstyrene 1.5 2 Dihydrodicyclopentadiene 0.9 3 Dimethylethylbenzene 2.5 4 Indene (1H-indene) 3.8 5 Methylindene 14.4 6 Dimethylindene 6.5 7 Naphthalene 28.7 8 Methylnaphthalene 12.5 9 Dimethylnaphthalene 6.0 10 Biphenyl 5.4 11 Remaining components 17.8

[0036] The filler of packed bed used in the examples is an inert alumina porcelain ball, and the average diameter thereof is 8˜11 mm. The hydrogenated mineral oil used in the examples is a low-viscosity saturated mineral oil with a distillation range of 250-400° C. and a bromine value ≤1.0 g/100 g.

[0037] The Fe—Mo/γ-Al.sub.2O.sub.3 hydrogenation catalyst used in the examples has a Fe/Mo molar ratio of 2:1, and a γ-Al.sub.2O.sub.3 content of 62.5 wt %.

[0038] The activated alumina was obtained by modifying with 1.5 wt % iron sulfate or aluminum sulfate, and has an average diameter of 13-17 mm.

[0039] The metal modified Pd in the metal-modified Pd/γ-Al.sub.2O.sub.3 catalyst used in the examples is Mo modified Pd; the γ-Al.sub.2O.sub.3 content is 98.7 wt %; the Mo modified Pd/γ-Al.sub.2O.sub.3 catalyst has a specific surface area of 160 m.sup.2/g, a pore volume of 0.5 cm.sup.3/g, a particle size of 4˜6 mm.

Example 1

[0040] (1) an ethylene tar was rectifying cut to obtain fraction A with a distillation range of 180˜260° C., which was passed through an alumina packed bed to reduce its gum to 20 ppm.

[0041] (2) fraction A mentioned above and a C5 monoolefin was mixed at a mass ratio of 1:0.15 to obtain ingredient B, wherein the composition of ingredient B is: 0.26% 1-pentene, 1.13% 2-pentene, 1.87% 2-methyl-1-butene, 2.65% 2-methyl-2-butene, 0.59% cyclopentene, 0.60% methylstyrene, 1.04% dihydrodicyclopentadiene, 4.27% indene, 15.43% methylindene, 6.68% dimethylindene, 26.51% naphthalene, 9.06% methylnaphthalene, 4.55% dimethylnaphthalene, the rest are inert components; first 40% of the total material mass of xylene and 0.7% of boron trifluoride ether catalyst were charged into a stirred reactor, then ingredient B was added dropwisely at −5° C. and the reaction was carried out for 2 h to obtain a polymerization solution.

[0042] (3) the polymerization solution in step (2) was alkali-washed, and then washed with water to neutral, the catalyst is removed (with a 10% alkali solution); then, vacuum distillation was carried out under a vacuum of −0.09 MPa and a temperature of 240° C. to remove the solvent and oligomers to obtain a resin liquid.

[0043] (4) the resin liquid in step (3) was diluted with a hydrogenated mineral oil at a mass ratio of 1:3, and then sent to a first-stage hydrogenation reactor, and reacted with H.sub.2 at a pressure of 11.5 MPa and a temperature of 320° C. in the presence of Fe—Mo/γ-Al.sub.2O.sub.3 hydrogenation catalyst to obtain a hydrogenated resin liquid A, wherein the liquid hourly space velocity LSHV was 0.5 h.sup.−1.

[0044] (5) the hydrogenated resin liquid A obtained in step (4) was sent to an activated alumina packed column to remove impurities such as halogen and gums at 150° C.; then to a second-stage hydrogenation reactor to react with H.sub.2 at a pressure of 12 MPa and a temperature of 270° C. in the presence of a metal modified Pd/γ-Al.sub.2O.sub.3 catalyst to obtain a hydrogenated resin liquid B, wherein the liquid hourly space velocity LSHV was 0.67 h.sup.−1;

[0045] (6) the hydrogenated resin liquid B obtained in step (5) was sent to an rectification column, and the rectification was carried out at a vacuum degree of −0.085 MPa and a temperature of 240° C., the solvent was recovered at the top of the column, and the bottom material was granulated to obtain a highly aromatic hydrogenated resin having a softening point of 101.5° C., a Gardner color number of 1.4, and an aromaticity of 10.3%.

Examples 2˜6

[0046] The ratio of the cut fraction A of the ethylene tar to the C5 monoolefins in the polymerization feedstock is a key factor in the process of the present invention. Table 3 below shows the effect of the main polymerizable monomers in ingredients B after the two were mixed on the resin products; the remaining conditions are the same as those in Example 1.

TABLE-US-00003 TABLE 3 Composition Example 2 Example 3 Example 4 Example 5 Example 6 Total C5 monoolefins, % 0 2.48 5.66 8.87 11.53 Indene and derivatives, % 28.65 25.47 24.50 19.96 16.41 Naphthalene and 49.20 44.15 41.23 38.56 35.77 derivatives, % Properties of highly aromatic hydrocarbon hydrogenated resins Gardner color 2.8 1.6 1.4 1.1 0.8 number, # Softening point, ° C. 117.1 106.0 102.5 100.2 94.5 Aromaticity, % 16.2 13.7 12.4 9.3 8.6 Mw/Mn 1.40 1.48 1.53 1.55 1.68

[0047] It can be seen from the above Examples 2˜6 that, as the total content of the C5 monoolefins in ingredient B increases, the softening point, the Gardner color number and the aromaticity of the hydrogenated resin all decrease, and the molecular weight distribution Mw/Mn tends to increase. When there is no C5 monoolefin as a modifier, the hydrogenated resin has the maximum aromaticity. The hydrogenated resin has a suitable aromaticity and molecular weight distribution, which can effectively enhance the compatibility with the elastomers such as SBS, SIS, and the like, and improve the cohesive strength of blends therefrom.

Examples 7˜10

[0048] Table 4 below is based on steps (1) to (3) of Example 1, wherein the process conditions of the first-stage Fe—Mo/γ-Al.sub.2O.sub.3 catalytic hydrogenation were adjusted, and their effects on hydrogenated resins were studied. The remaining conditions were the same as those in Example 1.

TABLE-US-00004 TABLE 4 Process conditions for hydrogenation Example 7 Example 8 Example 9 Example 10 Temperature, ° C. 280 320 320 350 Pressure, MPa 12 12 18 12 LSHV, h.sup.−1 0.5 0.5 0.5 1.0 Properties of highly aromatic hydrocarbon hydrogenated resins Gardner color 2.2 1.4 1.3 0.9 number, # Softening point, ° C. 105.5 102.0 102.3 93.8 Aromaticity, % 12.0 10.4 9.8 7.2 Mw/Mn 1.57 1.50 1.51 1.46

[0049] It can be seen from the above Examples 7˜10 that, in the first-stage hydrogenation process, the hydrogenation temperature has a more obvious effect on the performance of the hydrogenated resin. The first-stage hydrogenation process can increase the hydrogenation degree of hydrogenated resins, improve the thermal cracking tendency of the resin, which lowers the softening point and molecular weight distribution, and the aromaticity.

Examples 11˜13

[0050] The second-stage hydrogenation catalyst is a trace Mo modified Pd catalyst, and modified catalysts having a Pd content of 1.00% were compared in Examples 11˜13, and the remaining conditions are the same as those in Example 1.

TABLE-US-00005 TABLE 5 Example 11 Example 12 Example 13 Mo:Pd 0.03 0.09 0.15 Properties of highly aromatic hydrocarbon hydrogenated resins Gardner color 1.4 1.5 1.4 number, # Softening point, ° C. 102.3 100.5 100.8 Aromaticity, % 10.5 8.8 7.5 Mw/Mn 1.55 1.51 1.47

[0051] It can be seen from the above Table that, the change of the Mo content in the second-stage hydrogenation catalyst has a critical influence on the aromaticity and the molecular weight distribution of the hydrogenated resin. Mo in the second-stage hydrogenation catalyst can be used as its Lewis acid adsorption center, which is conducive to the adsorption of petroleum resin molecules on the carrier, thereby improving its activity and enhancing its hydrogenation selectivity to aromatic groups. The presence of Mo reduces the loss of Pd of the Pd catalyst during the reaction, improves the stability of the catalyst and prolongs the service life of the Pd catalyst.

Comparative Example 1

[0052] The resin liquid obtained in steps (1)˜(3) in Example 1 was diluted with a hydrogenated mineral oil at a mass ratio of 1:3 and then sent to a hydrogenation reactor. In the presence of Pd/γ-Al.sub.2O.sub.3 catalyst, it reacted with H.sub.2 at a pressure of 14.0 MPa and a temperature of 280° C. to obtain a hydrogenated resin liquid, wherein the liquid hourly space velocity LSHV is 0.5 h.sup.−1; then it was transported to a rectification column, and vacuum rectified at a vacuum of −0.085 MPa and a temperature of 240° C. The solvent was recovered at the top of the tower. After the bottom material was pelletized, a hydrogenated resin with a softening point of 105.5° C., a Gardner color number of 2.2 and an aromaticity of 16.7% was obtained.

[0053] The above-mentioned Pd/γ-Al.sub.2O.sub.3 catalyst is a general-purpose palladium-based catalyst with a Pd content of 0.95˜1.05% and the rest being γ-Al.sub.2O.sub.3. Due to lack of first-stage hydrogenation catalyst protection, the service life of the palladium-based catalyst is relatively short, usually less then 200 h.

Comparative Example 2

[0054] The resin liquid obtained in steps (1)˜(3) in Example 1 was diluted with a hydrogenated mineral oil at a mass ratio of 1:3 and then sent to a hydrogenation reactor. In the presence of Raney nickel catalyst, it reacted with H.sub.2 at a pressure of 11.0 MPa and a temperature of 270° C. to obtain a hydrogenated resin liquid, wherein the liquid hourly space velocity LSHV is 0.5 h.sup.−1; then it was transported to a rectification column, and vacuum rectified at a vacuum of −0.085 MPa and a temperature of 240° C. The solvent was recovered at the top of the tower. After the bottom material was pelletized, a hydrogenated resin with a softening point of 86.0° C., a Gardner color number of 1.5 and an aromaticity of 3.8% was obtained.

[0055] The above-mentioned Raney nickel catalyst has a Ni—Al structure, with a Ni content of 41% and an Al content of 59%. In the presence of the catalyst, the molecular bonds of petroleum resin were broken and degraded, the softening point was greatly reduced, and the aromatic groups were saturated in a large amount. Similarly, due to the influence of impurities such as halogen and sulfur, the service life of the Raney nickel catalyst is less than 200 h.