阅读说明：本技术 一种高含硫石油树脂加氢的方法 (Hydrogenation method for high-sulfur petroleum resin ) 是由 梁长海 李闯 宋承业 陈霄 于 2020-05-27 设计创作，主要内容包括：本发明公开了一种高含硫石油树脂加氢的方法,属于聚合物加氢技术领域。其特征是以负载型双金属合金催化剂作为预加氢脱硫催化剂,负载型金属催化剂作为加氢脱色催化剂,采用两段固定床连续加氢方式对树脂进行加氢反应,所得氢化树脂,树脂色相改善至水白且具有良好的热稳定性。本发明具有工艺简单,催化剂活性高,稳定性好,改善了树脂色度,提高了其热稳定性,软化点略有降低,且具有良好的经济效益及工业应用前景。(The invention discloses a method for hydrogenating high-sulfur petroleum resin, belonging to the technical field of polymer hydrogenation. The method is characterized in that a supported bimetallic alloy catalyst is used as a pre-hydrogenation desulfurization catalyst, a supported metal catalyst is used as a hydrogenation decolorization catalyst, and a two-section fixed bed continuous hydrogenation mode is adopted to carry out hydrogenation reaction on resin, so that the obtained hydrogenated resin has the advantages that the color phase of the resin is improved to be water white, and the resin has good thermal stability. The invention has the advantages of simple process, high catalyst activity, good stability, improved resin chromaticity, improved thermal stability, slightly reduced softening point, good economic benefit and good industrial application prospect.)

1. A method for hydrogenating petroleum resin with high sulfur content uses a sulfur-resistant eggshell-shaped noble metal alloy as a first-stage hydrodesulfurization catalyst and a supported metal catalyst as a second-stage hydrogenation decolorization catalyst, and adopts a two-stage hydrogenation mode to carry out hydrogenation reaction on the resin to prepare hydrogenated resin, wherein the color phase of the resin is improved to be water white, and the softening point is reduced; the method is characterized by comprising the following steps:

heating the solvent to 130-150 ℃, dissolving the solvent and the molten high-sulfur petroleum resin uniformly in a dynamic mixer, wherein the high-sulfur petroleum resin accounts for 10-30% of the mass ratio of the mixed substances, then feeding the mixture into an impurity removal reactor filled with a colloid absorbing adsorbent to remove colloid, partial chlorine or chlorineFluorine; then mixing with hydrogen and injecting the mixture into a hydrodesulfurization tower filled with a hydrodesulfurization catalyst, wherein the hydrodesulfurization catalyst removes sulfur, chlorine or fluorine in the resin, the feeding temperature is 260-300 ℃, the hydrogen partial pressure is 2-4MPa, and the volume space velocity is 1-4h^-1The volume ratio of hydrogen to oil is 100-200: 1; the hydrodesulfurization catalyst is an eggshell type noble metal alloy catalyst; the resin solution after hydrodesulfurization enters a stripping gas-liquid separation tower, the content of dissolved hydrogen sulfide in the resin solution is reduced through hydrogen stripping, and the separated hydrogen is washed and recycled; the resin solution after hydrodesulfurization is pressurized and mixed with hydrogen to enter a deep hydrogenation tower for hydrogenation and decolorization, wherein the feeding temperature is 240-280 ℃, the hydrogen partial pressure is 8-18MPa, and the volume space velocity is 0.5-1.5h^-1The volume ratio of hydrogen to oil is 200-600: 1; the catalyst used for hydrogenation and decoloration is a supported metal catalyst; injecting the resin solution subjected to hydrogenation and decoloration into a solvent removal tower, distilling the resin solution at normal pressure, circularly dissolving the high-sulfur petroleum resin by using a product solvent distilled from the top of the tower, allowing a product at the bottom of the tower to enter a devolatilization tower, performing negative pressure operation on the devolatilization tower, and ejecting high-boiling-point oligomers generated by petroleum resin cracking in the hydrogenation and decoloration process out of the devolatilization tower; hydrogenated resin is discharged from the bottom of the devolatilization tower, the color phase of the resin is improved to be water white, and the softening point is reduced.

2. The method for hydrogenating high-sulfur petroleum resin according to claim 1, wherein the hydrogenation comprises: the colloid-absorbing adsorbent is Ca/Al₂O₃Wherein the mesopore volume accounts for more than 80% of the total pore volume, the pore diameter is 20-50nm, and Ca is added²⁺The mass content of (A) is 0.3-1.0%.

3. The method for hydrogenating high-sulfur petroleum resin according to claim 1 or 2, wherein the hydrogenation comprises: in the eggshell type noble metal alloy catalyst, the noble metal alloy is PdM, and M is one or more than two of Ir, Re, Pt, Ru, Au and Ag.

4. The method for hydrogenating high-sulfur petroleum resin according to claim 3, wherein the hydrogenation comprises: m is Pt or Ir, the molar ratio of Pd to M is 4:1, and the mass content of Pd0.3% -1.0%, and Al as carrier₂O₃、SiO₂、TiO₂、SiO₂-Al₂O₃Or Al₂O₃-TiO₂。

5. The method for hydrogenating high-sulfur petroleum resin according to claim 1, 2 or 4, wherein the hydrogenation comprises the following steps: the supported metal catalyst is a noble metal catalyst, a high nickel catalyst or a skeletal nickel catalyst.

6. The method for hydrogenating high-sulfur petroleum resin according to claim 3, wherein the hydrogenation comprises: the supported metal catalyst is a noble metal catalyst, a high nickel catalyst or a skeletal nickel catalyst.

7. The method for hydrogenating high-sulfur petroleum resin according to claim 1, 2, 4 or 6, wherein the hydrogenation step comprises the following steps: the solvent is a mixture of cycloalkane and straight-chain alkane, and the cycloalkane accounts for 30-70% of the solvent by mass.

Technical Field

The invention belongs to the technical field of polymer hydrogenation, and relates to a method for hydrogenating high-sulfur petroleum resin.

Background

The petroleum resin has a large molecular weight, polymer molecules extend on the surface of the catalyst to form high steric hindrance, and the hydrogenation difficulty of the petroleum resin is determined by the molecular structure of the polymer molecules. The petroleum resin hydrogenation process is designed under harsh operating conditions, and the process types vary according to the production scale and the product requirements. At present, the representative of the foreign petroleum resin hydrogenation modification is American Exxon, Ismann, Japan crude and Japan bright dipping companies. At present, hydrogenated petroleum resin is more and more popular in the market, a catalyst is the key of the hydrogenated petroleum resin technology, a palladium catalyst and a nickel catalyst are mostly used abroad, and the development direction of the hydrogenation catalyst in the future is to improve the activity and the stability of the catalyst, prolong the service life of the catalyst, reduce side reactions and properly reduce the manufacturing cost. China should accelerate the research of petroleum resin hydrogenation catalysts and the localization of hydrogenation catalysts, and further promote the popularization of hydrogenated petroleum resin technology and the reduction of product cost.

The raw materials for producing petroleum resins mainly come from C5 and C9 fractions of an ethylene cracking unit. At present, the main raw material for ethylene cracking in China is naphtha, which accounts for about 60 percent. The typical recovery of ethylene from naphtha is approximately 33% in China, and then 300 million tons of naphtha are required for 100 million tons of ethylene. With the global oil upgrading and high sulfur content, naphtha S content produced by oil refining is high, and consequently sulfur content in C5 and C9 fractions as by-products of ethylene cracking is high, so that the S content of petroleum resin polymerized from C5 and C9 fractions is also increasing. Therefore, the hydrogenation of petroleum resin is not only based on the structural characteristics, but also takes into consideration the influence of impurities on the catalyst.

Aiming at the problem of resource utilization of rich high-sulfur petroleum resin, a sulfur-resistant eggshell-type noble metal alloy catalyst is used as a hydrodesulfurization catalyst, a supported metal catalyst is used as a two-stage hydrogenation and decoloration catalyst, the resin is subjected to hydrogenation reaction by adopting a two-stage fixed bed continuous hydrogenation mode, the catalyst is stable and ideal, the hue of the prepared hydrogenated petroleum resin is improved to be water white, the hydrogenated petroleum resin has good thermal stability, and the softening point is reduced little. The following known techniques all have some disadvantages:

chinese patent, publication No.: CN102633941A introduces a method for preparing high-grade resin by catalytic hydrogenation, which takes supported noble metal palladium as a first-stage hydrogenation catalyst and skeletal nickel as a second-stage hydrogenation catalyst, and adopts a two-stage kettle type or fixed bed continuous hydrogenation mode to carry out hydrogenation reaction on the resin. The reaction process and the catalyst are not suitable for resin containing high impurity, and the utilization rate of the first-stage noble metal Pd is low.

Chinese patent, publication No.: CN103386302A discloses a petroleum resin hydrogenation catalyst, namely Al₂O₃The catalyst is a carrier, noble metal Pd and an oxide auxiliary agent are loaded, and the metal palladium microcrystal with the particle size of less than 3nm accounts for more than 90 percent, and has the defect that the catalyst has impurity S^2-The catalyst is susceptible to poisoning and deactivation due to poor tolerance, and the catalyst life is affected.

Chinese patent, publication No.: CN104959136A introduces a preparation method for a resin hydrogenation eggshell type catalyst, noble metal particles are uniformly distributed on the surface of a carrier, the use amount of noble metals of a petroleum resin hydrogenation catalyst is reduced, and the cost of the catalyst is effectively reduced. Only the requirements of the resin structure on the catalyst structure are considered, but the influence of resin impurities on the catalyst is not considered.

Chinese patent, publication No.: CN104877077A introduces a method for preparing hydrogenated C9 petroleum resin, which takes Ni/ZnO catalyst as hydrogenation adsorption desulfurization and supported metal catalyst as hydrogenation decolorization catalyst, and adopts a two-section fixed bed continuous hydrogenation mode to carry out hydrogenation reaction on the resin. The sulfur capacity content of the hydrogenation adsorption desulfurization catalyst is limited and only accounts for 10-15% of the weight of the catalyst, the active center of the catalyst can be converted into NiS, and hydrogen sulfide is adsorbed on the carrier to generate acidity, so that the resin is promoted to crack, and the yield of the hydrogenated resin is reduced.

Chinese patent, publication No.: CN105367714A describes a method for preparing hydrogenated DCPD resin by using supported Ni/ZnO-SiO₂The catalyst is used as a pre-hydrogenation catalyst, the eggshell type Pd catalyst is used as a hydrogenation and decoloration catalyst, and the resin is subjected to hydrogenation reaction by adopting a two-section fixed bed continuous hydrogenation mode, so that the hydrogenated DCPD resin is prepared, the resin hue is improved to be water white, and the hydrogenated DCPD resin has good thermal stability. The colloid blocks the pore channel of the prehydrogenation catalyst, so that the catalyst is quickly deactivated.

Disclosure of Invention

The invention provides a method for hydrogenating high-sulfur petroleum resin, which solves the problem of quick inactivation of a resin hydrogenation catalyst. The invention has wide raw material range, takes high-grade hydrogenated resin as a target product, improves the chroma of the resin, improves the heat stability, slightly reduces the softening point rate of the resin and obviously improves the product yield.

The technical scheme of the invention is as follows:

a method for hydrogenating petroleum resin with high sulfur content uses a sulfur-resistant eggshell-shaped noble metal alloy as a first-stage hydrodesulfurization catalyst and a supported metal catalyst as a second-stage hydrogenation decolorization catalyst, and adopts a two-stage hydrogenation mode to carry out hydrogenation reaction on the resin to prepare hydrogenated resin, wherein the color phase of the resin is improved to be water white, and the softening point is reduced; the method comprises the following steps:

heating the solvent to 130-150 ℃, uniformly dissolving the solvent and the molten high-sulfur petroleum resin in a dynamic mixer, wherein the high-sulfur petroleum resin accounts for 10-30% of the mass ratio of the mixed substances, and then entering an impurity removal reactor filled with a colloid absorbing adsorbent to remove colloid, partial chlorine or fluorine; then mixing with hydrogen and injecting the mixture into a hydrodesulfurization tower filled with a hydrodesulfurization catalyst, wherein the hydrodesulfurization catalyst removes sulfur, chlorine or fluorine in the resin, the feeding temperature is 260-300 ℃, the hydrogen partial pressure is 2-4MPa, and the volume space velocity is 1-4h^-1The volume ratio of hydrogen to oil is 100-200: 1; the hydrodesulfurization catalyst is an eggshell type noble metal alloy catalyst; addingThe resin solution after hydrogen desulfurization enters a stripping gas-liquid separation tower, the content of dissolved hydrogen sulfide in the resin solution is reduced through hydrogen stripping, and the separated hydrogen is washed and recycled; the resin solution after hydrodesulfurization is pressurized and mixed with hydrogen to enter a deep hydrogenation tower for hydrogenation and decolorization, wherein the feeding temperature is 240-280 ℃, the hydrogen partial pressure is 8-18MPa, and the volume space velocity is 0.5-1.5h^-1The volume ratio of hydrogen to oil is 200-600: 1; the catalyst used for hydrogenation and decoloration is a supported metal catalyst; injecting the resin solution subjected to hydrogenation and decoloration into a solvent removal tower, distilling the resin solution at normal pressure, circularly dissolving the high-sulfur petroleum resin by using a product solvent distilled from the top of the tower, allowing a product at the bottom of the tower to enter a devolatilization tower, performing negative pressure operation on the devolatilization tower, and ejecting high-boiling-point oligomers generated by petroleum resin cracking in the hydrogenation and decoloration process out of the devolatilization tower; hydrogenated resin is discharged from the bottom of the devolatilization tower, the color phase of the resin is improved to be water white, and the softening point is reduced.

The colloid-absorbing adsorbent is Ca/Al₂O₃Wherein the mesopore volume accounts for more than 80% of the total pore volume, the pore diameter is 20-50nm, and Ca is added²⁺The mass content of (A) is 0.3-1.0%. Ca²⁺The introduction of (2) is beneficial to the removal of chlorine/fluorine in the residual initiator of the synthetic resin.

In the eggshell type noble metal alloy catalyst, the noble metal alloy is PdM, and M is one or more than two of Ir, Re, Pt, Ru, Au and Ag.

M is Pt or Ir, the molar ratio of Pd to M is 4:1, the mass content of Pd is 0.3-1.0%, and the carrier is Al₂O₃、SiO₂、TiO₂、SiO₂-Al₂O₃Or Al₂O₃-TiO₂。

The supported metal catalyst is a noble metal catalyst, a high nickel catalyst or a skeletal nickel catalyst. Preferably selecting a high nickel catalyst and a skeleton nickel catalyst, wherein the mass content of metal nickel in the high nickel catalyst is more than 30 percent; the skeletal nickel catalyst needs to be dealuminized, and the removal rate of aluminum needs to be more than 95 percent.

The solvent is a mixture of cycloalkane and straight-chain alkane, the cycloalkane accounts for 30-70% of the solvent by mass, and the proportion of the cycloalkane to the solvent is determined according to the solubility of the resin.

The invention has the beneficial effects that: the resin and the solvent are dynamically mixed, and the continuous operation of adsorption impurity removal, hydrodesulfurization, stripping desolventizing hydrogen sulfide, gas purification, hydrodecolorization, solvent removal and devolatilization is carried out. The method provided by the invention improves the impurity resistance, the reaction activity and the selectivity due to the use of a two-stage hydrogenation method. The method has wide adaptability to resin raw materials, and is particularly suitable for high-sulfur petroleum resin. The petroleum resin obtained by thermal polymerization or catalytic polymerization can be subjected to two-step hydrotreating by the method provided by the invention to obtain high-performance hydrogenated resin no matter the content of impurities in the resin solution is high, especially when the content of sulfur or fluorine/chlorine in the resin solution is high. Through first-stage hydrodesulfurization, sulfur, chlorine/fluorine in the resin are removed by using a sulfur-resistant eggshell type noble metal alloy catalyst, so that the second-stage hydrogenation metal catalyst is effectively protected, and the service life of the catalyst is greatly prolonged. Therefore, the invention has the advantages of simple process, high catalyst activity, good stability, improved resin chromaticity, improved resin thermal stability, slightly reduced softening point and good economic benefit.

Drawings

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

In the figure: 1a dynamic mixer; 2, removing impurities in a reaction tower; 3, a hydrodesulfurization reaction tower; 4 steam stripping gas-liquid separation tower; 5, washing the tower with water; 6, a deep hydrogenation tower; 7a desolventizing tower; 8 a devolatilization tower.

Detailed Description

The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.