阅读说明：本技术 一种冷聚石油树脂加氢制氢化石油树脂的方法 (Method for preparing hydrogenated petroleum resin by hydrogenation of cold-polymerized petroleum resin ) 是由 李闯 崔天云 孙学庆 梁长海 于 2021-11-08 设计创作，主要内容包括：本发明属于树脂加氢技术领域,公开了一种冷聚石油树脂加氢制氢化石油树脂的方法,以蛋壳型Pd-Pt-Ca-Mg-Al@Al-(2)O-(3)类水滑结构催化剂作为一段预加氢催化剂,脱除聚合残留的有机氯/有机氟,脱除的氯/氟吸附在载体上,避免产生酸性气体或增加深度加氢催化剂酸性增加树脂的解聚,降低氢化树脂收率。负载型Ni或骨架镍催化剂作为二段加氢脱色催化剂,采用两段固定床连续加氢方式对树脂进行加氢反应,所制得氢化石油树脂,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 belongs to the technical field of resin hydrogenation, and discloses a method for preparing hydrogenated petroleum resin by hydrogenation of cold-polymerized petroleum resin, which uses eggshell type Pd-Pt-Ca-Mg-Al @ Al 2 O 3 The quasi-hydro-slippery structure catalyst is used as a first-stage pre-hydrogenation catalyst to remove residual organic chlorine/organic fluorine in polymerization, and the removed chlorine/fluorine is adsorbed on a carrier, so that acidic gas is prevented from being generated or the acidity of a deep hydrogenation catalyst is increased to increase the depolymerization of resin, and the yield of hydrogenated resin is reduced. The supported Ni or skeleton nickel catalyst is used as a two-stage hydrogenation and decoloration catalyst, and the resin is subjected to hydrogenation reaction by adopting a two-stage fixed bed continuous hydrogenation mode, so that the prepared hydrogenated petroleum 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 and improved colorThe heat stability is improved, the softening point is slightly reduced, and the method has good economic benefit and industrial application prospect.)

1. A method for preparing hydrogenated petroleum resin by hydrogenation of cold-polymerized petroleum resin is characterized in that a solvent is used for dissolving and diluting molten cold-polymerized petroleum resin in a dissolving tank, wherein the mass percent of the cold-polymerized petroleum resin is 20-30%; then mixed with hydrogen gas, injected into the pre-adding device filled with hydrogenation adsorption dechlorination/fluorine catalystA hydrogen tower for removing chlorine/fluorine, diene and sulfur in the cold polymerized petroleum resin by a hydrogenation adsorption dechlorination/fluorine catalyst, wherein the feeding temperature is 160-^-1The volume ratio of hydrogen to oil is 100-300: 1; the hydrogenation adsorption dechlorination \ fluorine catalyst is eggshell type Pd-Pt-Ca-Mg-Al @ Al₂O₃A hydro-ski like structure catalyst; the resin solution after the pre-hydrogenation enters a hydrogenation and decoloration tower for hydrogenation and decoloration, the feeding temperature is 220-280 ℃, the hydrogen partial pressure is 10-15MPa, and the volume airspeed is 0.5-1.5h^-1The volume ratio of hydrogen to oil is 400-600: 1; the hydrogenation and decoloration catalyst is a supported Ni or skeleton nickel catalyst; the resin solution after hydrogenation and decoloration enters a high-molecular tank, and H is separated out₂Recycling; injecting the resin solution at the bottom of the high-molecular-weight tank into a desolventizing tower under reduced pressure, distilling under normal pressure, circularly dissolving the cold polymerized petroleum resin in the product solvent distilled from the top of the tower, allowing the 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 cracking the cold polymerized petroleum resin in a hydrogenation and decoloration process from the devolatilization tower; the hydrogenated resin is discharged from the bottom of the devolatilization tower, the color of the hydrogenated resin is improved to be water white, and the softening point is slightly reduced.

2. The method of claim 1, wherein the eggshell type Pd-Pt-Ca-Mg-Al @ Al is₂O₃The catalyst with a water-like sliding structure is prepared by adopting a coprecipitation method to carry Al on a carrier₂O₃Pd-Pt-Ca-Mg-Al hydrotalcite-like precursor grows on the surface, and Pd-Pt-Ca-Mg-Al @ Al is obtained by roasting and reducing₂O₃The hydrotalcite-like layer metal element has the characteristic of adjustability to prepare bimetallic catalysts with different Pd/Pt molar ratios; wherein the mass percent of Pd is 0.6-0.7%, the mass percent of Pt is 0.28-031%, and Pd/Pt is 4.

3. The method according to claim 1 or 2, wherein the hydrodewaxing catalyst is a supported Ni catalyst, and the carrier is SiO₂Or Al₂O₃And the NiO content is 40-60%.

4. The method of claim 1 or 2, wherein the solvent is one or more selected from cyclohexane, n-heptane, n-decane, D40, D60, and decalin.

5. The method of claim 3, wherein the solvent is one or more selected from cyclohexane, n-heptane, n-decane, D40, D60, and decalin.

Technical Field

The invention belongs to the technical field of petroleum resin hydrogenation, and relates to a method for preparing colorless, tasteless and high-grade resin with good thermal stability by hydrogenation.

Background

The catalytic polymerization is one of the methods commonly used in industry for producing petroleum resin, mainly refers to a cationic polymerization process initiated by Lewis acid or halide, and the like, and commonly used catalysts are HCl, HF and AlCl₃And BF₃And the like. The method has the advantages of mild reaction conditions (the polymerization temperature is generally below 100 ℃) and short polymerization time. Its disadvantages are high cost of catalyst, corrosion to equipment, waste water in production process, and tens ppm of chlorine/fluorine remained in the synthesized petroleum resin. Because of the difference of raw materials and polymerization conditions, the petroleum resin contains unsaturated double bonds and benzene rings, under the action of a catalyst, the petroleum resin is saturated by hydrogenation, and residual chlorine and sulfur elements in the polymerization process are removed, so that the chromaticity and the photo-thermal stability of the resin are improved, and the quality of a product is improved. As a catalyst in the hydrogenation of petroleum resins, it is of critical importance to the process, which determines the production cost and the quality of the subsequent products. In the hydrogenation process of petroleum resin, HCl generated by chlorine/fluorine and HF adsorbed on a catalyst carrier generate acidity, so that the cracking of the resin in the hydrogenation process is serious, the yield of hydrogenated resin is reduced, and the service life of a hydrogenation catalyst is shortened. The 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.

Aiming at the problem of resource utilization of abundant resin, the eggshell type Pd-Pt-Ca-Mg-Al @ Al is successfully developed₂O₃The hydro-dynamically structured catalyst is used as a pre-hydrogenation catalyst, a hydrotalcite-like compound is used as a precursor, the problem that active components of a noble metal catalyst are easy to run off is solved, Pd and Pt are introduced into a laminate of the hydrotalcite-like precursor to form Pd-Pt bimetal to increase the sulfur resistance of the hydrotalcite-like compound, the defect that the sulfur resistance of the noble metal resin hydrogenation catalyst is poor is solved, Ca-Mg-Al oxide has super-strong alkalinity and is beneficial to C-Cl bond breakage, HCl/HF generated by hydrogenation is adsorbed on the pre-hydrogenation catalyst, and the service life of the hydrogenation and decoloration catalyst is greatly prolonged. Supported Ni or skeletal nickel catalyst as hydrodesulphurizationThe color catalyst adopts a two-section fixed bed continuous hydrogenation mode to carry out hydrogenation reaction on the resin, so that the color phase 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 a little. The following known techniques all have some disadvantages:

chinese patent, publication No.: CN1736604 introduces an eggshell type metal, its preparation and application, which is an eggshell type supported metal catalyst using hollow silica as carrier, where the hollow silica carrier is a mesoporous material with a certain wall thickness and a certain pore diameter, and the eggshell type metal catalyst is prepared by adopting an immersion method or an in-situ supporting method. But has strict requirements on the carrier, complicated reaction steps and longer preparation period.

Chinese patent, publication No.: CN 103386302A 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.: CN1803871A, discloses a kettle-type hydrogenation decoloring and decoloring method for C5 and C9 petroleum resins, which has higher activity for resin hydrogenation, but has more serious hydrogenation degradation, low product resin yield and serious softening point reduction.

Disclosure of Invention

The invention provides a method for preparing hydrogenated petroleum resin by hydrogenation of cold-polymerized petroleum resin, which solves the problems of quick catalyst deactivation and low hydrogenated resin yield in the hydrogenation process of cold-polymerized petroleum resin. The hydrotalcite-like compound is used as a precursor, so that the problem that active components of a noble metal catalyst are easy to lose is solved, Pd and Pt are introduced into a laminate of the hydrotalcite-like compound precursor to form Pd-Pt bimetal so as to increase the sulfur resistance of the hydrotalcite-like compound, the defect that the sulfur resistance of a noble metal resin hydrogenation catalyst is poor is solved, Ca-Mg-Al oxide has super-strong alkalinity so as to facilitate C-Cl bond fracture, HCl/HF generated by hydrogenation is adsorbed on a pre-hydrogenation catalyst, and the service life of the hydrogenation and decoloration catalyst is greatly prolonged.

The technical scheme of the invention is as follows:

a method for preparing hydrogenated petroleum resin by hydrogenation of cold-polymerized petroleum resin comprises dissolving and diluting molten cold-polymerized petroleum resin in a dissolving tank by using a solvent, wherein the cold-polymerized petroleum resin accounts for 20-30% of the dissolving tank by mass percent; then mixing with hydrogen, injecting the mixture into a pre-hydrogenation tower filled with a hydrogenation adsorption dechlorination/fluorine catalyst, removing chlorine/fluorine, diene and sulfur in the cold polymerized petroleum resin by the hydrogenation adsorption dechlorination/fluorine catalyst, wherein the feeding temperature is 160-220 ℃, the hydrogen partial pressure is 4-8MPa, and the volume space velocity is 2-4h^-1The volume ratio of hydrogen to oil is 100-300: 1; the hydrogenation adsorption dechlorination \ fluorine catalyst is eggshell type Pd-Pt-Ca-Mg-Al @ Al₂O₃A hydro-ski like structure catalyst; the resin solution after the pre-hydrogenation enters a hydrogenation and decoloration tower for hydrogenation and decoloration, the feeding temperature is 220-280 ℃, the hydrogen partial pressure is 10-15MPa, and the volume airspeed is 0.5-1.5h^-1The volume ratio of hydrogen to oil is 400-600: 1; the hydrogenation and decoloration catalyst is a supported Ni or skeleton nickel catalyst; the resin solution after hydrogenation and decoloration enters a high-molecular tank, and H is separated out₂Recycling; injecting the resin solution at the bottom of the high-molecular-weight tank into a desolventizing tower under reduced pressure, distilling under normal pressure, circularly dissolving the cold polymerized petroleum resin in the product solvent distilled from the top of the tower, allowing the 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 cracking the cold polymerized petroleum resin in a hydrogenation and decoloration process from the devolatilization tower; the hydrogenated resin is discharged from the bottom of the devolatilization tower, the color of the hydrogenated resin is improved to be water white, and the softening point is slightly reduced.

The eggshell type Pd-Pt-Ca-Mg-Al @ Al₂O₃The catalyst with a water-like sliding structure is prepared by adopting a coprecipitation method to carry Al on a carrier₂O₃Pd-Pt-Ca-Mg-Al hydrotalcite-like precursor grows on the surface, and Pd-Pt-Ca-Mg-Al @ Al is obtained by roasting and reducing₂O₃The hydrotalcite-like layer metal element has the characteristic of adjustability to prepare bimetallic catalysts with different Pd/Pt molar ratios; wherein the mass percent of Pd is 0.6-0.7%, the mass percent of Pt is 0.28-031%, and Pd/Pt is 4.

The hydrogenation and decoloration catalyst is a supported Ni catalyst, and the carrier is SiO₂Or Al₂O₃And the NiO content is 40-60%.

The solvent is one or more of cyclohexane, n-heptane, n-decane, D40, D60 and decahydronaphthalene.

The petroleum resin is subjected to continuous operations of dissolving and diluting, pre-hydrogenation and impurity removal, hydrogenation and decoloration, solvent removal and oligomer removal.

The invention has the beneficial effects that: the eggshell type Pd-Pt-Ca-Mg-Al @ Al in the method provided by the invention₂O₃The quasi-hydro-slippery structure catalyst is used as a first-stage pre-hydrogenation catalyst to remove residual organic chlorine/organic fluorine in polymerization, and the removed chlorine/fluorine is adsorbed on a carrier, so that acidic gas is prevented from being generated or the acidity of a deep hydrogenation catalyst is increased to increase the depolymerization of resin, and the yield of hydrogenated resin is reduced. The supported Ni or skeleton nickel catalyst is used as a two-stage hydrogenation and decoloration catalyst, and the resin is subjected to hydrogenation reaction by adopting a two-stage fixed bed continuous hydrogenation mode, so that the prepared hydrogenated petroleum 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.

Drawings

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

In the figure: 1, a resin dissolving tank; 2, a pre-hydrogenation tower; 3, a hydrogenation decoloring tower; 4 a high pressure separator; 5 a desolventizing tower; 6 a devolatilization tower.

Detailed Description

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

Example 1: with Pd (NH)₃)₂Cl₂、Pt(NH₃)₂(NO₃)₄、Ca(NO₃)₂、Mg(NO₃)₂And Al (NO)₃)₃Adopts a precipitation method to assemble layered double hydroxide Pd (NH) on the surface of spherical alumina as a precursor₃)₂Cl₂ -Pt(NH₃)₂(NO₃)₄/CaMgAl-CO₃ ^2-Hydrotalcite-like shell structure, and Pd-Pt-Ca-Mg-Al @ Al is prepared by structure transformation₂O₃The core-shell catalyst with the water-like sliding structure is a supported catalyst prepared by using the hydrotalcite-like compound as a precursor, and active metal can be uniformly distributed on a carrier after being roasted and is not easy to move and fall off due to the good dispersion degree of cations on a laminate and the existence of an 'inhibition effect', so that the core-shell catalyst has higher activity and excellent stability in the catalytic process. Using D40 as solvent, cold polymerized C9 resin as raw material, the softening point of the resin is 110 ℃, the F content in the resin is 35ppm, the S content is 80ppm, the color number is 8, using D40 to prepare 20% resin liquid, and using eggshell type Pd-Pt-Ca-Mg-Al @ Al₂O₃The influence of reaction conditions on defluorination and desulfurization effects is examined by using the catalyst with the water-slipping-like structure as a pre-hydrogenation catalyst. See table 1 below for resin properties after prehydrogenation.

The colorimetric measurement is that the resin is prepared into 50 wt% toluene solution to be compared with standard Fe-Co colorimetric solution.

As can be seen from Table 1: when the reaction temperature is higher than 200 ℃, the catalyst has better defluorination effect, and when the reaction temperature is higher than 220 ℃, the catalyst has better desulfurization effect, the catalyst basically does not crack in the pre-hydrogenation process, and the softening point is only reduced by 2 ℃. When the air speed is more than 2, the desulfurization and defluorination effects are greatly reduced; when the hydrogen-oil ratio is more than 200, the hydrogen-oil ratio has no influence on the hydrogenation effect.

Example 2: eggshell type Pd-Pt-Ca-Mg-Al @ Al₂O₃The catalyst with the water-like sliding structure is a pre-hydrogenation catalyst, and the reaction conditions are that the feeding temperature is 220 ℃, the hydrogen partial pressure is 2MPa, and the volume space velocity is 2h^-1Hydrogen-oil volume ratio 200: 1, resin concentration 20%. Table 2 below shows the properties of the products obtained after 1000 hours of operation.

As shown in Table 2, the 1000-hour experiment results show that the sulfur, fluorine and bromine values of the eggshell type Pd-Pt-Ca-Mg-Al @ Al2O3 type water-slipping structure catalyst which is a prehydrogenation catalyst are basically unchanged compared with the initial experiment, and the technology has good stability. By running for the above time, the capacity of the catalyst for adsorbing fluorine and sulfur reaches more than 20 percent of the weight of the catalyst.

Example 3: the hydrogenation decolorization catalyst is investigated and calculated by the mass percent of NiO>45% load type Ni/SiO₂、 Ni/Al₂O₃And skeletal nickel catalyst is decolorization catalyst. On the basis of example 2, the pressure is 15MPa, the temperature is 240 ℃, and the space velocity is 0.9h^-1Hydrogen-oil ratio of 400: the hydrogenation decolorization experiment was performed under 1 condition. Table 3 below shows the reaction process conditions and the properties of the hydrogenated resin product obtained at the end.

Thermal stability: the resin sample was heat treated at 180 ℃ for 3 hours and the Fe-Co hue was measured.

As can be seen from Table 3, the supported Ni/SiO₂、Ni/Al₂O₃And the catalyst and the framework nickel catalyst show good hydrogenation and decoloration effects, and the product has good thermal stability. Supported Ni/Al₂O₃The softening point of hydrogenated resin of the catalyst is reduced more, which proves that cracking reaction is more; the hydrogenated resin obtained by the skeletal nickel catalyst has poor stability and contains double bonds without complete hydrogenation.

Example 4: by loading Ni/SiO₂The catalyst is a hydrogenation and decolorization catalyst, and the influence of reaction conditions on decolorization and desulfurization effects is examined. See table 4 below for hydrogenated resin properties after decolorization.

From Table 4, it can be seen that the eggshell type Pd-Pt-Ca-Mg-Al @ Al₂O₃The hydro-ski-like structure catalyst is a pre-hydrogenation catalyst and takes supported Ni/SiO₂The catalyst is a hydrogenation and decoloration catalyst, and the C9 resin is subjected to hydrogenation reaction by adopting a two-stage fixed bed hydrogenation mode to prepare the hydrogenated resin, the color phase of the resin is improved to be water white, the softening point is slightly reduced, and the hydrogenated resin has good thermal stability. The reaction conditions have certain influence on the properties of the hydrogenated resin, when the reaction temperature is higher than 240 ℃, the pressure is higher than 12MPa, and the volume space velocity is less than 1.2h^-1The hydrogen-oil ratio is more than 400, the available softening point is only reduced by 4 ℃, and the thermal stability is less than 1, thus obtaining the hydrogenated petroleum resin.

Example 5: Ni/SiO supported by high metal load₂Is a hydrogenation and decoloration hydrogen catalyst. On the basis of example 2 and example 4, the reaction conditions were: the feeding temperature is 240 ℃, the hydrogen partial pressure is 15MPa, and the volume space velocity is 0.9h^-1Hydrogen-oil volume ratio 400: 1, resin concentration 20%. The properties of the hydrogenated resin after 1000h of hydrodecoloration are shown in Table 5 below.

From Table 5, it can be seen that the process was run for 1000 hours with eggshell type Pd-Pt-Ca-Mg-Al @ Al₂O₃The water slide-like structure catalyst is a pre-hydrogenation catalyst, and the supported high-supported Ni/SiO₂The hydrogenation and decoloration catalyst is a hydrogenation and decoloration catalyst, a two-section fixed bed hydrogenation mode is adopted to carry out hydrogenation reaction on resin to prepare hydrogenated resin, the color phase of the resin is improved to be water white, the softening point is slightly reduced, and the hydrogenated resin has good thermal stability. The results show that the technology of the invention has good stability and long service life of the catalyst.