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Publication numberCN104710572 B
Publication typeGrant
Application numberCN 201510081990
Publication date16 Jun 2017
Filing date15 Feb 2015
Priority date15 Feb 2015
Also published asCN104710572A
Publication number201510081990.0, CN 104710572 B, CN 104710572B, CN 201510081990, CN-B-104710572, CN104710572 B, CN104710572B, CN201510081990, CN201510081990.0
Inventors陈小鹏, 王琳琳, 韦小杰, 梁杰珍, 周龙昌, 丁永辉, 唐伟超, 韦彩琴, 张鹏鹏
Applicant广西大学
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
跨临界反应系统加氢‑脱硫耦合改性c9/c5石油树脂的方法及装置 Hydrogenation of transcritical the reaction system - modifying desulfurization coupled c9 / c5 petroleum resin method and apparatus translated from Chinese
CN 104710572 B
Abstract  translated from Chinese
跨临界反应系统加氢‑脱硫耦合改性C9/C5石油树脂的方法,包括以下操作步骤:(1)将C9/C5石油树脂与溶剂并加入催化剂混合,加热,溶解;(2)通入H2和CO2混合气体进行加氢反应,反应温度为150℃~400℃,反应压力为3.0MPa~35.0MPa;(3)加氢反应过程中产生的气体H2S、剩余的混合气体H2和CO2进行分离,除去H2S,H2和CO2加压重新返回进行加氢反应循环使用;(4)加氢‑脱硫反应1~10h后,即得产品。 Hydrogenation of transcritical the reaction system - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, comprising the following steps: (1) C9 / C5 petroleum resin mixed with a solvent and adding the catalyst, is heated and dissolved; (2) into H2 CO2 gas mixture and hydrogenation reaction, the reaction temperature is 150 ℃ ~ 400 ℃, the reaction pressure is 3.0MPa ~ 35.0MPa; (3) generated during the hydrogenation reaction gases H2S, the remaining mixed gas of H2 and CO2 separation, removal of H2S, H2 and CO2 pressure return to be recycled hydrogenation reaction; (4) hydrogenation - 1 ~ 10h after desulfurization reaction, the product is obtained. 本发明方法在提高改性后的C9/C5石油树脂的质量的同时,提供一种能有效脱除C9/C5石油树脂中有机硫的方法,优化反应环境。 The method of the present invention to improve the quality of the modified C9 / C5 petroleum resin, while providing a method for effective removal of C9 / C5 petroleum resin of organic sulfur, to optimize the reaction environment.
Claims(10)  translated from Chinese
1. 跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于,包括以下操作步骤: (1) 将C9/C5石油树脂与溶剂按照质量比1:1〜10:1,加入催化剂混合,加热,溶解; (2) 通入H2和C02摩尔比为1:1〜20:1的混合气体进行加氢反应,反应温度为150C〜400 C,反应压力为3. OMPa〜35 • OMPa; (3) 加氢反应过程中产生的气体H2S、剩余的混合气体H2和C02进行分离,除去H2S,H2和C02加压重新返回进行加氢反应循环使用; ⑷加氢-脱硫反应1〜10h后,经减压后物料从加氢反应器中放出即为C9/C5石油树脂产品。 1. Hydrogenation reaction system is transcritical - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, characterized in that it comprises the following steps: (1) C9 / C5 petroleum resin and the solvent at a mass ratio of 1: 1~10: 1, the catalyst mixture was added, heated and dissolved; (2) into C02 and H2 molar ratio of 1: 1~20: 1 mixed gas is subjected to hydrogenation reaction, the reaction temperature is 150 C~400 C, a reaction pressure of 3. OMPa~35 • OMPa; (3) generated during the hydrogenation reaction gases H2S, H2 and the remaining mixed gas separated C02, removing H2S, H2 and C02 return to the pressurized recycle hydrogenation reaction; adding ⑷ hydrogen - desulfurization reaction 1~10h, is the release of the material by reduced pressure C9 / C5 petroleum resin product from the hydrogenation reactor.
2. 根据权利要求1所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:所述步骤(2)中流出的气体经过膨胀机后,进入气液分离器进行分离,所得到的溶剂液体回流到加氢反应器内,剩下的气体为出5、出和0)2,将气体通入吸收塔中,经吸收塔吸收H2S气体后,剩余H2和C02再通入透平压缩机。 2. The system of claim 1 transcritical claim hydrogenation reaction - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, wherein: the outflow (2) in the gas after the step of the expander, into the gas-liquid separator is separated, the solvent was refluxed liquid into the hydrogenation reactor, the remaining gas is 5, and a 0) 2, the gas introduced into the absorption column, after absorption of H2S gas absorption tower, and the remaining H2 C02 then pass into the turbine compressor.
3. 根据权利要求1所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:所述步骤(3)从加氢反应器中取出混合气体的流量为9〜12000m3/h,将气体通过膨胀机,膨胀机与透平压缩机连接,往透平压缩机内补充C02和H2混合气体,再将混合气体通入加氢反应器内。 3. The system of claim 1 transcritical claim Hydrogenation reaction - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, wherein: said step (3) removed from the mixed gas flow hydrogenation reactor 9 ~12000m3 / h, the gas through the expander, the expander turbine and a compressor connected to the turbine and the compressor supplement C02 H2 mixed gas, the mixed gas is then introduced into the hydrogenation reactor.
4. 根据权利要求1所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:步骤(1)中加入的催化剂的量为加入的C9/C5石油树脂与溶剂总量的质量分数1 〜30%,其中所述的催化剂为负载镍或钯的催化剂。 1 4. The system of claim transcritical Hydrogenation reaction - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, wherein: the amount of the step (1) was added as a catalyst added C9 / C5 petroleum resin and 1 mass fraction of ~ 30% of the total solvent, wherein said catalyst is a supported nickel or palladium catalyst.
5. 根据权利要求2所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:气液分离器的温度为彡50C,压力为<0.5MPa,液体流量为<l〇〇m3/h,气体流量为<10000m3/h。 Temperature gas-liquid separator is San 50 C, a pressure of <0.5MPa, liquid: Coupling method for desulfurizing modified C9 / C5 petroleum resin, characterized in that - 2 The hydrogenation of the reaction system is transcritical claim flow rate <l〇〇m3 / h, the gas flow rate of <10000m3 / h.
6. 根据权利要求1所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:步骤⑴中所述的溶剂为环己烷、乙基环己烷、n-己烷、n-庚烷、矿物精油、200#溶剂油中的一种。 1 according to the hydrogenation reaction system as claimed in claim transcritical - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, wherein: said step ⑴ solvent is cyclohexane, ethylcyclohexane, n- - hexane, N- heptane, mineral spirits, solvent naphtha # 200 a.
7. 根据权利要求1所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于,该方法采用如下装置,所述装置包括: 加氢反应器,其包括:多个加热管,设于加氢反应器内部;以及气体分布器,其包括进气口和多个用于排气的喷头;膨胀机,其与所述加氢反应器连接;以及透平压缩机,其与所述膨胀机连接,并通过所述膨胀机驱动所述透平压缩机工作,所述透平压缩机的出气口与所述加氢反应器连接。 1 according to the hydrogenation reaction system is transcritical claim - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, characterized in that the method using the following apparatus, the apparatus comprising: a hydrogenation reactor, which comprises: plurality of heat pipes, disposed inside the hydrogenation reactor; and a gas distributor, which includes an air inlet and a plurality of exhaust nozzles; expander connected to said hydrogenation reactor; and a compression turbine machine, which is connected to the expander, compressor and said turbine driven by the expander, the turbine compressor outlet is connected to the hydrogenation reactor.
8. 根据权利要求7所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:所述气体分布器呈“L”型,其底端为圆环管状,在该圆环管上均匀设有多个用于排气的喷头。 According to claim 7 transcritical hydrogenation reaction system requirements - Coupling The method of desulfurizing modified C9 / C5 petroleum resin, wherein: said gas distributor was "L" shaped, its bottom end an annular tube, in the annular nozzle is provided with a plurality of uniformly pipe for exhaust gas.
9.根据权利要求7所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:所述加热管为多个,呈平行均布在所述加氢反应器内部;所述气体分布器有多个,所述多个气体分布器相互连通,所述每个气体分布器设在所述加热管之间。 The plurality of heating tubes, are distributed in the form of parallel hydrogenation reactor: Modified Coupling desulfurization method C9 / C5 petroleum resin, characterized in that - 9. The hydrogenation of the reaction system was 7 transcritical claim interior; a plurality of the gas distributor, communicate with each other the plurality of gas distributors, each of said gas distributor is provided between the heating tubes.
10.根据权利要求7所述跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,其特征在于:所述用于C9/C5石油树脂共混加氢改性的装置,还包括:洛觯金,兵4 应器连接,用于溶解生产所需的原料;气液分离器,其与所述膨胀机连接;溶剂泵,其与所述气液分离器连接,用于将分离出的液体溶剂送至所述加氢反应器内;以及吸收塔,其进气口与所述气液分离器连接,出气口与所述透平压缩机连接,用于去除HsS气体。 Means C9 / C5 petroleum resin blend for the hydrogenated modified further: the desulfurization method of coupling modifying C9 / C5 petroleum resin, characterized in that - 10. The hydrogenation reaction of the 7 transcritical system according to claim comprising: Los goblet gold, soldiers 4 should be connected, for dissolving the materials is desired to produce; gas-liquid separator, which is connected to the expander; solvent pump, which is connected to the gas-liquid separator, for the separated liquid solvent to said hydrogenation reactor; and absorber, with its intake port connected to the gas-liquid separator, the gas outlet and a compressor connected to said turbine, for removing gas HsS.
Description  translated from Chinese

跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法及装置 Hydrogenation of transcritical the reaction system - Desulfurization coupled Modified C9 / C5 petroleum resin method and apparatus

技术领域 FIELD

[0001]本发明属于石油化工技术领域,涉及一种跨临界反应系统加氢-脱硫耦合改性C9/ C5石油树脂的方法及装置。 [0001] The present invention belongs to the field of petrochemical technology, relates to a reaction system is critical cross hydrogenation - Desulfurization coupled Modified C9 / C5 petroleum resin method and the apparatus.

背景技术 Background technique

[0002] C9/C5石油树脂是石油烃类高温裂解制备乙烯过程中的副产物一裂解汽油C9馏分经前处理、聚合、蒸馏形成的一种热塑性烃类树脂,软化点在60-16(TC,具有增黏性、黏结性和易与其它树脂相溶的特点,且酸值低、耐水、耐乙醇和耐化学品,化学稳定性和热稳定性好,并能调节粘性,广泛应用于油漆、橡胶、油墨、热溶胶、胶黏带和胶黏剂行业。油漆中加入C9/C5石油树脂,可以增加油漆光泽度,提高油漆附着度、硬度、耐酸和耐碱性;橡胶中加入C9/C5石油树脂可以起到增粘,补强、软化的作用;胶黏剂中加入C9/C5石油树脂可以提高粘合剂的粘合力、耐酸性、耐碱性及耐水性;油墨中加入C9/C5石油树脂可以起到展色、快干和增亮的作用。经过热聚合或催化聚合得到的C9/C5石油树脂都会存在一定量的双键不饱和化合物,颜色较深,软化度低,稳定性不好,在紫 [0002] C9 / C5 petroleum resin is an ethylene-product of pyrolysis of petroleum hydrocarbons in the C9 fraction of a pyrolysis gasoline by pretreatment, polymerization, distillation of a thermoplastic hydrocarbon resin is formed, a softening point of 60-16 (TC having increased viscosity, and ease of bonding compatibility with other resin characteristics, and low acid value, water resistance, chemical resistance, and ethanol, chemical stability and thermal stability, and can adjust the viscosity, widely used in paint , rubber, inks, hot-melt adhesives adhesive tape and paints industry added C9 / C5 petroleum resin, can increase the gloss paints, to improve paint adhesion, hardness, acid and alkali resistance; rubber was added C9 / C5 petroleum resin tackifying may function, reinforcing the softening effect; adhesive added C9 / C5 petroleum resin adhesive may improve adhesion, acid resistance, alkali resistance and water resistance; added to the ink C9 / C5 petroleum resin may function as color development, drying and brightening. certain amount of ethylenically unsaturated compound through C9 / C5 petroleum resins are catalytic polymerization or thermal polymerization obtained, the darker, low softening degree, stability is not good, in purple 线、氧或其他化学物质作用下易发生反应,使树脂热稳定性和氧化安定性变差,也会降低树脂与应用对象的相容性。因此,会影响C9/C5石油树脂的应用领域,减少了其可使用范围领域。C9/C5石油树脂通过催化加氢改性使树脂中含有的双键和部分苯环饱和,脱除C9/C5石油树脂在聚合中残留的硫化物、卤化物等杂质,以达到改善树脂的光热稳定性与互溶性,降低色度,提高软化点和品质,从而扩大加氢改性C9/C5石油树脂的应用领域和增加使用价值。比如在涂料行业,使用C9加氢改性石油树脂生产路标涂料,可改善其耐持久性和耐候性,使其寿命由原来的1年延长到3年。但C9/C5石油树脂加氢改性是一个较棘手的难题,特别是C9/C5石油树脂含有微量的有机硫, 既易于使催化剂中毒又限制了其应用范围。虽然现今有很多针对加氢改性C9/C5石油树脂的研宄,但是, Reactive occurs offline, the role of oxygen or other chemicals, the resin is deteriorated thermal stability and oxidation stability, compatibility with the resin will be reduced with the application object Thus, applications can affect C9 / C5 petroleum resin, which may be reduced using art range .C9 / C5 petroleum resin modified by catalytic hydrogenation of a benzene ring double bond and a portion of the resin contained in the saturated removal C9 / C5 petroleum resin remaining in the polymerization sulfide, halide, etc. impurities, in order to achieve thermal stability of the resin is improved compatibility with light and reduce the color, quality and increase the softening point, thereby expanding the modified hydrogenated C9 / C5 petroleum resin applications, and use value increases, such as in the paint industry, the use of Hydrogen production C9 petroleum resin paint signs, which can improve durability and resistance to weathering, so as to extend in a 3-year life of the original, but C9 / C5 petroleum resin Hydrogen is a more difficult problem especially C9 / C5 petroleum resin contains a trace amount of organic sulfur, both easy to poison the catalyst and limit its scope of application. While there are many today for Hydrogen C9 / C5 study based petroleum resin, however, 了上述所述改性后的C9/C5石油树脂内含有微量有机硫影响其使用等问题夕卜,目前改性的C9/C5石油树脂质量仍旧不尽人意,而且反应对设备、催化的要求非常高,从而造成成本的增加。目前,国内对加氢改性石油树脂的需求近年来急剧增加,但至今国内仍没有一家自主品牌的C9/C5石油树脂加氢改性产品生产厂家。 Requirements containing C9 / C5 petroleum resin after the above-described organic sulfur-modified microcentrifuge affect its problems Bu Xi, current-modified C9 / C5 petroleum resin mass is still unsatisfactory, and the reaction equipment, the catalyst is high, resulting in increased costs. At present, the domestic demand for petroleum resin-modified hydrogenated increased dramatically in recent years, but so far the country still is not an independent brand of C9 / C5 hydrogenation petroleum resin modified products manufacturer.

发明内容 SUMMARY

[0003] 本发明针对上述技术中存在的不足,发明一种跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法及装置,在提高改性后的C9/C5石油树脂的质量的同时,提供一种能有效脱除C9/C5石油树脂中有机硫的方法,优化反应环境。 [0003] The present invention is directed to the above-described deficiencies present in the art, to invent a hydrogenation reaction system is transcritical - coupling desulfurization modified C9 / C5 petroleum resin method and the apparatus, C9 after improving quality of the modified / C5 petroleum resin while providing a method for effective removal of C9 / C5 petroleum resin of organic sulfur, to optimize the reaction environment.

[0004] 为实现本发明的目的,本发明技术方案如下: [0004] To achieve the object of the present invention, the technical solution of the present invention are as follows:

[0005] 跨临界反应系统加氢-脱硫耦合改性C9/C5石油树脂的方法,包括以下操作步骤: [0005] Hydrogenation of transcritical the reaction system - C5 petroleum resin desulfurization method for coupling the modified C9 /, comprising the following steps:

[0006] (1)将C9/C5石油树脂与溶剂按照质量比1:1〜10:1,加入催化剂混合,加热,溶解; [0006] (1) The C9 / C5 petroleum resin and the solvent at a mass ratio of 1: 1~10: 1, the catalyst mixture was added, heated and dissolved;

[0007] (2)通入H2和C02摩尔比为1:1〜20:1的混合气体进行加氢反应,反应温度为150C 〜400C,反应压力为3 • OMPa〜35 • OMPa; [0007] (2) into C02 and H2 molar ratio of 1: 1 mixed gas is subjected to hydrogenation reaction, the reaction temperature is 150 C ~400 C, a reaction pressure of 3 • OMPa~35 • OMPa: 1~20 ;

[0008] (3)加氢反应过程中产生的气体H2S、剩余的混合气体H2和C〇2进行分离,除去H2S,H2 和C〇2加压重新返回进行加氢反应循环使用; [0008] (3) generated during the hydrogenation reaction gases H2S, H2 and the remaining mixed gas separated C〇2 remove H2S, H2 and pressurized return to C〇2 recycled hydrogenation reaction;

[0009] (4)加氢-脱硫反应1〜10h后,经减压后物料从加氢反应器中放出即为共混加氢改性松脂与C9/C5石油树脂产品。 [0009] (4) Hydrogenation - desulfurization reaction 1~10h, the material discharged after decompression is the blending of rosin-modified hydrogenated C9 / C5 petroleum resin product from the hydrogenation reactor.

[0010] 优选的是,所述步骤(2)中流出的气体经过膨胀机后,进入气液分离器进行分离, 所得到的溶剂液体回流到加氢反应器内,剩下的气体为H2S、HdPC〇2,将气体通入吸收塔中, 经吸收塔吸收H2S气体后,剩余H2和C02再通入透平压缩机。 [0010] Preferably, the effluent (2) in the gas after the step of the expander, into the gas-liquid separator for separating the solvent was refluxed liquid into the hydrogenation reactor, the remaining gas is H2S, HdPC〇2, the gas introduced into the absorption column, after absorption of H2S gas absorption tower, the residual H2 and C02 then pass into the turbine compressor.

[0011] 优选的是,所述步骤(3)从加氢反应器中取出混合气体的流量为0〜12000m3/h,将气体通过膨胀机,膨胀机与透平压缩机连接,往透平压缩机内补充C〇2和H2混合气体,再将混合气体通入加氢反应器内。 [0011] Preferably, the step (3) removed from the mixed gas flow rate of the hydrogenation reactor 0~12000m3 / h, the gas through the expander, the expander turbine and a compressor connected to the turbine compression C〇2 added and H2 mixed gas in the machine, and then the mixed gas is introduced into the hydrogenation reactor.

[0012] 优选的是,步骤⑴中加入的催化剂的量为加入的C9/C5石油树脂与溶剂总量的质量的1〜30%;其中所述的催化剂为负载镍或钯的催化剂。 [0012] Preferably, the amount of catalyst added in step ⑴ 1~30% by mass of the total amount of the added resin and C9 / C5 petroleum solvent; wherein said catalyst is a supported nickel or palladium catalyst.

[0013] 优选的是,步骤⑶中气液分离器的温度为0〜50C,压力为0.0〜0.5MPa,液体流量为0〜100m3/h,气体流量为0〜10000m3/h。 [0013] Preferably, the gas-liquid separator in step ⑶ temperature of 0~50 C, a pressure of 0.0~0.5MPa, liquid flow 0~100m3 / h, the gas flow rate 0~10000m3 / h.

[0014] 优选的是,步骤(1)中所述的溶剂为环己烷、乙基环己烷、n-己烷、n-庚烷、矿物精油、200#溶剂油中的一种。 [0014] Preferably, the step (1) in said solvent is cyclohexane, ethylcyclohexane, hexane N-, N- heptane, mineral spirits, solvent naphtha # 200 a.

[0015] —种加氢-脱硫耦合改性C9/C5石油树脂方法的装置,包括: [0015] - Species Hydrogenation - C9 modified coupling means desulfurization / C5 petroleum resin method, comprising:

[0016] 加氢反应器,其包括:多个加热管,设于加氢反应器内部;以及气体分布器,其包括进气口和多个用于排气的喷头;膨胀机,其与所述加氢反应器连接;以及透平压缩机,其与所述膨胀机连接,并通过所述膨胀机驱动所述透平压缩机工作,所述透平压缩机的出气口与所述加氢反应器连接。 [0016] The hydrogenation reactor, comprising: a plurality of heat pipes, disposed inside the hydrogenation reactor; and a gas distributor, which comprises a head and a plurality of intake ports for exhaust gas; expander with the said hydrogenation reactor; and a turbine compressor, which is connected to the expander, the expander driven by said turbine compressor, said turbine and said compressor outlet hydrogenation connected to the reactor.

[0017] 优选地,上述技术方案中,所述气体分布器呈“L”型,其底端为圆环管状,在该圆环管上均匀设有多个用于排气的喷头。 [0017] Preferably, the above-described aspect, the gas distributor as a "L" shaped, which is the bottom end of the tubular ring, the ring on the head is provided with a plurality of uniformly tube for exhaust gas.

[0018] 优选地,上述技术方案中,所述加热管为多个,呈平行均布在所述加氢反应器内部;所述气体分布器有多个,所述多个气体分布器相互连通,所述每个气体分布器设在所述加热管之间。 [0018] Preferably, the above-described aspect, a plurality of the heating tube, in a parallel uniform inside the hydroprocessing reactor; plurality, the plurality of communication with each other said gas distributor has a gas distributor , each of said gas distributor is provided between the heating tubes.

[0019] 优选地,上述技术方案中,所述用于松脂与C9/C5石油树脂共混加氢改性的装置, 还包括:溶解釜,其与所述加氢反应器连接,用于溶解生产所需的原料;气液分离器,其与所述膨胀机连接;溶剂泵,其与所述气液分离器连接,用于将分离出的液体溶剂送至所述加氢反应器内;以及吸收塔,其进气口与所述气液分离器连接,出气口与所述透平压缩机连接, 用于去除H2S气体。 [0019] Preferably, the above technical solution, the hydrogenated rosin-modified C5 petroleum resin blended with a device C9 / means for, further comprising: a dissolving tank, which is connected to the hydrogenation reactor for dissolving raw materials required to produce; gas-liquid separator, which is connected to the expander; solvent pump, which is connected to the gas-liquid separator for the separated liquid solvent to said hydrogenation reactor; and the absorption tower inlet and the gas-liquid separator is connected, outlet connected to said centrifugal compressor, for removing H2S gas.

[0020] 本发明方法把C9/C5石油树脂和溶剂加入熔解釜内加热熔解后压入加氢反应器内,充入H2和⑶2混合气体进行加氢反应。 [0020] The method of the present invention to C9 / C5 petroleum resin and the solvent added to the autoclave after the heat-melted melted pressed into the hydrogenation reactor, charged with a mixed gas of H2 and ⑶2 hydrogenation reaction. 由于C9/C5石油树脂中含有微量的有机硫,极易使加氢催化剂中毒失活,而且加氢副产物IfeS的累积不仅抑制了化学平衡朝加氢脱硫方向的移动,而且H2S还对加氢反应器有一定腐蚀作用,所以本发明采用加氢反应器不断地流出气相的方法,使加氢生成的H2S气体不断地离开加氢反应器,从而消除了副产物H2S积累而引起的反馈抑制作用,打破了C9/C5石油树脂加氢-脱硫的化学平衡,提高了加氢反应速率和平衡转化率,实现了加氢反应-脱硫的耦合。 Since C9 / trace amounts of organic sulfur-containing petroleum resin C5, easy to make of deactivation of hydrogenation catalyst, hydrogenation and accumulated not only by-products is suppressed IfeS chemical equilibrium toward the direction of hydrodesulfurization, hydrogenation but also H2S the reactor have a corrosive effect, the present invention is the method continuously hydrogenation reactor effluent gas phase hydrogenation of H2S gas is constantly leaving the hydrogenation reactor, thus eliminating the feedback inhibition by-products caused by the accumulation of H2S , breaking the C9 / C5 petroleum resin hydrogenation - desulfurization of chemical Ping Heng, the hydrogenation reaction rate and improve the equilibrium conversion, the hydrogenation reaction is achieved - coupling desulfurization.

[G021] 从加氢反应器流出的气相含有H2、C〇2、H2s和溶剂蒸汽,但是这些流出的物质经膨胀机膨胀降压后,溶剂蒸汽冷凝为液态从气液分离器分离出来,而H2S被吸收塔脱除,因此加压循环回进行加氢反应的气体仅为不凝气体H2和C02。 [G021] containing H2, C〇2, H2s and solvent vapor from the gas phase hydrogenation reactor effluent, but after these substances flowing through the expander expands the blood pressure, the solvent vapor is condensed to a liquid separated from the gas-liquid separator, and H2S absorber is removed, so the pressurized recycled to hydrogenation reaction gas only non-condensable gas and H2 C02. 由上可见驱动膨胀机的气体流量大于透平压缩机加压循环气体的流量,亦即是说膨胀机做出的膨胀功大于透平压缩机所需的压缩功,而系统所需增加的能量由加氢反应器内加氢放出的反应热和加热盘管供给热能以提高溶剂蒸汽流量;系统所需增加的能量由加氢反应器内加氢放出的反应热和加热盘管供给热能以提高溶剂蒸汽流量。 Clear from the gas flow driving the expander turbine compressor is greater than the flow rate of the pressurized circulating gas, that is to say the expander also made larger than the turbine expansion work required compression work of the compressor, and the energy required to increase the system the reaction heat energy supplied to the heating coil and discharged from the hydrogenation reactor, the hydrogenation solvent to increase the steam flow; heat of reaction required by the system increased energy emitted by hydrogenation and the hydrogenation reactor heating coil to increase the heat supply solvent vapor flow. 往透平压缩机内通入H2和C〇2的混合气体,膨胀机直接推动透平压缩机加压出和0)2循环回系统,然后再通入加氢反应器内。 To pass into the turbine compressor and C〇2 H2 mixed gas expander turbine compressor directly driven out and pressing 0) 2 recycled to the system, and then pass into the hydrogenation reactor. 又由于出与⑶2在加氢反应器内不断地循环和鼓泡流动,强化了加氢反应器内物料的搅拌和热质传递,而且出与〇〇2还产生“超空泡”效应,既可减省了加氢反应器内的搅拌器安装又最大限度地减少了C9/C5石油树脂高黏性物料间的传递阻力和加氢双键的空间位阻,大大地提高了C9/C5石油树脂加氢-脱硫耦合的反应效果。 Also, because a constant cycle and ⑶2 in the hydrogenation reactor and a bubble flow, stirring and strengthen the heat and mass transfer material in a hydrogenation reactor, and also illustrating the generation 〇〇2 "supercavitating" effect, both Save can save a stirrer installed in the hydrogenation reactor and minimize C9 / C5 petroleum resin transfer resistance between the high-viscosity material and the hydrogenation of the double bond steric hindrance, greatly improved C9 / C5 petroleum hydrogenation resin - desulfurization effect coupling reaction.

[0022] 本发明循环过程是压缩—反应—分离—跨临界膨胀—气液分离—压缩(蒸汽动力),从加氢反应器流出的气相,其中具体为由加氢反应器流出的C02,从超/亚临界状态跃迁为低温低压常态即称为跨临界状态,该变化使膨胀机膨胀做功驱动透平压缩机,以达到膨胀-压缩自循环。 [0022] The present invention is a compression cycle - reaction - separation - transcritical expansion - liquid separator - Compression (steam power) flowing from the gas phase hydrogenation reactor, wherein in particular by hydrogenation reactor effluent C02, from super / subcritical state transition is called a low-temperature low-pressure transcritical normal state, the change of the expander turbine expansion work drives the compressor, in order to achieve expansion - contraction from the circulation. 由反应系统放出的反应热或盘管内热源间接加热汽化的蒸汽直接做动力,热功转换效率约为100 %。 Indirect heating evaporation heat released in the reaction system by the reaction heat or direct steam powered coils, thermal power conversion efficiency of about 100%.

[0023]与现有的技术相比,本发明的有益效果是: [0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] 1、本发明采用加氢-脱硫耦合跨临界C02反应系统改性C9/C5石油树脂,能有效的除去C9/C5石油树脂中含有的微量的有机硫,提高改性后C9/C5石油树脂的质量,扩大其使用领域;同时提高改性后的C9/C5石油树脂的稳定性、色泽等。 [0024] 1, the present invention uses a hydrogenation - desulphurization reactor system coupled transcritical C02-modified C9 / C5 petroleum resin, can effectively remove the C9 / C5 petroleum resin containing a trace amount of organic sulfur, C9 / C5 improved after modification petroleum resin mass to expand its field of use; while increasing the C9 / C5 petroleum resin stability, the modified color and the like. 进一步的本发明加氢反应过程中能有效的除去生成的副产物H2S,使反应不断地朝着加氢-脱硫的方向进行,提高了加氢-脱硫反应速度和平衡转化率。 Further hydrogenation reaction of the present invention, the process can effectively remove the by-products generated H2S, so that the hydrogenation reaction is continuously toward - the direction of the desulfurization, hydrogenation improves - the desulfurization reaction rate and the equilibrium conversion.

[0025] 2、采用跨临界C〇2膨胀-压缩自循环技术,使从加氢反应器流出的高压气相经膨胀机膨胀直接推动透平压缩机加压H2和C〇2循环回系统,减少了热功转换过程:热能-> 机械能4电能4机械能的有效能损失,提1 了热能转换的热功效率。 [0025] 2, using transcritical C〇2 expansion - compression self-loop technique, the high-pressure gas flowing through the expander from the hydrogenation reactor directly promote the expansion turbine and the compressor pressure C〇2 H2 recycled to the system, reducing the thermal power of the conversion process: energy -> mechanical energy to electrical energy 4 4 exergy loss of mechanical energy, thermal power 1 mentioned energy conversion efficiency.

[0026] 3、超临界H#PC02在加氢反应器中不断地鼓泡循环流动搅拌和产生“超空泡”效应, 既减省了加氢反应器的搅拌机安装又最大限度地减少了高黏性C9/C5石油树脂物料间的传递阻力和空间位阻,大大地提高了加氢反应器的传热传质速度和加氢-脱硫反应效果。 [0026] 3, H # PC02 supercritical bubbled continuously circulating and stirring to produce "super-cavitation" effect in the hydrogenation reactor, both saving Save hydrogenation reactor impeller is mounted in turn minimizes high viscous C9 / C5 transfer resistance between the steric and petroleum resin materials, greatly improving the speed of heat and mass transfer hydrogenation reactor and a hydrogenation - desulfurization effect. t〇〇27] 4、加氢反应器采用超/亚临界H2及C02进行鼓泡搅拌,不需要安装机械搅拌器,更有利于高压设备的制造、操作、维修和防漏。 t〇〇27] 4, the hydrogenation reactor is ultra / subcritical H2 and C02 bubbling stirring, no need to install a mechanical stirrer, a high-pressure equipment is more conducive to manufacturing, operation, maintenance and leakproof.

附图说明 BRIEF DESCRIPTION

[0028] 图1为加氢-脱硫耦合改性C9/C5石油树脂方法流程图,其中1是溶解釜,2是加氢反应器,3是膨胀机,4是气液分离器,5是吸收塔,6是透平压缩机,7是溶剂栗。 [0028] FIG. 1 is a hydrogenation - Desulfurization coupled Modified C9 / C5 petroleum resin flowchart of a method, wherein 1 is a dissolving tank, 2 is the hydrogenation reactor, the expander 3, a gas-liquid separator 4, 5 is absorbed tower, turbine compressor 6, 7 Li solvent.

[0029] 图2是根据本发明加氢反应器的结构示意图,其中21是进料口,22是出气口,23是出料口,24是加热盘管,25为气体分布器,251是进气口,252是喷头。 [0029] FIG. 2 is a structural diagram of the present invention, the hydrogenation reactor, wherein the feed inlet 21, outlet 22, a discharge port 23, a heating coil 24, 25 is a gas distributor, into a 251 port, 252 is the head.

[0030] 图3是根据本发明加氢反应器中单个气体分布器的结构示意图。 [0030] FIG. 3 is a schematic diagram of the present invention in a hydrogenation reactor a single gas sparger in accordance with.

[0031] 图4是根据本发明加氢反应器中单个气体分布器的俯视图。 [0031] FIG. 4 is a plan view of the present invention, the hydrogenation reactor a single gas sparger in accordance with.

具体实施方式 detailed description

[0032]下面结合附图,对本发明的具体实施方式进行详细描述,但应当理解本发明的保护范围并不受具体实施方式的限制。 [0032] below with the accompanying drawings, specific embodiments of the present invention will be described in detail, it should be understood that the scope of the present invention is not limited to the specific embodiments.

[0033]除非另有其它明确表示,否则在整个说明书和权利要求书中,术语“包括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的元件或组成部分,而并未排除其它元件或其它组成部分。 [0033] Unless otherwise expressly indicated otherwise, throughout the specification and claims, the terms "including" or a conversion such as "comprises" or "comprising" and the like will be understood to include the Chen Shu elements or components of , and does not exclude other elements or other components.

[0034] 实施例1 [0034] Example 1

[0035]如图1-4所示,用于松脂与C9/C5石油树脂共混加氢改性的装置,包括:溶解釜1、加氢反应器2、膨胀机3、气液分离器4、吸收塔5、透平压缩机6、溶剂栗7。 [0035] shown in Figure 1-4, the apparatus rosin C9 / C5 petroleum resin blends for hydrogenation modification, comprising: a dissolving tank 1, the hydrogenation reactor 2, the expander 3, the gas-liquid separator 4 , absorption tower 5, turbine compressor 6, 7 Li solvent.

[0036]溶解釜1的出料口与所述加氢反应器2的进料口连接,溶解釜1用于溶解生产所需的原料。 [0036] The vessel 1 was dissolved spout connected to the feed inlet of the hydrogenation reactor 2, a dissolving vessel for dissolving raw materials required for production. 加氢反应器2,呈圆柱形,加氢反应器的上部设有进料口21、出气口22,底部设有出料口23,加氢反应器2包括加热管24,为加热盘管,其设于加氢反应器内部;气体分布器25, 其包括进气口251和多个用于排气的喷头252;膨胀机3与所述加氢反应器2的出气口连接。 Hydrogenation reactor 2 has a cylindrical shape, the upper portion of the hydrogenation reactor is provided with feed inlet 21, outlet 22, is provided with a bottom discharge opening 23, hydrogenation reactor 2 comprises a heating tube 24, heating coil, provided inside the hydrogenation reactor; gas distributor 25, which comprises a plurality of intake ports 251 and 252 for the exhaust nozzle; expander 3 is connected to the outlet port 2 of the hydrogenation reactor. 透平压缩机6与所述膨胀机3连接,并通过所述膨胀机3驱动所述透平压缩机6工作,所述透平压缩机6的出气口与所述加氢反应器2连接。 Turbine compressor 63 is connected to the expander, compressor and driving the turbine 6 operated by the expander 3, the turbine outlet and the compressor 6 to the hydrogenation reactor 2 is connected. 气液分离器4与所述膨胀机3连接,用于分离反应后产生的混合气体,分离出气体和液体。 Gas-liquid separator 43 is connected to the expander, a mixed gas produced after separation of the reaction for separating gas and liquid. 溶剂栗7与气液分离器2连接,用于将分离出的液体溶剂送至所述加氢反应器2内;吸收塔5的进气口与所述气液分离器4连接,出气口与所述透平压缩机6连接,用于去除需要去除的气体。 The solvent Li 72 connected to the gas-liquid separator for the separated liquid solvent to said hydrogenation reactor 2; absorber intake port 5 and the gas-liquid separator 4 is connected to the outlet the turbine 6 is connected to a compressor, for removing the gas to be removed.

[0037] 优选地,所述气体分布器25呈“L”型,其底端为圆环管状,在该圆环管上均匀设有多个用于排气的喷头252,所述喷头为“L”型,成同一方向倾斜设置。 [0037] Preferably, the gas distributor 25 as a "L" shaped, which is the bottom end of the tubular ring, the ring on the pipe for the exhaust gas uniformly provided with a plurality of nozzles 252, the head is " L "shaped, inclined to the same direction. 在呈环状的管上均布有多个排气喷头,使气体排放更为均匀,使得至于加氢反应器内的物料与气体充分接触,加快反应速率。 In the ring-shaped exhaust pipe a plurality of nozzles are uniformly distributed, so that more uniform gas emissions, such as for material and gas in the hydrogenation reactor sufficient contact to accelerate the reaction rate. 呈倾斜设置的喷头喷出的气体往同一方向倾斜喷出气体,使气泡呈旋转状在加氢反应器2内运动,使得反应的物料与气体充分接触,加快反应速度。 A gas discharge nozzle arranged inclined in the same direction inclined discharge gas, the shape of the bubble 2 moves rotationally in the hydrogenation reactor, the reaction gas such that material is sufficient contact, enhance the reaction rate.

[0038] 优选地,所述加热管24为多个,呈平行均布在所述加氢反应器2内部;所述气体分布器25有多个,所述多个气体分布器25相互连通,所述每个气体分布器25的圆环管设在所述加热管24之间。 [0038] Preferably, the plurality of heating tube 24, in a parallel uniformly distributed inside the hydrogenation reactor 2; a plurality of gas distributor 25, a plurality of gas distributor 25 communicate with each other, each ring of the gas distributor tube 25 is disposed between the heating tube 24.

[0039] 利用上述的装置作为反应装置,一种松脂与C9/C5石油树脂共混加氢改性的方法, 包括以下步骤:将原料C9/C5石油树脂和乙基环己烷按质量比1:1加入熔解釜1,加入原料总量的质量分数1 %的负载钯的催化剂混合,加热,熔解,形成混合物料,将H2和⑶2摩尔比为10:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和⑶2混合气体至加氢反应器2内压力为7.〇MPa,继续加热至25〇C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体出与0)2混合气体不断地流出,控制混合气体流出量为12000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器2流出的气相含有HhCOhIfeS和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度<50C,压力<0.5MPa,液体流量<100m3/h,气体流量<l〇〇〇 [0039] The apparatus used as the reaction apparatus, a rosin resin blended with hydrogenated C5 petroleum method of modifying C9 /, comprising the steps of: starting material C9 / C5 petroleum resin and the mass ratio of 1 ethylcyclohexane : 1 was added a melting vessel, mixing of the catalyst to the total amount of the raw material fraction of 1% by mass of palladium, heated, melted and mixed material is formed, the molar ratio of H2 and ⑶2 10: 1 mixed gas introduced into the hydrogenation reactor 2, then heating to 150 C, and continuously filled into the inner pressure of a mixed gas of H2 and ⑶2 to 7.〇MPa hydrogenation reactor, heating was continued until 25〇 C, and then open the hydrogenation reactor 2 air inlet valve of H2S generated during the hydrogenation reaction, the reaction with the remaining gas 0) 2 mixed gas constantly flows, the outflow of the mixed gas was controlled 12000m3 / h, after the expander expands into the gas-liquid separator 3 throttled 4, the effluent from the vapor phase hydrogenation reactor 2 containing HhCOhIfeS and solvent vapor, but the material was expanded down the expander 3 flows into the gas-liquid separator 4, the temperature of the gas-liquid separator 4 <50 C, a pressure <0.5MPa, liquid flow rate <100m3 / h, the gas flow rate <l〇〇〇 m3/h。 m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂泵7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out of the pump 7 into the solvent, recycled back into the system to play. 而h2、C〇2、H2S 这些余下的混合气相进入吸收塔5中,其中HsS被吸收塔5脱除,余下的气相h2、C02与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应,透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压,混合气体流出的流量约为l〇〇〇〇m3/h,并维持加氢反应器的压力为7 • OMPa,反应1 • 5h后,加氢反应器2加热升温至350C,控制反应温度保持在345C〜355C范围内,反应压力为14• OMPa〜15 • OMPa,在此反应条件下反应5. Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出。 And h2, C〇2, H2S gas mixture of these remaining 5 into the absorber, wherein the absorber 5 HsS is removed, the remaining vapor h2, supplemented with the new C02 H2, into the turbine compressor with C〇2- 6 pressurized recycled to the hydroprocessing reactor 2 hydrogenation reaction, the turbine work is carried out 6 the expander turbine 3 driven compressor 6 expansion work pressure, flow rate of the mixed gas flowing out from about l〇〇〇〇m3 / h, and maintain the hydrogenation reactor pressure was 7 • OMPa, 1 • 5h after the reaction, the hydrogenation reactor 2 is heated up to 350 C, the reaction temperature is maintained at 345 C~355 C range, the reaction a pressure of 14 • OMPa~15 • OMPa, under this reaction conditions 5. Oh, the product is obtained, C9 / C5 petroleum resin flows from the hydrogenation reactor discharge port 2 after modification. 经所得产品为改性C9/C5加氢石油树脂,溴值为1.0。 The resulting product was a modified C9 / C5 hydrogenated petroleum resin, a bromine number of 1.0.

[0040] 实施例2 [0040] Example 2

[0041] 使用的反应装置与实施例1相同,将原料C9/C5石油树脂和环己烷按质量比3:1加入熔解釜1,加入原料总量的质量分数30%的负载镍的催化剂混合,加热,熔解,形成混合物料,将抱和(:02摩尔比为1:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入出和0)2混合气体至加氢反应器2内压力为3. OMPa,继续加热至250 C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为7000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C〇2、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度彡50C,压力彡0 • 5MPa,液体流量彡100m3/h,气体流量彡10000m3/h。 [0041] The same reaction apparatus used in Example 1, the raw material C9 / C5 petroleum resin and cyclohexane mass ratio 3: 1 was added a melting tank 1, the mass fraction of the total amount of the mixed raw material was added 30% supported nickel catalyst heated, melted to form a mixed material, the hold and (: 02 molar ratio of 1: 1 mixed gas introduced into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged out, and 0) 2 mixed gas to the hydrogenation reactor pressure was 2 3. OMPa, heating was continued to 250 C, and then open the hydrogenation reactor outlet valve 2, the reaction of H2S generated during the hydrogenation, the reaction with the remaining gas mixture H2 C02 gas constantly flows, the control amount of the mixed gas flowing 7000m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C〇2, H2S and solvent vapor, However, these substances flowing through the expander 3 down into the expanded gas-liquid separator 4, the gas-liquid separator 4 San temperature 50 C, a pressure San 0 • 5MPa, San liquid flow 100m3 / h, the gas flow rate San 10000m3 / h . 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂泵7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out of the pump 7 into the solvent, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C〇2与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, supplemented with the new C〇2 H2, into the turbine compressor with C〇2- 6 pressurized recycled to the hydroprocessing reactor 2 hydrogenation reaction, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为5000m3/h,并维持加氢反应器的压力为3 • OMPa,反应3. Oh后,加氢反应器2加热升温至250 C,控制反应温度保持在250C〜255C范围内,反应压力为7 • OMPa〜8. OMPa,在此反应条件下反应5.0h,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为4.0。 Flowing the mixed gas flow rate of about 5000m3 / h, and maintain the pressure of the hydrogenation reactor 3 • OMPa, reaction 3. Oh, hydrogenation reactor 2 heating to 250 C, to control the reaction temperature was maintained at 250 C ~255 C within the range, the reaction pressure was 7 • OMPa~8. OMPa, in this 5.0H reaction conditions, the product is obtained, C9 / C5 petroleum resin from the discharge port hydrogenation reactor 2 after modification effluent, bromine is 4.0. [0042] 实施例3 [0042] Example 3

[0043] 使用的反应装置与实施例1相同,将C9/C5石油树脂和200#溶剂油按质量比5:1力口入熔解釜1,加入原料总量的质量分数20%的负载镍的催化剂混合,加热,熔解,形成混合物料,将H2和C02摩尔比为10:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和C02混合气体至加氢反应器2内压力为7.OMPa,继续加热至250 C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为5000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C02、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度彡50C,压力彡0 • 5MPa,液体流量彡100m3/h,气体流量彡10000m3/h。 [0043] The reaction apparatus identical to that used in Example 1, the C9 / C5 petroleum resin and 200 # solvent oil mass ratio of 5: 1 into the melting tank 1 opening force, the total mass fraction of 20% was added feed of supported nickel catalyst are mixed, heated, melted and mixed material is formed, the molar ratio of H2 and C02 is 10: 1 mixed gas introduced into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged into the mixed gas of H2 and C02 2 to the inner pressure in the hydrogenation reactor 7.OMPa, heating was continued to 250 C, and then open the hydrogenation reactor outlet valve 2, so that during the hydrogenation reaction produced H2S, H2 and the reaction gas remaining mixed gas C02 continuously flowing, the control amount of the mixed gas flowing 5000m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C02, H2S, and solvent vapors, but these effluents the material was expanded down the expander 3 into the gas-liquid separator 4, the gas-liquid separator 4 San temperature 50 C, a pressure San 0 • 5MPa, San liquid flow 100m3 / h, the gas flow rate San 10000m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂栗7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out into the solvent Li 7, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied H2, C〇2- entry into the compressor turbine plus 6 recycled to the hydroprocessing reactor pressure hydrogenation reaction 2, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为3000m3/h,并维持加氢反应器的压力为7 • OMPa,反应1 • 5h后,加氢反应器2加热升温至300 C,控制反应温度保持在300C〜310C范围内,反应压力为14• OMPa〜15• OMPa,在此反应条件下反应7. Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为< 1.0。 Flowing the mixed gas flow rate of about 3000m3 / h, and maintain the hydrogenation reactor pressure was 7 • OMPa, reaction 1 • 5h, the hydrogenation reactor is heated up to 2 300 C, to control the reaction temperature was maintained at 300 C ~310 C within the range, the reaction pressure was 14 • OMPa~15 • OMPa, under this reaction conditions 7. Oh, the product is obtained, C9 / C5 petroleum resin discharge from the hydrogenation reactor 2 after modification outflow port, a bromine number of <1.0.

[0044] 实施例4 [0044] Example 4

[0045] 使用的反应装置与实施例1相同,将C9/C5石油树脂和n-庚烷按质量比4:1加入熔解釜1,加入原料总量的质量分数5 %的负载钯的催化剂混合,加热,熔解,形成混合物料,将H2和C02摩尔比为15:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和C02混合气体至加氢反应器2内压力为7.0MPa,继续加热至25〇C,然后打开加氢反应器2 出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体112与(:02混合气体不断地流出, 控制混合气体流入量为3000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C〇2、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4气液分离器4的温度彡50C,压力彡0.5MPa,液体流量彡100m3/h,气体流量彡10000m3/h。溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂泵7中 [0045] The same reaction apparatus used in Example 1, the C9 / C5 petroleum resin and n- heptane in mass ratio 4: 1 was added a melting tank 1, the mass fraction of the total amount of the mixed raw material was added 5% palladium catalyst heated, melted and mixed material is formed, the molar ratio of H2 and C02 is 15: 1 mixed gas introduced into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged to a mixed gas of H2 and C02 plus 2 a hydrogen pressure of 7.0MPa reactor, heating was continued until 25〇 C, and then open the hydrogenation reactor outlet valve 2, the reaction of H2S generated during the hydrogenation, the reaction with residual gas 112 (: 02 mixed gas continuously flowing, the control amount of the mixed gas flowing 3000m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C〇2, H2S and solvent vapors, but these substances flowing through the expander 3 down into the expanded gas-liquid separator 4 San temperature gas-liquid separator 4 is 50 C, a pressure San 0.5MPa, liquid flow San 100m3 / h, the gas flow rate San 10000m3 / h. the solvent vapor It is separated from the condensed liquid out of the gas-liquid separator 4 into solvent pump 7 打回系统循环使用。而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、⑶2与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氛反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。混合气体流出的流量约为1000m3/h,并维持加氢反应器的压力为7. OMPa,反应1.5h后,加氢反应器2加热升温至350 C,控制反应温度保持在345C〜355C范围内,反应压力为14.0MPa〜15.0MPa,在此反应条件下反应3. Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为< 1_0〇 Recycled back into the system to play, while the H2, C02, H2S these remaining mixed vapor into the absorber 5, where H2S absorption tower 5 is removed, the remaining gas phase H2, ⑶2 and add new H2, C〇2- entry into 6 turbocompressors pressurizing recycled to the hydrogenation reactor 2 is added to the reaction atmosphere, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. effluent flow rate of the mixed gas of about 1000m3 / H, and maintain pressure to the hydrogenation reactor 7. OMPa, reaction 1.5h, warmed hydrogenation reactor 2 is heated to 350 C, the reaction temperature is maintained at 345 C~355 C range, the reaction pressure was 14.0MPa~15.0MPa, under reaction conditions 3. Oh, the product is obtained, C9 / C5 petroleum resin flows from the hydrogenation reactor discharge port 2 after modification, bromine number of <1_0〇

[0046] 实施例5 [0046] Example 5

[0047] 使用的反应装置与实施例1相同,将C9/C5石油树脂和n-己烷按质量比7:1加入熔解釜1,加入原料总量的质量分数10%的负载钯的催化剂混合,加热,熔解,形成混合物料, 将H2和C〇2摩尔比为12:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入出和〇}2混合气体至加氢反应器2内压力为8 • OMPa,继续加热至270C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为1000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C02、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度彡50C,压力彡0 • 5MPa,液体流量彡100m3/h,气体流量彡10000m3/h。 [0047] The reaction apparatus identical to that used in Example 1, the C9 / C5 petroleum resin and n- hexane at a mass ratio of 7: 1 was added melting vessel 1, the mass fraction of the total amount of the mixed raw material was added 10% palladium catalyst heated, melted and mixed material is formed, the molar ratio of H2 and C〇2 12: 1 mixed gas introduced into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged into a mixing and a square 2} gas to the hydrogenation reactor pressure was 2 8 • OMPa, heating was continued to 270 C, and then open the hydrogenation reactor outlet valve 2, the reaction of H2S generated during the hydrogenation, the reaction with the remaining gas mixture H2 C02 gas constantly flows, the control amount of the mixed gas flowing 1000m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C02, H2S, and solvent vapors, but these flowing material was expanded down into the expander 3 gas-liquid separator 4, the gas-liquid separator 4 San temperature 50 C, a pressure San 0 • 5MPa, San liquid flow 100m3 / h, the gas flow rate San 10000m3 / h. ,溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂栗7中,打回系统循环使用。 The solvent is separated from the steam is condensed to a liquid-liquid separator 4 out into the solvent Li 7, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02与新补充的H2、C02—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied H2, C02- entry into the compressor turbine pressurization cycle 6 back to the hydrogenation reactor 2 hydrogenation reaction, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为500m3/h,并维持加氢反应器的压力为8 • OMPa,反应1 • 5h后,加氢反应器2加热升温至39〇C,控制反应温度保持在380C〜400C范围内,反应压力为9 • OMPa〜10 • OMPa,在此反应条件下反应9. Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为< 1-0〇 Flowing the mixed gas flow rate of about 500m3 / h, and maintain the hydrogenation reactor pressure of 8 • OMPa, reaction 1 • 5h, the hydrogenation reactor is heated up to 39〇 2 C, controlling the reaction temperature was maintained at 380 the C~400 C range, the reaction pressure was 9 • OMPa~10 • OMPa, under this reaction conditions 9. Oh, the product is obtained, C9 / C5 petroleum modified resin from the hydrogenation reactor 2 spout, a bromine number of <1-0〇

[0048] 实施例6 [0048] Example 6

[0049] 使用的反应装置与实施例1相同,将C9/C5石油树脂和乙基环己烷按质量比6:1力口入熔解釜1,加入原料总量的质量分数15%的负载镍的催化剂混合,加热,熔解,形成混合物料,将出和0)2摩尔比为13:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和C02混合气体至加氢反应器2内压力为8• OMPa,继续加热至250C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为500m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C〇2、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度<50C,压力<0 • 5MPa,液体流量彡100m3/h,气体流量< 10000m3/h。 [0049] The reaction apparatus identical to that used in Example 1, the C9 / C5 petroleum resin and ethylcyclohexane mass ratio of 6: 1 force the mouth melting tank 1, the mass fraction of the raw material to the total amount of supported nickel 15% the catalyst mixture is heated, melted and mixed material is formed, and the out 0) 2 molar ratio of 13: 1 mixed gas into a hydrogenation reactor 2, and then heating to 150 C, and charged with H2 and the constant C02 mixed gas to the hydrogenation reactor pressure was 2 8 • OMPa, heating was continued to 250 C, and then open the hydrogenation reactor outlet valve 2, the reaction of H2S generated during the hydrogenation, the reaction with the remaining H2 gas C02 gas mixture continuously flowing out of the control amount of the mixed gas flowing into 500m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C〇2, H2S, and the solvent steam, but these substances flowing through the expander 3 down into the expanded gas-liquid separator 4, the temperature of the gas-liquid separator 4 <50 C, pressure <0 • 5MPa, San liquid flow 100m3 / h, the gas flow rate <10000m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂泵7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out of the pump 7 into the solvent, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02与新补充的h2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied h2, C〇2- entry into the compressor turbine plus 6 recycled to the hydroprocessing reactor pressure hydrogenation reaction 2, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为300m3/h,并维持加氢反应器的压力为8 • OMPa,反应1.5h后,加氢反应器2加热升温至3〇〇C,控制反应温度保持在300C〜305C范围内,反应压力为23 • OMPa〜25. OMPa,在此反应条件下反应5 • Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值< 1.0。 Flowing the mixed gas flow rate of about 300m3 / h, and maintain the hydrogenation reactor pressure of 8 • OMPa, reaction 1.5h, the hydrogenation reactor is heated up to 3〇〇 2 C, controlling the reaction temperature was maintained at 300 the C~305 C range, the reaction pressure was 23 • OMPa~25. OMPa, under this reaction conditions 5 • Oh, the product is obtained, C9 / C5 petroleum modified resin from the hydrogenation reactor 2 spout, a bromine number of <1.0.

[0050] 实施例7 [0050] Example 7

[0051] 使用的反应装置与实施例1相同,将C9/C5石油树脂和200#溶剂油按质量比6:1加入熔解釜1,加入原料总量的质量分数25%的负载镍的催化剂混合,加热,熔解,形成混合物料,将出和0)2摩尔比为10:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和C02混合气体至加氢反应器2内压力为7 • OMPa,继续加热至250C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为300m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C02、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度彡50C,压力<0.5MPa,液体流量彡100m3/h,气体流量< 10000m3/h。 [0051] The same reaction apparatus used in Example 1, the C9 / C5 petroleum resin and 200 # solvent oil mass ratio of 6: 1 was added a melting tank 1, the total amount of added material mixed mass fraction of 25% supported nickel catalyst heated, melted and mixed material is formed, and the out 0) 2 molar ratio of 10: 1 mixed gas introduced into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged into the mixed gas of H2 and C02 2 to the hydrogenation reactor pressure was 7 • OMPa, heating was continued to 250 C, and then open the hydrogenation reactor outlet valve 2, so that during the hydrogenation reaction produced H2S, H2 and the reaction gas remaining mixed gas C02 continuously flowing, the control amount of the mixed gas flowing into 300m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C02, H2S, and solvent vapors, but these effluents the material was expanded down the expander 3 into the gas-liquid separator 4, the gas-liquid separator 4 San temperature 50 C, pressure <0.5MPa, liquid flow San 100m3 / h, the gas flow rate <10000m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂杲7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out into the solvent Gao 7, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied H2, C〇2- entry into the compressor turbine plus 6 recycled to the hydroprocessing reactor pressure hydrogenation reaction 2, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为100m3/h,并维持加氢反应器的压力为7.010^,反应1.511后,加氢反应器2加热升温至200 C,控制反应温度保持在200C〜210C范围内,反应压力为14.0MPa〜15.0MPa,在此反应条件下反应8. Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为3_0〇 Flowing the mixed gas flow rate of about 100m3 / h, and maintain the hydrogenation reactor pressure was 7.010 ^ 1.511 After the reaction, the hydrogenation reactor 2 is heated up to 200 C, to control the reaction temperature was maintained at 200 C~210 C within the range, the reaction pressure is 14.0MPa~15.0MPa, under this reaction conditions 8. Oh, the product is obtained, C9 / C5 petroleum resin flows from the hydrogenation reactor discharge port 2 after modification, bromine number as 3_0〇

[0052] 实施例8 [0052] Example 8

[0053] 使用的反应装置与实施例1相同,将C9/C5石油树脂和环己烷按质量比4:1加入熔解釜1,加入原料总量的质量分数8%的负载钯的催化剂混合,加热,熔解,形成混合物料,将H2和C02摩尔比为6:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2 和C02混合气体至加氢反应器2内压力为5.010^,继续加热至250(:,然后打开加氢反应器2 出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出, 控制混合气体流入量为50m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C〇2、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度彡50C,压力彡0.5MPa,液体流量彡100m3/h,气体流量彡10000m3/h。溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂泵7中,打 [0053] The same reaction apparatus used in Example 1, the C9 / C5 petroleum resin and cyclohexane mass ratio 4: 1 was added a melting tank 1, the total amount of feedstock added mass fraction of a mixed catalyst of 8% of palladium, heated, melted, mixed material is formed, the C02 and H2 molar ratio of 6: 1 gas mixture into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged to a mixed gas of H2 and hydrogenated C02 the pressure in the reactor was 5.010 ^, heating was continued to 250 (:, hydrogenation reactor 2 and open the outlet valve, so that during the hydrogenation reaction to produce H2S, H2 and the remaining gas reaction gas mixture continuously flowing out of C02 controlling an amount of the mixed gas flowing 50m3 / h, into the gas-liquid separator through the expander 3 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C〇2, H2S and solvent vapors, but these outflow 3 expanded by the expander material down into the gas-liquid separator 4, the gas-liquid separator temperature of 50 C 4 San, San pressure 0.5MPa, liquid flow San 100m3 / h, the gas flow rate San 10000m3 / h. the solvent vapor was condensed separate liquid from the gas-liquid separator 4 out into the solvent pump 7, hit 系统循环使用。而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。混合气体流出的流量约为20m3/h,并维持加氢反应器的压力为5 • OMPa,反应1 • 5h后,加氢反应器2加热升温至280 C,控制反应温度保持在280C〜290C范围内,反应压力为10.OMPa〜11.OMPa,在此反应条件下反应3.0h,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为2.0〇 Recycling system, while H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied H2, entry into the turbine C〇2- the compressor 6 pressurized recycled to the hydroprocessing reactor 2 hydrogenation reaction, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. effluent flow rate of the mixed gas is about 20m3 / h, hydrogenation reactor and maintaining a pressure of 5 • OMPa, 1 • 5h after the reaction, the hydrogenation reactor 2 is heated up to 280 C, the reaction temperature is maintained at 280 C~290 C range, the reaction pressure was 10 .OMPa~11.OMPa, in this 3.0H reaction conditions, the product is obtained, C9 / C5 petroleum resin flows from the hydrogenation reactor discharge port 2 after modification, bromo value 2.0〇

[0054] 实施例9 [0054] Example 9

[0055] 使用的反应装置与实施例1相同,将C9/C5石油树脂和环己烷按质量比2:1加入熔解釜1,加入原料总量的质量分数1%的负载钯的催化剂混合,加热,熔解,形成混合物料,将H2和C02摩尔比为3:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2 和C02混合气体至加氢反应器2内压力为5.010^,继续加热至250(:,然后打开加氢反应器2 出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体112与0)2混合气体不断地流出, 控制混合气体流入量为9m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C02、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度<50C,压力<0 • 5MPa,液体流量< 100m3/h,气体流量< 10000m3/ h。 [0055] The same reaction apparatus used in Example 1, the C9 / C5 petroleum resin and cyclohexane mass ratio 2: 1 was added a melting vessel, the total amount of feedstock added mass fraction of 1% of a mixed catalyst of palladium, heated, melted, mixed material is formed, the C02 and H2 molar ratio of 3: 1 mixed gas introduced into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged to a mixed gas of H2 and hydrogenated C02 the pressure in the reactor was 5.010 ^, heating was continued to 250 (:, hydrogenation reactor 2 and open the outlet valve of H2S generated during the hydrogenation reaction, a reaction with residual gas 112 0) 2 mixed gas continuously flows out, the control amount of the mixed gas flowing 9m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C02, H2S, and solvent vapors, but these outflow 3 expanded by the expander material down into the gas-liquid separator 4, the temperature of the gas-liquid separator 4 <50 C, pressure <0 • 5MPa, liquid flow rate <100m3 / h, the gas flow rate <10000m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂泵7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out of the pump 7 into the solvent, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02 与新补充的H2、C02—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应,透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied H2, C02- entry into the compressor turbine pressurization cycle 6 back to the hydrogenation reactor 2 hydrogenation reaction, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为5m3/h,并维持加氢反应器的压力为5.OMPa,反应1 • 5h后,加氢反应器2加热升温至250C,控制反应温度保持在245C〜255C范围内,反应压力为16 .OMPa〜17. OMPa,在此反应条件下反应10. Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为1.0。 Flowing the mixed gas flow rate of about 5m3 / h, the pressure was maintained hydrogenation reactor is 5.OMPa, 1 • 5h after the reaction, the hydrogenation reactor 2 is heated up to 250 C, to control the reaction temperature was maintained at 245 C ~255 C within the range, the reaction pressure was 16 .OMPa~17. OMPa, under this reaction conditions 10. Oh, the product is obtained, C9 / C5 petroleum resin modified after discharge from the hydrogenation reactor 2 outflow port, a bromine number of 1.0.

[0056] 实施例1〇 [0056] Example 1〇

[0057] 使用的反应装置与实施例1相同,将C9/C5石油树脂和乙基环己烷按质量比10:1加入熔解釜1,加入原料总量的质量分数12%的负载钯的催化剂混合,加热,熔解,形成混合物料,将H2和C02摩尔比为20:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和C02混合气体至加氢反应器2内压力为9.0MPa,继续加热至250C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为8000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C〇2、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度<50C,压力<0 • 5MPa,液体流量< 10〇m3/h,气体流量< 10000m3/h。 [0057] The same reaction apparatus used in Example 1, the C9 / C5 petroleum resin and ethylcyclohexane mass ratio of 10: 1 was added a melting tank 1, the mass fraction of the total amount of starting material was added 12% palladium catalyst mixed, heated, melted and mixed material is formed, the molar ratio of H2 and C02 is 20: 1 mixed gas introduced into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged to a mixed gas of H2 and C02 2 is 9.0MPa pressure hydrogenation reactor, heating was continued to 250 C, and then open the hydrogenation reactor outlet valve 2, the reaction of H2S generated during the hydrogenation, the reaction with the remaining gas H2 mixed gas continuously C02 outflow, controlling inflow of the mixed gas 8000m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C〇2, H2S and solvent vapors, but these effluents the material was expanded down the expander 3 into the gas-liquid separator 4, the temperature of the gas-liquid separator 4 <50 C, pressure <0 • 5MPa, liquid flow rate <10〇m3 / h, the gas flow rate <10000m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂栗7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out into the solvent Li 7, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02与新补充的H2、C02—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied H2, C02- entry into the compressor turbine pressurization cycle 6 back to the hydrogenation reactor 2 hydrogenation reaction, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为5000m3/h,并维持加氢反应器的压力为9 • OMPa,反应1 • 5h后,加氢反应器2加热升温至280 C,控制反应温度保持在275C〜285C范围内,反应压力为10. OMPa〜11. OMPa,在此反应条件下反应6.0h,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值< 1.0。 Flowing the mixed gas flow rate of about 5000m3 / h, and maintain the pressure of the hydrogenation reactor 9 • OMPa, 1 • 5h after the reaction, the hydrogenation reactor 2 is heated up to 280 C, to control the reaction temperature was maintained at 275 C ~285 C within the range, the reaction pressure was 10. OMPa~11. OMPa, in this 6.0H reaction conditions, the product is obtained, C9 / C5 petroleum resin from the discharge port hydrogenation reactor 2 after modification outflow bromo-value <1.0.

[0058] 实施例11 [0058] Example 11

[0059] 使用的反应装置与实施例1相同,将C9/C5石油树脂和乙基环己烷按质量比4:1加入熔解釜1,加入原料总量的质量分数28 %的负载镍的催化剂混合,加热,熔解,形成混合物料,将H2和⑶2摩尔比为6:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和C02混合气体至加氢反应器2内压力为28 • OMPa,继续加热至250C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为4000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氧反应器流出的气相含有H2、C〇2、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度彡5〇C,压力彡0 • 5MPa,液体流量彡100m3/h,气体流量彡10000m3/h。 [0059] The same reaction apparatus used in Example 1, the C9 / C5 petroleum resin and ethylcyclohexane mass ratio 4: 1 was added a melting tank 1, the total amount of raw material added mass fraction of 28% supported nickel catalyst mixed, heated, melted and mixed material is formed, the molar ratio of H2 and ⑶2 6: 1 gas mixture into the hydrogenation reactor 2, and then heating to 150 C, and continuously charged to a mixed gas of H2 and C02 2 is a pressure in the hydrogenation reactor 28 • OMPa, heating was continued to 250 C, and then open the hydrogenation reactor outlet valve 2, the reaction of H2S generated during the hydrogenation, the reaction with the remaining gas H2 mixed gas continuously C02 flows out, the control amount of the mixed gas flowing 4000m3 / h, into the gas-liquid separator through the expander 3 4 throttling expansion, flows out from the gas phase reactor contains oxygen plus H2, C〇2, H2S and solvent vapors, but these flowing material was expanded down into the expander 3 gas-liquid separator 4, the temperature of the gas-liquid separator 4 San 5〇 C, a pressure San 0 • 5MPa, San liquid flow 100m3 / h, the gas flow rate San 10000m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂泵7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out of the pump 7 into the solvent, recycled back into the system to play. 而H2、C〇2、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、⑶2与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C〇2, these remaining H2S gas mixture into the absorption column 5, wherein the H2S absorption tower 5 is removed, the remaining gas H2, ⑶2 new supplemental H2, into the turbine compressor with C〇2- 6 pressurized recycled to the hydroprocessing reactor 2 hydrogenation reaction, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为3000m3/h,并维持加氢反应器的压力为28. OMPa,反应3. Oh后,加氢反应器2加热升温至330C,控制反应温度保持在325C〜335C范围内,反应压力为34MPa〜35MPa,在此反应条件下反应1. Oh,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值为3.0〇 Flowing the mixed gas flow rate of about 3000m3 / h, and maintain the pressure of the hydrogenation reactor 28. OMPa, the reaction 3. Oh, hydrogenation reactor 2 heating to 330 C, to control the reaction temperature was maintained at 325 C ~335 C within the range, the reaction pressure is 34MPa~35MPa, under this reaction conditions 1. Oh, the product is obtained, C9 / C5 petroleum resin flows from the hydrogenation reactor discharge port 2 after modification, bromine value 3.0〇

[0060] 实施例12 [0060] Example 12

[0061] 使用的反应装置与实施例1相同,将C9/C5石油树脂和乙基环己烷按质量比2:1力口入熔解釜1,加入原料总量的质量分数9%的负载钯的催化剂混合,加热,熔解,形成混合物料,将H2和⑶2摩尔比为6:1混合气体通入加氢反应器内2,然后加热升温至150C,并不断的充入H2和C02混合气体至加氢反应器2内压力为5 .OMPa,继续加热至250 C,然后打开加氢反应器2出气口阀门,使加氢反应过程中产生的H2S,反应剩余的气体H2与C02混合气体不断地流出,控制混合气体流入量为6000m3/h,经膨胀机3节流膨胀后进入气液分离器4,从加氢反应器流出的气相含有H2、C02、H2S和溶剂蒸汽,但是这些流出的物质经膨胀机3膨胀降压进入气液分离器4,气液分离器4的温度彡50C,压力<0 • 5MPa,液体流量彡100m3/h,气体流量彡10000m3/h。 [0061] The reaction apparatus identical to that used in Example 1, the C9 / C5 petroleum resin and ethylcyclohexane mass ratio of 2: 1 into the melting tank 1 opening force, the total amount of the raw material mass fraction of 9% palladium the catalyst mixture is heated, melted and mixed material is formed, the molar ratio of H2 and ⑶2 6: 1 gas mixture into the hydrogenation reactor 2, and then heating to 150 C, and charged with H2 and constantly mixed C02 gas to the hydrogenation reactor 2 inner pressure of 5 .OMPa, heating was continued to 250 C, and then open the hydrogenation reactor outlet valve 2, the reaction of H2S generated during the hydrogenation, the reaction with the remaining gas mixture H2 C02 gas constantly flows, the control amount of the mixed gas flowing 6000m3 / h, through the expander 3 into the gas-liquid separator 4 throttling expansion, from the gas phase hydrogenation reactor effluent containing H2, C02, H2S, and solvent vapors, but these flowing material was expanded down into the expander 3 gas-liquid separator 4, the gas-liquid separator temperature of 50 C 4 San pressure <0 • 5MPa, San liquid flow 100m3 / h, the gas flow rate San 10000m3 / h. 溶剂蒸汽冷凝为液态从气液分离器4分离出来,进入溶剂栗7中,打回系统循环使用。 The solvent vapor is condensed to a liquid separated from the gas-liquid separator 4 out into the solvent Li 7, recycled back into the system to play. 而H2、C02、H2S这些余下的混合气相进入吸收塔5中,其中H2S被吸收塔5脱除,余下的气相H2、C02与新补充的H2、C〇2—同进入透平压缩机6加压循环回加氢反应器2进行加氢反应, 透平机6进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。 And H2, C02, H2S these remaining mixed gas into the absorber 5, wherein H2S absorption tower 5 is removed, the remaining gas H2, C02 and newly supplied H2, C〇2- entry into the compressor turbine plus 6 recycled to the hydroprocessing reactor pressure hydrogenation reaction 2, the turbine work is carried out 6 the expander turbine 3 driven expansion work pressure compressor 6. 混合气体流出的流量约为5000m3/h,并维持加氢反应器的压力为5 • OMPa,反应1 • 5h后,加氢反应器2加热升温至370 C,控制反应温度保持在375C〜385C范围内,反应压力为10. OMPa〜11. OMPa,在此反应条件下反应3.0h,即得产品,改性后的C9/C5石油树脂从加氢反应器2的出料口流出,溴值< 1.0。 Flowing the mixed gas flow rate of about 5000m3 / h, and maintain the hydrogenation reactor pressure was 5 • OMPa, reaction 1 • 5h, the hydrogenation reactor is heated up to 2 370 C, to control the reaction temperature was maintained at 375 C ~385 C within the range, the reaction pressure was 10. OMPa~11. OMPa, in this 3.0H reaction conditions, the product is obtained, C9 / C5 petroleum resin from the discharge port hydrogenation reactor 2 after modification outflow bromo-value <1.0.

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Classifications
International ClassificationB01J8/00, C08F8/04, C08F4/80, C08F240/00, C08F2/01
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