Petroleum resin hydrotreating method

Abstract

The invention provides a petroleum resin hydrotreating method. The method comprises the following steps that (1) dissolved petroleum resin raw materials enter a first section hydrofining reactor where catalysts are loaded in a staged mode, a reaction is carried out under the conditions that the reaction pressure is 8-17.0 MPa, the reaction temperature is 230-270 DEG C, the air speed is 0.3-0.7 h<-1>, and the hydrogen / oil ratio is 300-800 v / v, the topmost portion of the first section hydrofining reactor is filled with a protecting agent, a main catalyst is a non-noble metal sulfide state supporting catalyst, and the bottom of the first section hydrofining reactor is filled with a sweetening catalyst; (2) after first section reaction products are washed with water and subjected to gas-liquid separation, liquid substances are sent into a stripping tower to be subjected to steam stripping, and hydrogen sulfide is further removed; (3) the liquid substances subjected to steam stripping enter a second section hydrogenation and dearomatization reactor and make contact with a supporting type Ni catalyst, and a reaction is carried out under the conditions that the reaction pressure is 4-10.0 MPa, the reaction temperature is 230-260 DEG C, the air speed is 0.5-0.7 h<-1>, and the hydrogen / oil ratio is 300-800 v / v; and (4) after reaction products obtained in the second section hydrogenation and dearomatization reactor are subjected to gas-liquid separation, solvent and petroleum resin products are separated, and the solvent is reused after being recycled. According to the method, the operation cost is low, and the yield of high-value products is high.

Description

technical field [0001] The invention relates to a petroleum resin hydrogenation treatment method. Background technique [0002] Because the petroleum resin production process contains halogen sulfur elements in the raw materials, a certain amount of unsaturated double bonds will remain after the polymerization reaction, etc., the crude resin is easy to undergo oxidation and substitution reactions with other compounds, which affects the oxidation resistance and thermal stability of petroleum resins. It has a greater impact, and its compatibility with some organic solvents is correspondingly reduced, which greatly limits its application in related fields. Hydrofining is a treatment method to improve the color and light and heat stability of the resin. Under the action of a catalyst, the unsaturated aromatic ring in the resin can be saturated after hydrogenation modification, and the residual sulfur and halogen can be removed. The resin The color becomes colorless and transpar...

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Problems solved by technology

[0026] 2. The polymer molecules stretch on the surface of the catalyst (chain and ring structure), forming a high steric hindrance, which makes it difficult for the raw material molecules to reach the surface of the inner pores of the catalyst for catalytic hydrogenation reaction. The catalytic hydrogenation reaction mainly depends on the catalyst The active center on the outer surface, so when using the noble metal-supported catalyst with the highest activity of unsaturated bond hydrogenation, even if the active noble metal content is as high as 0.5-2.0%, the price of the catalyst is high, but its hydrogenation activity is not ideal, compared to distillate In the application of oil hydrofinishing, the reaction activity of catalysts such as olefin saturation and benzene ring hydrogenation in the process of resin hydrofinishing is relatively low, which is also the main consideration for the research and development of powder bulk catalyst slurry bed hydrogenation technology

[0027] 3. Petroleum resin contains halides (fluorine, chlorine, bromine, etc.), sulfur, nitrogen, phosphorus, silicon, metal ions (Na, Ma, Al, Si, P, K, Ca, Mn, Ni, Fe, Zn, Cd, Se, etc.) and colloids, gels, in addition, the C9 fraction will also produce some thiadenes and their derivatives during the polymerization process, noble metal (Pt, Pd) catalysts are good for these substances Extremely sensitive, easily poisoned, deactivated by coking

[0035] For example: the effect of thiophene on the Pt / KL hexane aromatization catalyst, the sulfur concentration is in the range of 50-200ppb, and the sulfur accelerates the aggregation and growth of Pt at the pore position of the molecular sieve, while the electronic characteristics of the metal position have not changed; 4. γ-Al in Hydrogenation of Hydronaphthalene 2 o 3 In the case of sulfur poisoning of supported Pt catalysts, it was found that the adsorption of sulfur can lead to the formation of surface sulfide or bulk sulfide, and the sulfur adsorbed on the metal-support interface can reduce the interaction between the metal and the support and lead to the aggregation of metal particles. The sulfur adsorbed on the metal site is easy to form platinum sulfide with strong fluidity and no catalytic activity, which leads to catalyst deactivation due to two reasons.

[0036] In addition, due to its special structure, petroleum resin will undergo resin degradation reaction when the temperature rises (usually higher than 260°C). Once the resin degradation occurs, the resin yield will decrease, the softening point will decrease, and the economy will become worse Difference

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