阅读说明：本技术 一种硫化态加氢催化剂的后处理方法 (Post-treatment method of sulfurized hydrogenation catalyst ) 是由 李景锋 向永生 王高峰 柏介军 姚文君 张永泽 高海波 常晓昕 谢元 边虎 王书 于 2019-11-28 设计创作，主要内容包括：本发明涉及一种硫化态加氢催化剂后处理方法。按照工业白油与车用柴油的质量比为9:1-1:9的比例混合配置特定馏分油,向硫化态加氢催化剂浸渍含有芳烃、正构烷烃、异构烷烃等多种组分的特定馏分油,后除去易挥发轻组分。本发明方法使硫化态加氢催化剂的内外表面形成包覆层,该包覆层与催化剂内外表面的粘附力强、可完全溶解于汽油中,同时实现了硫化态加氢催化剂在包装、运输、装填过程中无安全风险及其在开工初期加氢活性不降低的目标。(The invention relates to a post-treatment method of a sulfurized hydrogenation catalyst. Mixing industrial white oil and vehicle diesel oil according to the mass ratio of 9:1-1:9 to prepare specific distillate oil, impregnating the specific distillate oil containing various components of aromatic hydrocarbon, normal paraffin, isoparaffin and the like into a sulfurized hydrogenation catalyst, and then removing volatile light components. The method of the invention forms a coating layer on the inner and outer surfaces of the hydrogenation catalyst in a sulfurized state, the coating layer has strong adhesive force with the inner and outer surfaces of the catalyst, and can be completely dissolved in gasoline, and simultaneously, the purposes of no safety risk and no reduction of hydrogenation activity in the initial start-up period of the hydrogenation catalyst in a sulfurized state in the processes of packaging, transporting and filling are realized.)

1. A post-treatment method of a sulfurized hydrogenation catalyst is characterized in that specific distillate oil is impregnated into the sulfurized hydrogenation catalyst, volatile light components are removed after impregnation is completed, and the specific distillate oil mainly contains aromatic hydrocarbon, normal paraffin and isoparaffin.

2. The method for post-treating a sulfurized hydrogenation catalyst as defined in claim 1, wherein the specific distillate is obtained by mixing industrial white oil and diesel oil for vehicles in a mass ratio of 9:1 to 1: 9.

3. The method as claimed in claim 1, wherein the specific distillate has an average molecular weight of 200-450g/mol, a density of 0.800-0.900g/mL, a carbon number distribution of C16-C31, and a kinematic viscosity at 40 ℃ of 6.1-16.5m²And/s, the opening flash point is 135-160 ℃, and the water-soluble acid-base composite material does not contain moisture, mechanical impurities and water.

4. The method of claim 1, wherein the impregnation temperature is in the range of 40 to 200 ℃.

5. The method of claim 1, wherein the impregnation is an equal volume impregnation or an excess impregnation.

6. The method for post-treating a sulfurized catalyst as defined in claim 1, wherein the volatile light components are removed by flash evaporation at 60-300 deg.C under normal pressure or vacuum for 0.5-5.0 hr.

7. The post-treatment method of the sulfurized hydrogenation catalyst as claimed in claim 1, wherein the sulfurized hydrogenation catalyst is supported, the carrier is one or more of alumina, silica, titania and molecular sieve, and the active phase is Co, Ni-Mo or W-S.

8. The method of claim 1, wherein the amount of Co or Ni is 0.2-20.0 wt% and the amount of Mo or W is 0.3-30.0 wt% based on the total weight of the catalyst.

Technical Field

The invention relates to a post-treatment method of a hydrogenation catalyst.

Background

With the development of crude oil towards heaviness and deterioration, the quality standard of clean oil products is increasingly strict, the demand of refineries on hydrogenation technology is continuously increased, and the core of the hydrogenation technology is a hydrogenation catalyst. The hydrogenation catalyst generally consists of oxides with Co (Ni) -Mo (W) metals as active components, and in order to obtain higher hydrogenation activity, selectivity and stability, the non-noble metal oxidation state catalyst must be vulcanized before use. Therefore, the sulfiding effect of such catalysts becomes the key to the development of the optimal hydrogenation activity, selectivity and stability of the catalyst.

The sulfidation technology of hydrogenation catalysts can be divided into in-situ sulfidation technology and out-of-situ sulfidation technology according to the place where sulfidation reaction is performed. The in-reactor vulcanization technology is the traditional vulcanization technology of hydrogenation catalysts, namely, firstly, an oxidation state hydrogenation catalyst is loaded into a hydrogenation reactor, and then hydrogen and a vulcanizing agent are introduced into the reactor in the temperature rising process.

The in-situ sulfurization technology uses oxidation state catalyst with stable property, so that the catalyst is very safe in the processes of packaging, transporting and filling, but has the following disadvantages: firstly, the catalyst has long vulcanization time and high energy consumption and labor cost for start-up; secondly, the refinery needs to set up vulcanizing equipment to store inflammable, toxic and harmful vulcanizing agents; and thirdly, high-concentration hydrogen sulfide generated in the vulcanizing process of the vulcanizing agent is easy to cause corrosion of a high-pressure reactor and related equipment, and potential safety hazards of harm to the environment and personnel exist.

Aiming at the defects of the in-vitro vulcanization technology, scientific researchers provide an out-of-vitro vulcanization technology. The degree of vulcanization in the ex-situ vulcanization technique can be divided into two ways. One of the methods is ex-situ presulfurization (sulfur loading), i.e. under the condition of inert atmosphere and low temperature, firstly introducing the vulcanizing agent into the pore channel of oxidation state hydrogenation catalyst by adopting sublimation, melting or impregnation method, then under the inert atmosphere making the catalyst be partially vulcanized by means of heating treatment, after cooling, loading the partially vulcanized catalyst into hydrogenation reactor, under the condition of heating and in the presence of hydrogen gas making the complete vulcanization of catalyst be completed. For example, CN103406132B discloses a preparation method of a sulfur-supported hydrogenation catalyst, which comprises the following specific preparation steps: mixing the sulfurized olefin oil, elemental sulfur and the vulcanization accelerator to obtain a uniform mixed sulfurized oil with a total sulfur concentration of 18-30%; under the conditions that the pressure is normal pressure or negative pressure and the temperature is 30-60 ℃, the mixed sulfurized oil agent is sprayed and soaked in the hydrogenation catalyst and is mixed for 40-50 minutes; and drying the soaked and mixed hydrogenation catalyst under the condition of sealing and isolating air (or nitrogen atmosphere) to form the catalyst wrapped by thin-layer carbon deposition, thus preparing the sulfur-carrying hydrogenation catalyst. When the catalyst is used in a refinery, the refinery does not need to set up a vulcanizing device for storing flammable, toxic and harmful vulcanizing agents, but still needs a longer activation process. The other mode is complete vulcanization outside the device, namely hydrogen sulfide or easily decomposed organic sulfide is adopted on a vulcanization device and is subjected to certain temperature, pressure and airComplete the full vulcanization of the catalyst in the speed range. Compared with the in-situ vulcanization and the in-situ prevulcanization, the advantage that the out-situ complete vulcanization is carried out in the work starting of the refinery is as follows: the catalyst does not need to be vulcanized, the start-up time is greatly shortened, and the energy consumption and the labor cost for start-up are low. However, the catalyst in an off-site fully sulfided state is unstable when exposed to air and encounters O₂Will generate SO₂And heat, which tends to self-heat or burn below 200 ℃.

For this reason, researchers have proposed techniques for passivating catalysts in an ex-situ fully sulfided state. Existing passivation techniques generally fall into two broad categories: chemical passivation techniques and physical passivation techniques. The chemical passivation technology takes oxygen-containing gas or oxygen-containing liquid as a passivating agent to enable the surface of the metal sulfide of the sulfide catalyst to generate passivation reaction so as to form a metal oxide thin layer. For example, CN1602999A discloses a method for the ex-situ pretreatment of hydrogenation catalysts. The method comprises the following steps: (1) ex-situ gas phase presulfiding of hydrogenation catalyst in oxidation state: adding an oxidation-state hydrogenation catalyst into a vulcanization reactor, and introducing a vulcanization gas into the vulcanization reactor to perform a vulcanization reaction; (2) gas-phase passivation treatment of a sulfided catalyst: and (2) adding the catalyst vulcanized in the step (1) into a passivation reactor, and passivating the vulcanized catalyst by using passivated gas containing oxygen. CN1768952A discloses a method for treating an ex-situ sulfided hydrogenation catalyst, which comprises the steps of filling the sulfided hydrogenation catalyst into a container with deoxygenated water, and completely immersing the sulfided hydrogenation catalyst in the water for sealed storage for later use. CN102284299A provides a method for presulfiding a hydrogenation catalyst outside a hydrogenation reactor-activating inside the hydrogenation reactor, which comprises the following steps: (1) pre-sulfurizing the catalyst outside the hydrogenation reactor; (2) passivating the catalyst; (3) and (4) reactivation of the catalyst. Patents CN1602999A, CN1768952A and CN102284299A all show that chemical passivation technology reduces the sulfur holding rate and activity of the catalyst to different degrees, so that the catalyst needs to be activated twice to reach the highest activity when in use. Journal article "research on liquid passivation process of presulfurization hydrogenation catalyst [ J ]. haifeng, dongfang, yangchun, chemical technology, 2008,16(4): 29-32." passivating the presulfurization hydrogenation catalyst by using liquid oxygen-containing hydrocarbon, and examining the influence of the usage amount of oxygen-containing hydrocarbon, passivation temperature, passivation time and content of unsaturated hydrocarbon on the passivation effect of the hydrogenation catalyst; the method comprises the following steps of taking catalytic diesel as a raw material, evaluating the activity of a catalyst before and after passivation by using a fixed bed continuous micro-reactor, and evaluating the self-heating maximum temperature of the passivated catalyst by using an ONU self-heating test device to determine the optimal passivation process condition, wherein the experiment result shows that the process of passivating a pre-vulcanized hydrogenation catalyst by using oxygenated hydrocarbon is feasible, and the optimal passivation process condition is that the using amount of the oxygenated hydrocarbon accounts for 40% of the pore volume of the catalyst; the passivation time is 10 min; the passivation temperature is 40 ℃; the unsaturated hydrocarbon content was 100%.

The physical passivation technique is to preheat the catalyst in a sulfurized state to a temperature above the melting point of the special inert material, and then to coat a protective layer made of the special inert material on the outer surface of the preheated catalyst. For example, US 49563222 isolates the outer surface of the sulphidic catalyst from air by coating it with a removable protective film comprising a linear alkane and a paraffin wax. However, the protective film coated by the technology is easy to fall off, so that the vulcanized catalyst has safety risks in the processes of packaging, transporting and filling.

Disclosure of Invention

The invention provides a post-treatment method of a sulfurized hydrogenation catalyst, aiming at the problems that the existing sulfurized hydrogenation catalyst physical passivation technology has safety risks and the chemical passivation technology needs secondary activation of the catalyst.

The carrier of the hydrogenation catalyst is one or a compound of more of alumina, silicon oxide, titanium oxide, molecular sieve and the like; the metal active phase of the catalyst is Co (Ni) -Mo (W) -S.

The hydrogenation catalyst comprises the following metals in percentage by weight calculated as oxides in the catalyst, based on the total weight of the catalyst: co₂O₃(NiO)0.2-20.0wt％；MoO₃(WO₃)0.3-30.0wt％。

The post-treatment method of the sulfurized hydrogenation catalyst provided by the invention comprises the following main steps:

(1) firstly, soaking specific distillate oil containing a plurality of components such as aromatic hydrocarbon, normal paraffin, isoparaffin and the like into a sulfuration state hydrogenation catalyst;

(2) then removing volatile light components through flash evaporation, and forming coating layers on the inner surface and the outer surface of the vulcanized hydrogenation catalyst.

The inner and outer surface coating layers of the catalyst contain a plurality of components such as aromatic hydrocarbon, normal alkane, isoparaffin and the like, have strong adhesion with the inner and outer surfaces of the catalyst, do not fall off in the processes of packaging, transporting and filling the catalyst, and avoid the safety risk of the existing physical passivation technology; meanwhile, the inner surface coating layer and the outer surface coating layer of the catalyst can be completely dissolved in gasoline, active sites can be completely released in the subsequent start-up process of the catalyst, the problem that the chemical passivation technology needs secondary activation of the catalyst is solved, and the start-up period of the device can be effectively shortened.

The specific distillate oil used in the invention needs to be prepared before use, and the preparation method is to mix the industrial white oil and the vehicle diesel oil according to the mass ratio of 9:1-1: 9.

The average molecular weight of the specific distillate used in the invention is 200-450 g/mol.

The density of the specific distillate oil used in the invention is 0.800-0.900 g/mL.

The carbon number distribution of the specific distillate oil used in the invention is C16-C31.

The kinematic viscosity (40 ℃) of the specific distillate oil used in the invention is 1.0-40.0m²/s。

The flash point (opening) of the specific distillate oil used in the invention is 60-170 ℃.

The special distillate oil used in the invention contains no moisture, mechanical impurities and water-soluble acid and alkali.

The impregnation temperature of the sulfurized hydrogenation catalyst and the specific distillate oil is 40-200 ℃.

The impregnation atmosphere of the sulfurized hydrogenation catalyst and the specific distillate oil is inert gases such as nitrogen, helium, argon and the like.

The impregnation mode of the sulfurized hydrogenation catalyst and the specific distillate oil can be equal-volume impregnation or excessive impregnation.

The flash evaporation temperature of the sulfuration state hydrogenation catalyst and the specific distillate oil is 60-300 ℃.

The flash pressure of the sulfurized hydrogenation catalyst and the specific distillate oil is normal pressure or vacuum.

The flash evaporation time of the sulfurized hydrogenation catalyst and the specific distillate oil is 0.5-5.0 h.

Compared with the prior art, the post-treatment method of the sulfurized hydrogenation catalyst provided by the invention has the following characteristics:

(1) the invention adopts a physical passivation method, adopts self-made non-oxygen-containing hydrocarbon containing various components such as aromatic hydrocarbon, normal paraffin, isoparaffin and the like as specific distillate oil, and the specific distillate oil and the catalyst active phase do not generate oxidation reaction;

(2) carrying out post-treatment on the vulcanized hydrogenation catalyst in a flash evaporation mode after dipping specific distillate oil to form a coating layer on the inner surface and the outer surface of the vulcanized hydrogenation catalyst;

(3) the coating layer contains a plurality of components such as aromatic hydrocarbon, normal paraffin, isoparaffin and the like, has strong adhesive force with the inner surface and the outer surface of the catalyst, and does not fall off in the process of packaging, transporting and filling the catalyst;

(4) the coating layer can be completely dissolved in gasoline, and active sites can be completely released in the subsequent start-up process of the catalyst.

(5) Compared with the existing physical passivation method, the physical passivation method of the invention has the advantages that the treated vulcanized catalyst does not fall off in the processes of packaging, transporting and filling, thereby avoiding the safety risk of the existing physical passivation technology; and meanwhile, the internal and external surface coating layers of the treated sulfurized catalyst can be completely dissolved in gasoline, and active sites of the sulfurized catalyst can be completely released in the subsequent start-up process.

Detailed Description

The method of working up a sulfided hydrogenation catalyst of the present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

Example 1

This example prepares the oxidation state protecting agent GDS-10 for FCC gasoline hydro-upgrading andthe treated sulfuration state protective agent GDS-10(S) comprises 3.5 wt% of NiO and MoO based on the weight of the catalyst₃5.1 wt% and 91.4 wt% mesoporous alumina.

580g of pseudo-boehmite powder HC-07 (produced by Shandong Xingdu chemical Co., Ltd., alumina with water loss of about 30 wt%) and 32.5g of sesbania powder are weighed and mixed uniformly, 16.9g of concentrated nitric acid (65 wt%) and 490g of deionized water are added, after full mixing and kneading, the mixture is extruded into a clover strip with the length of 3.0mm in an extruding machine, and the clover strip is dried at the temperature of 120 ℃ for about 4 hours, roasted at the temperature of 550 ℃ for about 4 hours, cooled and sieved to prepare the GDS-10 carrier with the length of 3-10 mm. According to the water absorption rate of the carrier, the content of molybdenum of a target catalyst and the amount of the used carrier, impregnation liquid containing 54.5g of hydrated nickel nitrate, 11.9g of ammonium heptamolybdate and 140g of strong ammonia water is prepared, the impregnation liquid is impregnated on 400g of the carrier, and after aging for about 8 hours at room temperature, drying for about 4 hours at 120 ℃ and roasting for about 4 hours at 520 ℃, the oxidation state protective agent GDS-10 for the hydrogenation modification of FCC gasoline is obtained.

Then the protective agent GDS-10 is placed in a fixed bed reactor, dimethyl disulfide is taken as a vulcanizing agent, the vulcanizing pressure is 0.34-36MPa, the vulcanizing temperature is 220-14 ℃, the vulcanizing time is 12-14h, the hydrogen purity is 14-16 v%, and the vulcanizing airspeed can be 250-350h^-1The vulcanization space velocity is 290-^-1Under the conditions of (1), vulcanization is carried out.

After the vulcanization is finished, firstly placing the vulcanized GDS-10 in a rotary dipping pot, preparing specific distillate oil according to the mass ratio of 7:3 of the industrial white oil to the vehicle diesel oil, and under certain conditions (nitrogen atmosphere, normal pressure and 80 ℃), adding the specific distillate oil (with the average molecular weight of 300g/mol, the carbon number distribution of C18-C25 and the kinematic viscosity (40 ℃) of 9.0m²(s) the open flash point is 145 ℃), and impregnating the catalyst on the vulcanized GDS-10 catalyst in an equal-volume impregnation mode; then, the mixture is flashed for 1.0h under the conditions of normal pressure and 150 ℃ to obtain the treated sulfurized state protective agent GDS-10(S) for the hydro-upgrading of FCC gasoline.

Example 2

This example prepares an oxidized form of pre-hydrogenation catalyst GDS-22 for use in the hydro-upgrading of FCC gasoline and a treated sulfided form of pre-hydrogenation catalyst GDS-22(S) based on the weight of the catalyst，NiO11.6wt％，MoO₃7.5 wt%, 80.9 wt% alumina. The procedure was the same as in example 1, except for the amount of the supported catalyst.

Example 3

This example prepares an oxidation state selective hydrogenation catalyst GDS-32 for FCC gasoline hydro-upgrading and its treated sulfided GDS-32(S), based on the weight of the catalyst, Co₂O₃ 3.2wt％，MoO₃12.0 wt% and 84.8 wt% of mesoporous-macroporous alumina.

Weighing 600g of pseudo-boehmite powder HC-07 (produced by Shandong Xingdu chemical Co., Ltd., alumina with water loss of about 30 wt%), 34.0g of sesbania powder and 12.0g of pore-expanding agent, uniformly mixing, adding 17.5g of concentrated nitric acid (65 wt%) and 500g of deionized water, fully kneading, extruding into 2.6mm clover strips in a strip extruder, drying at 120 ℃ for about 5 hours, roasting at 660 ℃ for about 6 hours, cooling and screening to prepare the GDS-32 carrier with the length of 3-10 mm.

According to the water absorption of the carrier, the content of molybdenum of the target catalyst and the amount of the used carrier, an impregnation solution containing 52.9g of cobalt acetate, 28.0g of ammonium heptamolybdate and 130g of strong ammonia water is prepared, the impregnation solution is impregnated on 400g of the carrier, and after aging for about 8 hours at room temperature, drying for about 4 hours at 120 ℃ and roasting for about 4 hours at 520 ℃, the oxidation state pre-hydrogenation catalyst GDS-32 for FCC gasoline hydrogenation modification is obtained.

Then, after the vulcanization according to the same procedure as in example 1, the vulcanized GDS-32 was placed in a dipping pot equipped with a stirrer, and specific distillate oil was prepared according to the mass ratio of the industrial white oil to the vehicle diesel oil of 8:2, and under certain conditions (helium atmosphere, -0.01MPa, 85 ℃), specific distillate oil (average molecular weight 310g/mol, carbon number distribution C19-C26, kinematic viscosity (40 ℃) 9.5m²(ii)/s, open flash point 150 ℃), impregnating onto the sulfided GDS-32 catalyst in an excess impregnation mode; then, after flash evaporation is carried out for 0.5h under the conditions that the pressure is minus 0.01MPa and the temperature is 160 ℃, the treated sulfuration state pre-hydrogenation catalyst GDS-32(S) for FCC gasoline hydrogenation modification is obtained.

Example 4

This example prepares FCC gasoline selective hydrogenation catalysts GDS-42 and GDS42(S), by weight of the catalyst, Co₂O₃ 1.5wt％，MoO₃4.2 wt%, 67.4 wt% of mesoporous alumina and 26.9 wt% of mesoporous ZSM-5 molecular sieve.

Weighing 375g of pseudo-boehmite powder HC-07 (produced by Shandong Xingdu chemical Co., Ltd., prepared alumina with water loss of about 30 wt%) and 81.5g of sesbania powder (produced by Zhongshi Dabeijing Green Co., dry basis of about 95 wt%), mixing uniformly, adding 43.6g of concentrated nitric acid (65 wt%) and 320g of deionized water, fully kneading, extruding into 1.7mm clover strips in a strip extruder, drying at 120 ℃ for about 5 hours, roasting at 520 ℃ for about 4 hours, cooling and screening to prepare the GDS-42 carrier with the length of 3-10 mm.

According to the water absorption rate of the carrier, the content of molybdenum of the target catalyst and the amount of the used carrier, an impregnation solution containing 52.9g of cobalt acetate, 28.0g of ammonium heptamolybdate and 130g of strong ammonia water is prepared, the impregnation solution is impregnated on 400g of the carrier, and after aging for about 8 hours at room temperature, drying for about 4 hours at 120 ℃ and roasting for about 4 hours at 520 ℃, GDS-42 is obtained.

According to the water absorption of the carrier, the molybdenum content of the target catalyst and the amount of the used carrier, an impregnation solution containing 27.0g of ammonium heptamolybdate and 80g of strong ammonia water is prepared, the impregnation solution is impregnated on 400g of the carrier, and after aging for about 8 hours at room temperature, drying for about 4 hours at 120 ℃ and roasting for about 4 hours at 520 ℃, a GDS-42 primary impregnation product is obtained. According to the water absorption rate of the GDS-42 primary extract, impregnation liquid containing 29.2g of cobalt nitrate and 8.0g of ammonium nitrate is impregnated on the GDS-42 primary extract, and after aging for about 7 hours at room temperature, drying for about 5 hours at 120 ℃ and roasting for about 5 hours at 520 ℃, the oxidation state selective hydrodesulfurization catalyst GDS-42 for FCC gasoline hydro-upgrading is obtained.

Then, after the vulcanization according to the same procedure as in example 1, the vulcanized GDS-42 was placed in a dipping pot equipped with a stirrer, and specific distillate oil was prepared according to the mass ratio of the industrial white oil to the vehicle diesel oil of 9:1, and under certain conditions (helium atmosphere, -0.02MPa, 90 ℃), specific distillate oil (average molecular weight 320g/mol, carbon number distribution C19-C27, kinematic viscosity (40 ℃) 10.0m²The open flash point is 155 ℃) and is impregnated on the vulcanized GDS-42 catalyst in an equal-volume impregnation mode; then, at a pressure of-0And carrying out flash evaporation for 0.6h under the conditions of 02MPa and 163 ℃ to obtain the treated sulfide state selective hydrodesulfurization catalyst GDS-42(S) for FCC gasoline hydrogenation modification.

Comparative example 1

In the comparative example, the GDS-10/22/32/42 series FCC gasoline hydro-upgrading catalysts are taken as examples, and the performance of the post-treated off-site sulfurized state hydrogenation catalyst and the performance of the in-site sulfurized state hydrogenation catalyst are compared and evaluated.

Test part:

(1) testing device

The treated catalyst GDS-10(S)/22(S) vulcanized outside the reactor and the catalyst GDS-10/22 vulcanized inside the reactor, the treated catalyst GDS-10(S)/32(S) vulcanized outside the reactor and the catalyst GDS-10/32 vulcanized inside the reactor are all filled in an up-and-down composite mode, a 200mL isothermal bed evaluation device is adopted for evaluation, the filling height-diameter ratio of the reactor is 38, and the temperature difference between the inside and the outside of the reactor is controlled to be +/-0.5 ℃; the treated catalyst GDS-42(S) vulcanized outside the reactor and the catalyst GDS-42 vulcanized inside the reactor adopt a 250mL adiabatic bed evaluation device, the ratio of the filling height to diameter of the reactor is 46, and the temperature difference between the inside and the outside of the reactor is controlled to be +/-0.5 ℃. The hydrogen is controlled by a gas mass flow meter, and a one-time passing mode is adopted, wherein the temperature control precision is +/-1 ℃, and the oil mass control precision is +/-5 g. During the catalyst process evaluation, samples were taken every 24 hours to analyze the sulfur content and mercaptan content of the instantaneous hydrogenation product. Uses the Hu petrochemical FCC full-distillate gasoline and the pre-hydrogenated heavy gasoline as raw materials, and the properties of the gasoline are respectively shown in the table 1 and the table 2.

(2) Raw oil properties and sources

FCC gasoline FCC full-fraction gasoline from China Binhaote petrochemical company and pre-hydrogenated heavy gasoline are used as raw materials, and the properties of the raw materials are respectively shown in tables 1 and 2.

TABLE 1 FCC FULL-FRACTION GASOLINE PROPERTIES

TABLE 2 Hupetrochemical prehydrogenation FCC gasoline heavy component Properties Table

Evaluation results were as follows:

(1) GDS-22 and GDS-22(S) performance comparative evaluation

The process conditions are as follows: the inlet temperature is 105 ℃, the pressure is 1.8MPa, and the space velocity is 2.6h^-1And the hydrogen-oil ratio is 5-7. The evaluation results are shown in table 3. As can be seen from Table 3, the performance of GDS-22 is comparable to that of GDS-22(S) under the same process conditions.

TABLE 3 GDS-22 and GDS-22(S) comparative evaluation of Activity data after 516 hours

(2) Evaluation of GDS-32/42 in tandem comparison with GDS-32(S)/42(S)

The process conditions are as follows: the inlet temperature of the first reaction and the second reaction is 260 ℃, the inlet pressure of the first reaction and the second reaction is 1.8MPa, and the space velocities of the first reaction and the second reaction are 2.6 and 1.5h respectively^-1The hydrogen-oil ratio of the first reaction and the second reaction is 400: 1. The evaluation results are shown in Table 4. As can be seen from the data in Table 4, the performance of GDS-32/42 is comparable to that of GDS-32(S)/42(S) under the same process conditions.

TABLE 4 GDS-32/42 Activity data after 516 hours in tandem comparison with GDS-32(S)/42(S)

(3) Comparison of blended product Properties

Table 5 is comparative data comparing properties of blended products evaluated in series. From table 5, it can be seen that the overall performance of the post-treated ex-situ sulfided hydrogenation catalyst is comparable to that of the in-situ sulfided catalyst under the same process conditions.

Table 5 comparative series evaluation of blend product Properties

The comparative evaluation results show that under the same evaluation conditions, the catalytic performance of the post-processor external sulfurized state hydrogenation catalyst is equivalent to that of the traditional in-processor sulfurized state catalyst, which indicates that the post-processor external sulfurized state hydrogenation catalyst is not oxidized in the processes of packaging, transporting and filling, and the active sites of the post-processor external sulfurized state hydrogenation catalyst can be completely released.

Comparative example 2

Firstly, two kinds of distillate oil with different properties are adopted to carry out aftertreatment on the FCC gasoline hydro-upgrading catalyst of GDS-10(S)/22(S)/32(S)/42(S) series, and then the series comparative evaluation is carried out on the treated catalyst by adopting the same procedure as that of the comparative example 2.

The property data for the two different distillates are shown in table 6 below. As can be seen from Table 1, the average molecular weight, density, carbon number distribution, kinematic viscosity and open flash point of distillate 2 are all within the control indexes, while the average molecular weight, density, carbon number distribution, kinematic viscosity and open flash point of distillate 2 are all higher than the control indexes. The series of catalysts obtained after the treatment of distillate 1 and distillate 2 are respectively counted as a series of catalysts 1 and a series of catalysts 2. Comparative series evaluation of series catalyst 1 and series catalyst 2 reconciled product properties are shown in table 7 below. As can be seen from table 7, the desulfurization activity and olefin aromatization activity of the series catalyst 1 are both higher than those of the series catalyst 2, which indicates that the properties of the distillate oil used have a significant influence on the performance of the treated sulfided hydrogenation catalyst.

Table 6 property data of two different distillates

Table 7 comparative series evaluation of series catalyst 1 and series catalyst 2 blend product properties