CN109679683B - Method for measuring activity of desulfurization adsorbent - Google Patents
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Abstract
本发明涉及一种脱硫吸附剂活性测量方法，该方法包括：a、将待测脱硫吸附剂进行再生处理；b、将重量为Mc的步骤a中所得再生吸附剂进行还原处理；c、将步骤b中所得还原吸附剂与连续进料的含噻吩类化合物的烃油原料接触并在临氢条件下进行脱硫吸附反应，至多得到重量为Mo脱硫产物；d、采用公式(1)计算单位重量的待测脱硫吸附剂的脱硫活性It，公式(1)为：e、将新鲜脱硫吸附剂进行步骤b‑d的处理，得到新鲜脱硫吸附剂的脱硫活性If；f、采用公式(2)计算待测脱硫吸附剂的相对脱硫活性指数，公式(2)为：
本发明方法简单易行，能够快速和准确地对吸附剂的活性进行测定。The invention relates to a method for measuring the activity of a desulfurization adsorbent. The method comprises: a. regenerating the desulfurizing adsorbent to be tested; b. reducing the regenerated adsorbent obtained in step a with a weight of Mc; c . In step b, the obtained reducing adsorbent is contacted with the hydrocarbon oil feedstock containing thiophene compounds continuously fed and subjected to a desulfurization adsorption reaction under hydrogen conditions, to obtain a desulfurization product with a weight of M o at most; d, using formula (1) calculation unit The desulfurization activity I t of the desulfurization adsorbent to be tested by weight, the formula (1) is: 
E, the fresh desulfurization adsorbent is carried out the processing of step b-d, obtains the desulfurization activity I f of the fresh desulfurization adsorbent; F, adopts formula (2) to calculate the relative desulfurization activity index of the desulfurization adsorbent to be measured, and formula (2) is : The method of the invention is simple and easy to implement, and can quickly and accurately measure the activity of the adsorbent.
Description
Technical Field
The invention relates to a method for measuring the activity of a desulfurization adsorbent.
Background
With the increasing emphasis on environmental protection, the limit on the sulfur content in light hydrocarbons as fuel is becoming more and more strict. In the case of gasoline, the European Union has specified a sulfur content of not more than 50 μ g/g in 2005 and a sulfur content of less than 10 μ g/g in the European V gasoline standard planned to be implemented in 2010. The national III standard implemented in China beginning at No. 12 and No. 31 in 2009 specifies that the sulfur content of gasoline is not more than 150 mug/g, and plans to be popularized and implemented in 2014 nationwide in China as a national IV standard that the sulfur content of gasoline is not more than 50 mug/g.
The S-Zorb gasoline adsorption desulfurization process is rapidly popularized in China due to the characteristics of high desulfurization depth, low hydrogen consumption, low octane number loss and the like. According to the methods disclosed by US6274533, US6869522, US7427581 and the like, when the catalytic cracking is subjected to adsorption desulfurization, sulfur in the catalytic cracking gasoline can be removed to be below 10 micrograms/gram, the explosion-resistant index loss of the product is not more than 0.6 unit, the reaction conditions are 0.1-10.3 MPa, 37.7-537.7 ℃ and the weight hourly space velocity is 0.5-50 h-1And under hydrogen conditions. The adsorbent is prepared by using a mixture of zinc oxide, silica and alumina as a carrier, wherein the zinc oxide accounts for 10-90 wt%, the silica accounts for 5-85 wt%, and the alumina accounts for 5-30 wt%. The active component is loaded reduction metal, and is composed of one or more of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, vanadium and the like loaded on a carrier. The adsorbent is obtained by mixing, molding, drying and roasting the carrier and the metal component.
The S-Zorb desulfurization adsorbent mainly plays roles in desulfurization and sulfur storage in the reaction process. Under the reaction condition of hydrogen, the Ni active center on the adsorbent converts the sulfide in the sulfur-containing hydrocarbon oil into Ni-S intermediate, and then transfers the sulfur to ZnO with the help of hydrogen to form ZnS, so as to achieve the purpose of capturing and storing the sulfur in the reaction material into the adsorbent, and then the sulfur stored on the adsorbent is burned off through a regeneration system, thereby realizing the recovery of the desulfurization activity of the adsorbent. Therefore, in the process of the adsorption desulfurization reaction, the reactivity of the desulfurization adsorbent, especially the content of ZnO in the adsorbent, is important to achieve the purpose of deep desulfurization. The research on the reason that the deactivation of the adsorbent in the gasoline desulfurization process of the S-Zorb device is analyzed, the adsorbent is slowly released and the like, and petroleum refining and chemical engineering.2011, 42(12):1-6 shows that the basic reason that the deactivation of the S-Zorb adsorbent occurs in the application process is that active ZnO on the adsorbent continuously reacts with an aluminum source and a silicon source in a carrier to generate inactive zinc-aluminum spinel and willemite, and the two phases can not be converted into ZnO with desulfurization activity in the regeneration process, so that the activity of the adsorbent is continuously reduced.
Chinese patent CN 101718766a discloses a device for measuring the penetrated sulfur capacity and a method of use thereof. According to the invention, hydrogen sulfide gas is used as a sulfuration medium, a mixed gas containing hydrogen sulfide is contacted with a desulfurizer, a silver nitrate solution is used as a detector, when black precipitation appears in the detector, the flow of the hydrogen sulfide gas with known concentration of a wet gas flowmeter is recorded, and the penetrating sulfur capacity of the desulfurizer is obtained through calculation. The sulfuration medium used in the method can only be hydrogen sulfide gas, and the volume percentage content of the hydrogen sulfide gas in the mixed gas is limited to 3.8-4.2%.
Chinese patent CN 103789003a discloses a method for determining desulfurization activity of a desulfurization adsorbent. The invention uses catalytic gasoline with known sulfur content as raw material, evaluates the desulfurization activity of the desulfurization adsorbent, and evaluates the activity of the adsorbent by analyzing the desulfurization rate of products in different periods. Although the method can obtain the desulfurization rate of products in different periods, the evaluation period is too long, six cycles can be needed at most, and the net reaction time is more than 84 hours.
At present, the content of ZnO in the adsorbent is measured by using an X-ray diffraction (XRD) method, and an adsorbent sample is obtained from an industrial device and then sent to a professional institution to analyze and measure the content of ZnO in the adsorbent.
Disclosure of Invention
The invention aims to provide a method for measuring the activity of a desulfurization adsorbent, which is simple and feasible and can quickly and accurately measure the activity of the adsorbent.
In order to achieve the above object, the present invention provides a desulfurization adsorbent activity measuring method, comprising:
a. contacting a desulfurization adsorbent to be detected with oxygen-containing gas and carrying out regeneration treatment to obtain a regenerated adsorbent;
b. the weight is McContacting the regenerated adsorbent obtained in the step a with a hydrogen reduction gas and carrying out reduction treatment to obtain a reduction adsorbent;
c. contacting the reduction adsorbent obtained in the step b with a continuously fed hydrocarbon oil raw material containing thiophene compounds, and performing desulfurization adsorption reaction under the hydrogen condition to obtain M at mostoDesulfurization products; wherein the sulfur content of the hydrocarbon oil raw material is m in terms of sulfur element and based on the weight of the hydrocarbon oil raw material1(ii) a The total sulfur content of the desulfurization product is m based on the weight of the desulfurization product and the sulfur element2The sulfur content of the desulfurization product is less than 0.001 wt%;
d. calculating the desulfurization activity I of the desulfurization adsorbent to be measured in unit weight by using the formula (1)tThe formula (1) is:
e. taking the fresh desulfurization adsorbent as the desulfurization adsorbent to be detected to carry out the treatment of the steps b to d to obtain the desulfurization activity I of the fresh desulfurization adsorbentf；
f. Calculating the relative desulfurization activity index of the desulfurization adsorbent to be detected by adopting a formula (2), wherein the formula (2) is as follows:
optionally, in step a, the regeneration treatment conditions include: the temperature is 400 ℃ and 800 ℃, the pressure is 0-1.5 MPa, and the gas hourly space velocity is 0.01-1000 liters of oxygen in the oxygen-containing gas per gram of the desulfurizing adsorbent to be detected.
Optionally, in step a, the oxygen-containing gas is at least one selected from the group consisting of air, oxygen, a mixed gas of air and nitrogen, a mixed gas of oxygen and nitrogen, a mixed gas of air and an inert gas, and a mixed gas of oxygen and an inert gas; the inert gas is helium and/or argon.
Optionally, in step b, the reduction treatment conditions include: the temperature is 300 ℃ and 700 ℃, the pressure is 0.1-10 MPa, and the gas hourly space velocity is 0.01-1000 liters of the hydrogen reduction gas per gram of the regenerated adsorbent.
Optionally, in step b, the hydrogen reducing gas includes at least one selected from hydrogen gas, hydrogen-containing gas and hydrogen donor capable of providing hydrogen gas under the condition of hydrogen reducing treatment.
Optionally, in step c, the desulfurization adsorption reaction conditions include: the temperature is 300 ℃ and 700 ℃, the pressure is 0.1-10 MPa, and the weight hourly space velocity is 0.1-20 h-1The molar ratio of hydrogen to oil is 0.5-100.
Optionally, in step c, the thiophene compound is at least one selected from thiophene, alkyl-substituted thiophene, benzothiophene, alkyl-substituted benzothiophene, dibenzothiophene and alkyl-substituted dibenzothiophene.
Optionally, in step c, the olefin content of the hydrocarbon oil raw material is less than 5 wt%, the carbon number of the hydrocarbon in the hydrocarbon oil raw material is 5 to 20, and the sulfur content of the hydrocarbon oil raw material is 0.001 to 30 wt%.
Optionally, in step c, the olefin content of the hydrocarbon oil raw material is less than 2 wt%, and the sulfur content of the hydrocarbon oil raw material is 0.01-5 wt%.
Optionally, at least one method selected from an oxygen bomb method, a lamp burning method, a tube furnace method, a microcoulomb method, an infrared absorption method, an ultraviolet fluorescence method and an electrical detection method is used for detecting the sulfur content in the hydrocarbon oil raw material and the desulfurization product.
Optionally, in step a, the desulfurization adsorbent to be detected is an industrial equilibrium adsorbent.
Compared with the prior art, the invention has the following technical effects:
the method can accurately measure the desulfurization activity of different types of adsorbents, wherein the different types of adsorbents comprise fresh desulfurization adsorbents, spent adsorbents, regenerated adsorbents, balancing agents, waste agents and the like.
2 the method of the invention is simple, convenient and fast to operate, and can be realized by each refinery unit by utilizing the existing equipment technology and personnel.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for measuring the activity of a desulfurization adsorbent, which comprises the following steps:
a. contacting a desulfurization adsorbent to be detected with oxygen-containing gas and carrying out regeneration treatment to obtain a regenerated adsorbent;
b. the weight is McContacting the regenerated adsorbent obtained in the step a with a hydrogen reduction gas and carrying out reduction treatment to obtain a reduction adsorbent;
c. contacting the reduction adsorbent obtained in the step b with a continuously fed hydrocarbon oil raw material containing thiophene compounds, and performing desulfurization adsorption reaction under the hydrogen condition to obtain M at mostoDesulfurization products; wherein the sulfur content of the hydrocarbon oil raw material is m in terms of sulfur element and based on the weight of the hydrocarbon oil raw material1(ii) a The total sulfur content of the desulfurization product is m based on the weight of the desulfurization product and the sulfur element2The sulfur content of the desulfurization product is less than 0.001 wt%, and the sulfur content of the desulfurization product is preferably detected on line (namely, the desulfurization product discharged continuously is detected in real time);
d. calculating the desulfurization activity I of the desulfurization adsorbent to be measured in unit weight by using the formula (1)tThe formula (1) is:
e. taking the fresh desulfurization adsorbent as the desulfurization adsorbent to be detected to carry out the treatment of the steps b to d to obtain the desulfurization activity I of the fresh desulfurization adsorbentf；
f. Calculating the relative desulfurization activity index of the desulfurization adsorbent to be detected by adopting a formula (2), wherein the formula (2) is as follows:
the method for measuring the desulfurization activity of the desulfurization adsorbent provided by the invention is to regenerate the desulfurization adsorbent in the oxygen-critical atmosphere, then reducing the desulfurization adsorbent, reacting the reduced desulfurization adsorbent under the reaction condition of hydrogen, the desulfurization product is collected and weighed, the sulfur content in the desulfurization product is analyzed, the weight of the desulfurization product with the sulfur weight fraction of less than 0.001 percent is multiplied by the sulfur difference before and after the desulfurization of the hydrocarbon oil raw material and then divided by the weight of the regenerated adsorbent to obtain the desulfurization activity of the desulfurization adsorbent in unit weight, the ratio of the desulfurization activity of the desulfurization adsorbent in unit weight to the desulfurization activity of the fresh desulfurization adsorbent in unit weight measured by the method is multiplied by 100 to obtain the relative desulfurization activity index of the adsorbent to be measured, and the relative desulfurization activity index is applied to guide industrial production.
According to the invention, the regeneration treatment refers to contacting the desulfurizing adsorbent to be tested with oxygen-containing gas in a reaction device, burning off sulfur and carbon possibly existing on the adsorbent at the regeneration temperature, fully regenerating the adsorbent and recovering the activity. In step a, the regeneration treatment conditions may include: the temperature is 400-800 ℃, preferably 450-650 ℃, the pressure (gauge pressure) is 0-1.5 MPa, preferably 0-0.5 MPa, and the gas hourly space velocity is 0.01-1000L of oxygen in the oxygen-containing gas per gram of desulfurizing adsorbent to be detected.
According to the present invention, in step a, the oxygen-containing gas is a gas containing a certain content, and may be at least one selected from the group consisting of air, oxygen, a mixed gas of air and nitrogen, a mixed gas of oxygen and nitrogen, a mixed gas of air and an inert gas, and a mixed gas of oxygen and an inert gas, for example; the inert gas may be helium and/or argon.
The desulfurization adsorbent according to the present invention is well known to those skilled in the art, and preferably applied to an S-Zorb platform, and generally comprises nickel oxide and zinc oxide, and in addition to nickel oxide and zinc oxide components, the adsorbent generally comprises silica, alumina, and a non-nickel active metal, wherein the zinc oxide, silica, and alumina serve as support components of the adsorbent, and the nickel oxide and the non-nickel active metal serve as active components of the adsorbent; the non-nickel active metal may be at least one selected from the group consisting of cobalt, copper, iron, manganese, molybdenum, tungsten, silver, tin, and vanadium.
A preferable adsorbent ratio is that zinc oxide accounts for 10-90 wt%, silicon dioxide accounts for 5-85 wt%, and aluminum oxide accounts for 5-30 wt% of the desulfurization adsorbent to be detected based on the dry weight of the desulfurization adsorbent to be detected and calculated by oxide weight; the total weight content of the non-nickel active metal and the nickel in the desulfurization adsorbent to be tested is 5-30 wt% based on the dry weight of the desulfurization adsorbent to be tested and calculated by the weight of elements.
According to the invention, the fresh desulfurization adsorbent or the desulfurization adsorbent to be tested is subjected to reduction treatment, so that the NiO in the adsorbent is reduced into Ni (ZnO is not reduced into Zn), the obtained reduction adsorbent is conveniently contacted with the hydrocarbon oil raw material under the condition of a hydrogenation reaction, and sulfur contained in the hydrocarbon oil raw material is transferred and loaded on the adsorbent. In step b, the reduction treatment conditions may include: the temperature is 300-700 ℃, preferably 350-500 ℃, the pressure is 0.1-10 MPa, preferably 0.5-5 MPa, and the gas hourly space velocity is 0.01-1000 liters of hydrogen reduction gas/g of regenerated adsorbent. The hydrogen reducing gas may include at least one selected from hydrogen gas, a hydrogen-containing gas, and a hydrogen donor capable of providing hydrogen gas under the condition of the hydrogen reducing treatment, the hydrogen-containing gas may be a mixture of hydrogen gas and an inert gas, and the hydrogen donor may be at least one selected from tetralin, decalin, and indane.
According to the invention, in step c, the desulfurization adsorption reaction is used for making the reducing adsorbent fully adsorb sulfur, and the mass fraction of sulfur in the desulfurization product is not less than 0.001% as the standard of adsorption saturation of the reducing adsorbent, and the conditions of the desulfurization adsorption reaction can include: the temperature is 300-700 ℃, preferably 350-500 ℃, the pressure (gauge pressure) is 0.1-10 MPa, preferably 0.5-5 MPa, and the weight hourly space velocity is 0.1-20 h-11-10 hours-1The molar ratio of hydrogen to oil is 0.5 to 100, preferably 1.0 to 10. The evaluation reaction apparatus used for the desulfurization adsorption reaction may be a fixed bed reaction apparatus or a fluidized bed reaction apparatus.
According to the present invention, the hydrocarbon oil raw material is configured or selected according to the composition of sulfur in the actual hydrocarbon oil so as to better simulate the real reaction situation, and therefore, the hydrocarbon oil raw material of the present invention uses a thiophene compound as the sulfur-containing compound, in step c, the thiophene compound may be at least one selected from thiophene, alkyl-substituted thiophene, benzothiophene, alkyl-substituted benzothiophene, dibenzothiophene and alkyl-substituted dibenzothiophene, the olefin content of the hydrocarbon oil raw material may be less than 5 wt%, preferably less than 2 wt%, the carbon number of the hydrocarbon in the hydrocarbon oil raw material may be 5 to 20, and the sulfur content of the hydrocarbon oil raw material may be 0.001 to 30 wt%, preferably 0.01 to 5 wt%.
In the invention, the sulfur content in the hydrocarbon oil raw material and the desulfurization product can be determined by adopting the existing method, and the method can be summarized in the reference of' analysis method of sulfur content in Yangfeng. petrochemical field 2006,37 (2): 57-62 ", for example, the sulfur content in the hydrocarbon oil feedstock and the desulfurized product is measured by at least one method selected from the group consisting of an oxygen bomb method, a lamp method, a tube furnace method, an infrared absorption method, a microcoulomb method, an ultraviolet fluorescence method, and an electrical detection method. The weight of the desulfurization product can be measured by collecting and weighing the desulfurization product, or by measuring the hydrocarbon oil raw material by an instrument such as a gravimetric flow meter.
In the invention, the desulfurization adsorbent to be detected can be an industrial equilibrium adsorbent or a fresh desulfurization adsorbent. The fresh desulfurization adsorbent refers to an qualified adsorbent which is not used yet and is produced by a manufacturer, and the desulfurization adsorbent to be tested is preferably an industrial equilibrium adsorbent which is obtained by industrial use of the fresh desulfurization adsorbent, can be a spent adsorbent loaded with a certain amount of sulfur and carbon from a reactor, and can also be a regenerated adsorbent from a regenerator.
The determination method of the present invention will be further illustrated by the following examples, but the present invention is not limited thereto.
The small-sized fixed bed reactor used in the examples and comparative examples of the present invention was 10 ml, and the infrared carbon sulfur analyzer used was a CS600 carbon sulfur analyzer manufactured by LECO corporation.
The fresh desulfurization sorbent is of the commercial grade FCAS, with zinc oxide, silica and alumina as carriers, loaded with Ni as the active component. After the FCAS fresh desulfurization adsorbent is applied to an industrial device, 3 desulfurization adsorbent samples to be tested are collected after use, and the desulfurization adsorbent samples to be tested are respectively marked as S1, S2 and S3.
Comparative examples 1 to 4
Comparative examples 1 to 4 illustrate the activity measurements of the fresh desulfurization adsorbent FCAS and the desulfurization adsorbents S1, S2, and S3 to be tested, respectively, using the existing X-ray diffraction method.
For comparison, the desulfurization adsorbents to be tested, S1, S2 and S3, were first subjected to a regeneration process before analysis, the regeneration process being: 16 g of the adsorbent is loaded in a fluidized bed reactor, and the regeneration conditions are as follows: a regeneration stage 1, wherein the regeneration temperature is 480 ℃, the pressure is normal pressure, the regeneration gas is a mixed gas of air and nitrogen (8 liters/hour of air +8 liters/hour of nitrogen), and the regeneration is carried out for 2 hours; a regeneration stage 2, wherein the regeneration temperature is 510 ℃, the pressure is normal pressure, the regeneration gas is a mixed gas of air and nitrogen (12 liters/hour of air +4 liters/hour of nitrogen), and the regeneration is carried out for 2 hours; and in the regeneration stage 3, the regeneration temperature is 530 ℃, the pressure is normal pressure, the regeneration gas is 16 liters/hour of air, and the regeneration is carried out for 2 hours.
Using X-ray diffraction (XRD), on a TTR 3X-ray diffractometer manufactured by Japan science, the tube voltage is 40 kV, the tube current is 250 mA, the slit is 0.3 mm (RS), the scanning range is 10-80 degrees,at a scanning rate of 0.4 DEG/min, full spectrum fitting was performed on XRD spectral lines by Jade7 software (Rietveld method), and phase analyses were performed on samples of fresh desulfurization adsorbent FCAS (comparative example 1), regenerated desulfurization adsorbent S1 to be tested (comparative example 2), regenerated desulfurization adsorbent S2 to be tested (comparative example 3), and regenerated desulfurization adsorbent S3 to be tested (comparative example 4). The results of the analysis are shown in Table 1, wherein the activity index IZnOTaking the ZnO content in the fresh desulfurizer FCAS as 100, and taking the ratio of the ZnO content data in other comparative examples to the ZnO content in the fresh agent as the activity index I of the corresponding adsorbentZnO。
Example 1
16 g of fresh desulfurization adsorbent FCAS is loaded in a small fixed bed reactor, the adsorbent is firstly reduced for 2 hours under the conditions of 2.5 MPa of pressure, 16 liters/hour of hydrogen and 400 ℃ of temperature, and then a thiophene + n-octane (analytically pure, 99%) solution with 0.2 percent of sulfur weight fraction is used as a hydrocarbon oil raw material under the conditions of 2.5 MPa of pressure, 16 liters/hour of hydrogen and 5 hours of weight hourly space velocity-1And carrying out desulfurization adsorption reaction under the reaction condition that the temperature is 400 ℃ and the molar ratio of hydrogen to oil is 1, analyzing the sulfur content of the product by using a SINDIE online total sulfur analyzer, and stopping feeding when the weight fraction of sulfur in the desulfurization product is more than 0.001%. The weight of the raw material entering the reactor for contact reaction with the adsorbent is measured by a feed weight flow meter as the weight of the desulfurization product. And the relative desulfurization activity index K of the adsorbent was calculated using the formulas (1) and (2) in the activity measurement method of the present invention, and the results are shown in table 2.
Example 2
16 g of desulfurization adsorbent S1 to be tested is loaded in a small fixed bed reactor, and the adsorbent is firstly regenerated under the following conditions: a regeneration stage 1, wherein the regeneration temperature is 430 ℃, the pressure is normal pressure, the regeneration gas is a mixed gas of air and nitrogen (8 liters/hour of air +8 liters/hour of nitrogen), and the regeneration is carried out for 2 hours; a regeneration stage 2, wherein the regeneration temperature is 480 ℃, the pressure is 0.1 MPa, the regeneration gas is a mixed gas of air and nitrogen (12 liters/hour of air +4 liters/hour of nitrogen), and the regeneration is carried out for 2 hours; regeneration stage 3, regeneration temperature 530 deg.C, pressure 0.1 MPa, regeneration gas 16LAir/hour, 2 hours of regeneration. Then the absorbent is reduced for 0.5 hour under the conditions of 2.5 MPa of pressure, 16 liters/hour of hydrogen and 400 ℃ of temperature, and then thiophene + n-octane (analytically pure, 99%) solution with 0.2 percent of sulfur weight fraction is used as hydrocarbon oil raw material, and the reaction pressure is 2.5 MPa, the hydrogen is 16 liters/hour and the weight hourly space velocity is 5 hours-1And carrying out desulfurization adsorption reaction under the reaction condition that the temperature is 400 ℃ and the molar ratio of hydrogen to oil is 1, analyzing the sulfur content of the product by using a SINDIE online total sulfur analyzer, and stopping feeding when the weight fraction of sulfur in the desulfurization product is more than 0.001%. The weight of the raw material entering the reactor for contact reaction with the adsorbent is measured by a feed weight flow meter as the weight of the desulfurization product. And the relative desulfurization activity index K of the adsorbent was calculated using the formulas (1) and (2) in the activity measurement method of the present invention, and the results are shown in table 2.
Example 3
16 g of desulfurization adsorbent S2 to be tested is loaded in a small fluidized bed reactor, and the adsorbent is firstly regenerated under the following conditions: in the regeneration stage 1, the regeneration temperature is 430 ℃, the pressure is 0.5 MPa, the regeneration gas is a mixed gas of air and nitrogen (8 liters/hour of air +8 liters/hour of nitrogen), and the regeneration is carried out for 2 hours; a regeneration stage 2, wherein the regeneration temperature is 480 ℃, the pressure is 0.5 MPa, and the regeneration gas is a mixed gas of air and nitrogen (12 liters/hour of air +4 liters/hour of nitrogen); regeneration is carried out for 2 hours, and in a regeneration stage 3, the regeneration temperature is 530 ℃, the pressure is 0.5 MPa, the regeneration gas is 16 liters/hour of air, and the regeneration is carried out for 2 hours. Then reducing the adsorbent for 2 hours under the conditions of 1.5 MPa of pressure, 32 liters/hour of hydrogen and 400 ℃ of temperature, then using thiophene + n-octane (analytically pure, 99%) solution with 0.2 percent of sulfur weight fraction as hydrocarbon oil raw material, and reacting for 1.5 MPa of pressure, 32 liters/hour of hydrogen and 1 hour of weight hourly space velocity-1Carrying out desulfurization adsorption reaction under the reaction condition that the temperature is 450 ℃ and the molar ratio of hydrogen to oil is 10, analyzing the sulfur content of the product by using a SINDIE online total sulfur analyzer, and stopping feeding when the weight fraction of sulfur in the desulfurization product is more than 0.001%. The weight of the raw material entering the reactor for contact reaction with the adsorbent is measured by a feed weight flow meterWeight of desulfurization product. And the relative desulfurization activity index K of the adsorbent was calculated using the formulas (1) and (2) in the activity measurement method of the present invention, and the results are shown in table 2.
Example 4
16 g of desulfurization adsorbent S3 to be tested is loaded in a small fixed bed reactor, and the adsorbent is firstly regenerated under the following conditions: the regeneration temperature is 530 ℃, the pressure is normal pressure, the regeneration gas is 16 liters/hour of air, and the regeneration is carried out for 6 hours. Then reducing the adsorbent for 1 hour under the conditions of 0.5 MPa of pressure, 32 liters/hour of hydrogen and 430 ℃ of temperature, then using thiophene + n-octane (analytically pure, 99%) solution with 0.2 percent of sulfur weight fraction as hydrocarbon oil raw material, and reacting for 1 hour at the conditions of 0.5 MPa of reaction pressure, 32 liters/hour of hydrogen and 1 hour of weight hourly space velocity-1And carrying out desulfurization adsorption reaction on the adsorbent under the reaction condition that the temperature is 430 ℃ and the molar ratio of hydrogen to oil is 10, analyzing the sulfur content of the product by using a SINDIE online total sulfur analyzer, and stopping feeding when the weight fraction of sulfur in the desulfurization product is more than 0.001%. The weight of the raw material entering the reactor for contact reaction with the adsorbent is measured by a feed weight flow meter as the weight of the desulfurization product. And the relative desulfurization activity index K of the adsorbent was calculated using the formulas (1) and (2) in the activity measurement method of the present invention, and the results are shown in table 2.
Example 5
16 g of desulfurization adsorbent S3 to be tested is loaded in a small fixed bed reactor, and the adsorbent is firstly regenerated under the following conditions: the regeneration temperature is 530 ℃, the pressure is normal pressure, the regeneration gas is 16 liters/hour of air, and the regeneration is carried out for 6 hours. Then reducing the adsorbent for 1 hour under the conditions of 0.5 MPa of pressure, 32 liters/hour of hydrogen and 430 ℃ of temperature, then using benzothiophene with 0.1 percent of sulfur by weight and straight-run naphtha solution as hydrocarbon oil raw materials, and reacting at 2.0 MPa of pressure, 32 liters/hour of hydrogen and 5 hours of weight hourly space velocity-1And carrying out desulfurization adsorption reaction under the reaction condition that the temperature is 430 ℃ and the molar ratio of hydrogen to oil is 2, analyzing the sulfur content of the product by using a SINDIE online total sulfur analyzer, and stopping feeding when the weight fraction of sulfur in the desulfurization product is more than 0.001%. By feeding heavy materialsThe mass flow meter measures the weight of the raw material entering the reactor for contact reaction with the adsorbent as the weight of the desulfurization product. And the relative desulfurization activity index K of the adsorbent was calculated using the formulas (1) and (2) in the activity measurement method of the present invention, and the results are shown in table 2.
As can be seen from the data of comparative examples 1 to 4 and examples 1 to 5, the relative desulfurization activity index of the desulfurization adsorbent measured by the present method is very identical to the activity index measured by the XRD method, and the desulfurization activity status of the adsorbent can be accurately reflected. TABLE 1
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Desulfurization adsorbent | FCAS | S1 | S2 | S3 |
| ZnO weight fraction/% | 47.1 | 40.2 | 25.6 | 7.9 |
| Activity index IZnO | 100 | 85 | 54 | 17 |
TABLE 2
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Desulfurization adsorbent | FCAS | S1 | S2 | S3 | S3 |
| Relative desulfurization activity index K | 100 | 83 | 52 | 19 | 17 |
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