阅读说明：本技术 一种捕硅剂及其制备方法 (Silicon capturing agent and preparation method thereof ) 是由 杨成敏 姚运海 刘丽 段为宇 李扬 周勇 郭蓉 孙进 郑步梅 丁莉 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种捕硅剂及其制备方法。本发明的捕硅剂,包括载体和加氢活性组分,加氢活性组分为第VIB族金属硫化物、第VIB族金属氧化物和第VIII族金属氧化物,以捕硅剂的总重量为基准,第VIB族金属硫化物为0.3wt%-18.3wt%,第VIB族金属氧化物为0.1wt%-5.0wt%,第VIII族金属氧化物计为0.2wt%-12.0wt%。本发明捕硅剂的制备方法,包括如下内容：(1)用含第VIB族金属的浸渍液浸渍催化剂载体,然后干燥处理,干燥后的物料进行硫化处理；(2)用含第VIB族和第族金属的浸渍液浸渍到步骤(1)硫化后的的物料,然后在惰性气氛下,进行干燥和焙烧,得到捕硅剂。本发明捕硅剂的活性组分具有较高的硫化度,捕硅剂具有较高的容硅能力,适用于焦化干气、焦化石脑油、焦化柴油等含硅油品的脱硅和捕硅。(The invention discloses a silicon capturing agent and a preparation method thereof. The silicon capturing agent comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIB group metal sulfide, VIB group metal oxide and VIII group metal oxide, and based on the total weight of the silicon capturing agent, the VIB group metal sulfide is 0.3wt% -18.3wt%, the VIB group metal oxide is 0.1wt% -5.0wt%, and the VIII group metal oxide is 0.2wt% -12.0 wt%. The preparation method of the silicon capturing agent comprises the following steps: (1) impregnating catalyst carrier with the impregnating solution containing VIB group metal, drying, and sulfurizing the dried materialProcessing; (2) by containing groups VIB and)

1. A silicon capture agent comprises a carrier and a hydrogenation active component, and is characterized in that: the hydrogenation active components are VIB group metal sulfide, VIB group metal oxide and VIII group metal oxide; based on the total weight of the silicon capturing agent, the VIB group metal sulfide accounts for 0.3wt% -18.3wt%, the VIB group metal oxide accounts for 0.1wt% -5.0wt%, and the VIII group metal oxide accounts for 0.2wt% -12.0 wt%.

2. The silicon capture agent according to claim 1, characterized in that: based on the total weight of the silicon capturing agent, the VIB group metal sulfide accounts for 2.0-11.0 wt%; 0.2wt% -3.0wt% of group VIB metal oxide; 0.3wt% to 6.0wt% calculated on group VIII metal oxide.

3. The silicon capture agent according to claim 1, characterized in that: wherein the VIB group metal is Mo and/or W, and the VIII group metal is Co and/or Ni.

4. The silicon capture agent according to claim 1, characterized in that: the silicon capturing agent is subjected to vulcanization and then is analyzed by XPS energy spectrum, wherein the molar ratio of the +4 valence VIB group metal content to the total VIB group metal content is 70-100%.

5. The silicon capture agent according to claim 1, characterized in that: the silicon capturing agent carrier is porous inorganic refractory oxide and is selected from one or more of oxides of elements in II group, III group, IV group and IVB group in the periodic table.

6. The silicon capture agent according to claim 1, characterized in that: the silicon catching agent carrier is one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide and aluminum magnesium oxide, a hydrocracking catalyst containing silicon oxide or a hydrocracking catalyst containing a molecular sieve.

7. A method for producing a silicon capture agent according to any one of claims 1 to 6, characterized by comprising: (1) impregnating a catalyst carrier with an impregnating solution containing VIB group metals, drying, and vulcanizing the dried material; (2) by containing groups VIB andand (3) dipping the vulcanized material obtained in the step (1) in dipping liquid of the group metal, and then drying and roasting the dipped material in an inert atmosphere to obtain the silicon catching agent.

8. The method of claim 7, wherein: the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.

9. The method of claim 7, wherein: the vulcanization treatment in the step (1) is dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide.

10. The method of claim 7, wherein: the vulcanization treatment conditions in the step (1) are as follows: the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 hours.

11. The method of claim 7, wherein: the inert atmosphere in the step (2) is N₂And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

12. The silicon capture agent as defined in any one of claims 1 to 6 is applied to hydrogenation of coking dry gas, hydrogenation of coking naphtha, reforming pre-hydrogenation and hydrogenation of coking diesel oil.

Technical Field

The invention relates to the technical field of oil product desilication, in particular to a coking naphtha silicon capturing agent and a preparation method thereof.

Background

The coking naphtha hydrofining technology can remove or partially remove impurities such as silicon, olefin, sulfur, nitrogen, aromatic hydrocarbon and the like in the raw materials, and the products can be used as fuel gasoline and chemical raw materials. The implementation of this technology can convert low value coker naphtha to high value added products. Coker naphtha contains a significant amount of silicon which deposits on the hydrofinishing catalyst, causing catalyst deactivation. In order to slow down or avoid silicon poisoning deactivation of the hydrofinishing catalyst, the inlet portion of the reactor is typically filled with a silicon capture agent.

The development direction of the silicon capturing agent is to improve the desiliconization capability and the silicon containing capability. CN101343565A discloses a hydrofining method of silicon-containing distillate oil. The hydrogenation catalyst with the silicon capturing function has larger pore volume and specific surface area and relatively lower metal content. CN102051202A discloses a coking naphtha silicon capturing agent and application thereof. The silicon capturing agent takes alumina as a carrier, silicon dioxide as an auxiliary agent and W, Mo and Ni as hydrogenation components. CN103920524A discloses a desiliconization agent and a preparation method and application thereof. The desiliconization agent contains a carrier and a hydrogenation active metal component loaded on the carrier, wherein the carrier is pseudo-boehmite and a mesoporous Y-type molecular sieve. The improvement of the silicon capturing agent of the patent is mainly focused on the carrier, and the improvement of the active component of the catalyst is less involved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a silicon capture agent and a preparation method thereof. The active component of the invention has higher sulfuration degree, and the silicon catching agent has higher silicon capacity, thus being applicable to the desilication and silicon catching of silicon-containing oil products such as coking dry gas, coking naphtha, coking diesel oil and the like.

The silicon capturing agent comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIB group metal sulfide, VIB group metal oxide and VIII group metal oxide, wherein the VIB group metal is preferably Mo and/or W, and the VIII group metal is preferably Co and/or Ni; based on the total weight of the silicon capturing agent, the VIB group metal sulfide accounts for 0.3wt% -18.3wt%, preferably 2.0wt% -11.0 wt%; group VIB metal oxides from 0.1 wt.% to 5.0 wt.%, preferably from 0.2 wt.% to 3.0 wt.%; from 0.2% to 12.0% by weight, preferably from 0.3% to 6.0% by weight, calculated as group VIII metal oxide.

The silicon capturing agent is subjected to vulcanization and then is analyzed by XPS energy spectrum, wherein the molar ratio of the +4 valence VIB group metal content to the total VIB group metal content is 70-100%. Typical vulcanization process conditions are: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

The silicon capturing agent carrier is a porous inorganic refractory oxide, is selected from one or more oxides of elements in II group, III group, IV group and IVB group in the periodic table, is more preferably selected from one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, magnesium silicon oxide and aluminum magnesium oxide, and is further preferably aluminum oxide. The silicon capturing agent carrier can be modified according to the requirement, for example, modification elements such as B, P, F are adopted for modification, and the weight percentage of the modification elements is 0.5wt% -10wt% based on the weight of the modified hydrogenation catalyst carrier. The silicon capturing agent carrier can also partially adopt other crushed catalyst powder, such as a hydrocracking catalyst containing silicon oxide and a hydrocracking catalyst containing a molecular sieve.

The preparation method of the silicon capturing agent comprises the following steps:

(1) impregnating a catalyst carrier with an impregnating solution containing VIB group metals, drying, and vulcanizing the dried material;

(2) by containing groups VIB andand (3) dipping the vulcanized material obtained in the step (1) in dipping liquid of the group metal, and then drying and roasting the dipped material in an inert atmosphere to obtain the silicon catching agent.

In the method of the present invention, the method for preparing the group VIB metal impregnation solution in step (1) is well known to those skilled in the art, and for example, a phosphate or ammonium salt solution is generally used, and an equal volume impregnation or other impregnation methods can be used. The group VIB metal is preferably Mo and/or W.

In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.

In the method of the present invention, the vulcanization treatment in step (1) is well known to those skilled in the art, and usually adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 hours.

In the process of the present invention, the groups VIB and VIB in step (2)Preparation method of immersion liquid of group metalIt is well known to those skilled in the art that equivalent volume impregnation or other impregnation means may be employed, such as nitrate, acetate, sulfate solutions, etc., and the group VIB metal is preferably Mo and/or WThe group metals are preferably Ni and/or Co.

In the method of the invention, the inert atmosphere in the step (2) is N₂And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

The silicon capturing agent is applied to the processes of coking dry gas hydrogenation, coking naphtha hydrogenation, reforming prehydrogenation, coking diesel oil hydrogenation and the like.

The silicon capturing agent of the invention needs to be vulcanized before application, and the general vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 hours.

The traditional catalyst exists in an oxidation state before vulcanization, while VIB group metals are difficult to vulcanize, VIII group metals are easy to vulcanize, the phenomenon that the VIII group metals in a vulcanization state are wrapped by the VIB group metals in a vulcanization state is easy to cause, the VIII group metals cannot fully play the function of an auxiliary agent, and the activity of the catalyst is reduced. The inventor develops a new method, by the way of dipping and vulcanizing different active metals step by step, firstly dipping VIB group metal on a carrier and vulcanizing in advance, and then dipping VIB group metal and sulfide on the carrierA group metal. The stepwise impregnation enablesThe group metal covers the surface of the VIB group metal in a vulcanized state and gives full play toThe group metal auxiliary agent functions to create the condition of interaction between the two; the VIB group elements in the second impregnation process can disperse the VIII group elements in the impregnation process, so that the promotion effect of the VIII group elements is further improved, and the activity of the silicon capturing agent is further improved. The silicon capturing agent can reduce the quantity of active components, increase the pore volume and the specific surface area of a finished catalyst product and improve the desiliconization and silicon capturing performances of the finished catalyst product due to the improvement of the performance of the active components.

Detailed Description

The invention is characterized in that the desilication and silicon capturing performance of the silicon capturing agent is enhanced by improving the unit activity of the hydrogenation component, and the hydrogenation component with lower content is used, so that higher specific surface area and pore volume are reserved.

The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention. The catalyst composition provided by the invention is characterized by inductively coupled plasma ICP and XPS energy spectrum. The catalyst provided by the invention has metal vulcanization degree of Mo⁴⁺Or W⁴⁺The content represents the degree of metal sulfidation of the catalyst. Using 30mL/min of H at 320 DEG C₂S sulfurizing for 2h, characterizing the metal valence state of the surface of the sample by an XPS PEAK spectrometer, respectively fitting and peak-splitting Mo3d, W4f, Co2p and Ni2p energy spectrums by adopting XPS PEAK version4.0, and calculating according to the peak area to obtain the metal sulfurization degree.

Example 1

Soaking ammonium molybdate aqueous solution on alumina carrier in equal volume to make MoO on a section of semi-finished product₃The content is 5% (taking 470 ℃ roasting analysis as a standard), and then the product is dried for 2 hours at 95 ℃ to obtain a semi-finished product A1. Then vulcanizing A1 by dry vulcanization to convert Mo into MoS₂And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 340 ℃ and under the pressure of 3.6MPa to obtain a semi-finished product A2. Under the protection of nitrogen, adopting mixed aqueous solution of ammonium molybdate and nickel nitrate to perform equal-volume impregnation on A2 so as to newly add MoO in the latter₃0.5% (based on the analysis after firing at 470 ℃) and 0.5% NiO (based on the analysis after firing at 470 ℃), then in nitrogenDrying at 65 ℃ for 6h in gas atmosphere, and roasting at 300 ℃ for 3h to obtain MoS₂-MoO₃-NiO/Al₂O₃Catalyst a 3.

Example 2

Soaking ammonium molybdate aqueous solution on alumina carrier in equal volume to make MoO on a section of semi-finished product₃The content is 3 percent (taking the analysis after roasting at 470 ℃ as a standard), and then the product is dried for 2 hours at 95 ℃ to obtain a semi-finished product B1. Then vulcanizing B1 by dry vulcanization to convert Mo into MoS₂And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 340 ℃ and under the pressure of 3.6MPa to obtain a semi-finished product B2. Under the protection of nitrogen, the mixed aqueous solution of ammonium molybdate and nickel acetate is adopted to perform equal-volume impregnation on B2, so that the MoO is newly added to the B2₃The content of 1.9% (taking the analysis after roasting at 470 ℃ as a standard) and the NiO content of 7.0% (taking the analysis after roasting at 470 ℃ as a standard), and then drying for 6h at 65 ℃ in a nitrogen atmosphere, and roasting for 3h at 210 ℃ to obtain MoS₂-MoO₃-NiO/Al₂O₃Catalyst B3.

Example 3

Equal volume of aqueous ammonium metatungstate solution was impregnated on an alumina support to make a section of the semi-finished product WO₃The content of 11% (taking 470 ℃ roasting analysis as a standard), and then drying for 2h at 95 ℃ to obtain a semi-finished product C1. Then vulcanizing C1 by dry vulcanization to convert W into WS₂And vulcanizing the mixture for 7 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 340 ℃ under the condition of 2.6MPa to obtain a semi-finished product C2. Under the protection of nitrogen, C2 is soaked in a mixed aqueous solution of ammonium molybdate and nickel acetate in an equal volume, so that MoO is newly added in the mixed aqueous solution₃2.8% (using 470 ℃ roasting analysis as standard) and NiO content 5.0% (using 470 ℃ roasting analysis as standard), then drying at 65 ℃ for 6h under nitrogen atmosphere, roasting at 350 ℃ for 3h to obtain WS₂-MoO₃-NiO/Al₂O₃Catalyst C3.

Example 4

Equal volume of aqueous ammonium metatungstate solution was impregnated on an alumina support to make a section of the semi-finished product WO₃The content is 2 percent (taking 470 ℃ roasting analysis as a standard), and then the product is dried for 2 hours at 95 ℃ to obtain a semi-finished product D1. Then using a dryerProcess vulcanization D1 was vulcanized to convert W therein to WS₂And vulcanizing the mixture for 8 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 340 ℃ under the condition of 2.9MPa to obtain a semi-finished product D2. Under the protection of nitrogen, D2 is subjected to equal-volume impregnation by using a mixed aqueous solution of ammonium metatungstate and nickel acetate, so that WO is newly added to the D2₃4.0% (using 470 ℃ roasting analysis as standard) and NiO content 3.0% (using 470 ℃ roasting analysis as standard), then drying at 65 ℃ for 6h under nitrogen atmosphere, and roasting at 390 ℃ for 3h to obtain WS₂-WO₃-NiO/Al₂O₃Catalyst D3.

Example 5

In SiO₂Soaking a silicon-containing alumina carrier with the content of 4.7% in an ammonium molybdate aqueous solution with equal volume to ensure that MoO is on a section of semi-finished product₃The content is 1.1% (based on the analysis after roasting at 470 ℃) and then the semi-finished product E1 is obtained after drying for 2 hours at 95 ℃. Then E1 was sulfided using dry sulfiding to convert Mo therein to MoS₂And vulcanizing the mixture for 4.5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 340 ℃ and under the pressure of 5.1MPa to obtain a semi-finished product E2. Under the protection of nitrogen, E2 was impregnated with a mixed aqueous solution of ammonium molybdate and cobalt nitrate in equal volume, so that the latter was newly added with MoO₃4.5% (analysis after baking at 470 ℃ is taken as standard) and 2.1% (analysis after baking at 470 ℃ is taken as standard), then drying for 6h at 65 ℃ in nitrogen atmosphere, and baking for 3h at 430 ℃ to obtain MoS₂-MoO₃-CoO/Al₂O₃-SiO₂Catalyst E3.

Example 6

In SiO₂Soaking 2.7% silicon-containing alumina carrier in ammonium molybdate water solution in equal volume to obtain MoO on the semi-finished product₃The content was 9.6% (based on the analysis after calcination at 470 ℃ C.) and then dried at 95 ℃ for 2 hours to obtain a semi-finished product F1. Then F1 is vulcanized by dry vulcanization to convert Mo into MoS₂And vulcanizing the mixture for 4.5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 340 ℃ under the pressure of 4.0MPa to obtain a semi-finished product F2. Under the protection of nitrogen, the F2 is soaked in a mixed aqueous solution of ammonium molybdate and cobalt nitrate in an equal volume, so that MoO is newly added in the latter₃The content is 1.1% (analyzed after roasting at 470 ℃ C.)Standard) and a CoO content of 4.5% (taking 470 ℃ roasting analysis as a standard), then drying at 65 ℃ for 6h under a nitrogen atmosphere, and roasting at 280 ℃ for 3h to obtain MoS₂-MoO₃-CoO/Al₂O₃-SiO₂Catalyst F3.

Example 7

Mixing 11% of mixed hydrocracking catalyst powder into alumina powder, granulating, drying and roasting to obtain SiO₂Content of 3.2%, WO₃The carrier contains 1.5 percent of NiO and 0.3 percent of NiO (both are analyzed as a standard after being roasted at 470 ℃). The carrier is dipped with ammonium molybdate aqueous solution in equal volume, so that MoO is newly added on a section of semi-finished product₃The content is 7.3% (based on the analysis after roasting at 470 ℃) and then the product is dried for 2 hours at 95 ℃ to obtain a semi-finished product G1. Then, G1 is vulcanized by dry vulcanization to convert Mo into MoS₂And vulcanizing the mixture for 6.0 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 340 ℃ and under the pressure of 4.0MPa to obtain a semi-finished product G2. Under the protection of nitrogen, G2 is subjected to equal-volume impregnation by using a mixed aqueous solution of ammonium molybdate and nickel nitrate, so that MoO is newly added to the G2₃0.9 percent (taking the analysis after roasting at 470 ℃ as a standard) and 5.5 percent of NiO (taking the analysis after roasting at 470 ℃ as a standard), then drying for 6 hours at 65 ℃ in a nitrogen atmosphere, and roasting for 3 hours at 470 ℃ to obtain MoS₂-WS₂-Ni₂S₃-MoO₃-NiO/Al₂O₃-SiO₂Catalyst G3.

Comparative example 1

This comparative example is compared to example 2.

Soaking ammonium molybdate and nickel acetate aqueous solution on an alumina carrier in equal volume to ensure that MoO is coated on a section of semi-finished product₃4.9 percent of NiO (both taking the analysis after roasting at 470 ℃ as a standard), then drying at 95 ℃ for 2h, and roasting at 210 ℃ for 3h to obtain MoO₃-NiO/Al₂O₃And (4) catalyst DB.

Comparative example 2

This comparative example is compared to example 5.

In SiO₂Soaking a silicon-containing alumina carrier with the content of 4.7 percent in ammonium molybdate and cobalt nitrate aqueous solution in an equal volume way to form a sectionMoO on semi-finished product₃5.6 percent of content and 2.1 percent of CoO content (analysis is taken as standard after roasting at 470 ℃), then drying for 2h at 95 ℃, and roasting for 3h at 430 ℃ to obtain MoO₃-CoO/Al₂O₃-SiO₂Catalyst DE.

Example 8

This example illustrates the reactivity of the silicon capture agent provided by the present invention to coker naphtha. Representing the influence degree of the active components on the pore volume and the specific surface area of the silicon catching agent through the specific surface area loss rate of the silicon catching agent immediately after vulcanization; the hydrogenation performance of the active component is measured by the carbon deposition amount on the silicon capturing agent after operation; the desiliconization and silicon capturing performance of the silicon capturing agent is measured by the content of saturated silicon on the silicon capturing agent after operation.

The evaluation feedstock used was coker naphtha supplied from a refinery in medium petrochemicals.

Catalysts A3 to G3, comparative examples DB and DE were each evaluated for reaction performance using a 200mL trickle bed hydrogenation unit.

Presulfurizing conditions of the catalyst: using a catalyst containing 3.1wt% CS₂The space velocity of the aviation kerosene is 1.0h^-1Presulfurizing the catalyst at the pressure of 3.7MPa with the hydrogen-oil volume ratio of 350: 1.

The prevulcanisation process is as follows: feeding pre-vulcanized oil at 110 ℃, feeding oil for 2h, vulcanizing at constant temperature for 2h, heating to 140 ℃ at 15 ℃/h, vulcanizing at constant temperature for 4h, heating to 220 ℃ at 6 ℃/h, vulcanizing at constant temperature for 10h, heating to 270 ℃ at 6 ℃/h, vulcanizing at constant temperature for 6h, heating to 310 ℃ at 12 ℃/h, vulcanizing at constant temperature for 6h, naturally cooling to 110 ℃, and finishing the pre-vulcanization.

The evaluation reaction conditions were: the operating pressure is 3.5MPa, the reaction temperature is 270 ℃, and the volume space velocity is 1.5h^-1The hydrogen-oil volume ratio was 350:1, and the evaluation results are shown in Table 1.

TABLE 1 Properties of catalyst and evaluation results

The above evaluation results show that the active metal of the silicon capturing agent has higher sulfidation degree, the loss of the specific surface area of the catalyst after the completion of the sulfidation is low, the carbon deposition amount is low after the operation is finished, and the saturated silicon capacity is high.