CN112745905B

CN112745905B - Selective mercaptan removal method

Info

Publication number: CN112745905B
Application number: CN201911053884.6A
Authority: CN
Inventors: 李会峰; 刘锋; 李明丰; 褚阳; 夏国富; 张登前; 郑仁垟; 王薇
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2022-11-15
Anticipated expiration: 2039-10-31
Also published as: CN112745905A

Abstract

The invention relates to the field of mercaptan removal, and discloses a selective mercaptan removal method, which comprises the following steps: (1) Under the condition of mercaptan removal, an oil product is in contact reaction with a first catalyst to obtain a first material flow; (2) Contacting the first stream with a supported silver-containing catalyst for reaction; wherein the first catalyst comprises a supported zinc-containing catalyst and a supported sulfided metal hydrogenation catalyst and/or a supported nickel-based catalyst. The method provided by the invention has high mercaptan removal selectivity, and can selectively remove mercaptan in the oil product on the premise of small octane number loss, thereby effectively reducing the total sulfur content in the oil product.

Description

Selective mercaptan removal method

Technical Field

The invention relates to the field of mercaptan removal, in particular to a selective mercaptan removal method.

Background

The increasing awareness of environmental protection and stricter regulations of environmental protection force the oil refining industry to pay more attention to the development of clean fuel production technology, and how to economically and reasonably produce ultra-low sulfur oil products becomes one of the problems to be solved in the oil refining industry at present and in a certain period in the future. In order to produce clean gasoline, the research on the high-selectivity catalytic cracking gasoline deep hydrodesulfurization catalyst with excellent performance is being dedicated at home and abroad. Olefins in catalytically cracked gasolineHydrocarbons have a higher octane number, but are easily saturated under hydrodesulfurization reaction conditions, resulting in octane number loss and increased hydrogen consumption. To solve this problem, it is necessary to design and construct an active phase having high hydrodesulfurization activity and selectivity. However, researches show that olefin and H exist in the process of carrying out hydrodesulfurization on catalytic cracked gasoline by adopting a selective hydrodesulfurization process ₂ S reaction to produce mercaptan and mercaptan hydrodesulfurization to produce olefin and H ₂ The reversible reaction process of S can remove the original mercaptan from the hydrogenated product, but can generate a small amount of mercaptan sulfur, which is called regenerated mercaptan. The lower the sulfur content in the gasoline fraction after fixed bed hydrodesulfurization, the larger the proportion of the regenerated mercaptan. In order to reduce the content of the regenerated mercaptan, hydrogenation is carried out under more severe conditions, which leads to a significant increase in the octane number loss of the product gasoline.

Although some sweetening techniques can significantly reduce the content of mercaptans in the oil, because only mercaptans are converted into disulfides or sulfides or other forms of sulfides, which remain in the oil, the total sulfur content of the oil is not correspondingly significantly reduced, resulting in the total sulfur content of the oil still being high.

Therefore, in order to produce low-sulfur and ultra-low-sulfur gasoline, effective technical means must be adopted to selectively remove the regenerated mercaptan from the hydrogenated gasoline fraction and simultaneously reduce the total sulfur content in the product on the premise of small octane number loss.

Disclosure of Invention

The invention aims to overcome the defects of harsh reaction conditions, high olefin saturation rate and large gasoline octane number loss in the process of removing regenerative mercaptan from hydrogenated gasoline fractions in the prior art, and provides a method for selectively removing mercaptan.

In order to achieve the above object, the present invention provides a method for selectively removing mercaptans, the method comprising:

(1) Under the condition of mercaptan removal, an oil product is in contact reaction with a first catalyst to obtain a first material flow;

(2) Contacting the first stream with a supported silver-containing catalyst for reaction;

wherein the first catalyst comprises a supported zinc-containing catalyst and a supported sulfided metal hydrogenation catalyst and/or a supported nickel-based catalyst.

Preferably, the supported sulfided metal hydrogenation catalyst comprises a first carrier, and an active component a and an active metal component B which are loaded on the first carrier, wherein the active metal component a is selected from at least one of group VIII metal elements, and the active metal component B is selected from at least one of group VIB metal elements.

Preferably, the supported zinc-containing catalyst comprises a second support and zinc oxide supported on the second support.

Preferably, the supported silver-containing catalyst comprises a third carrier and a silver-containing compound supported on the third carrier.

Preferably, the supported nickel-based catalyst includes a fourth carrier and an active component nickel supported on the fourth carrier.

According to the embodiment of the invention, after hydrogenation, heavy gasoline (mercaptan content 28 mug/g, total sulfur content 65 mug/g, olefin volume fraction 25.6%) is subjected to selective mercaptan removal by adopting the selective mercaptan removal method provided by the invention, on the premise of small octane value loss, the mercaptan content is reduced to be less than 3 mug/g, and the total sulfur content is reduced to be 37 mug/g. The method for selectively removing the mercaptan has high total sulfur and mercaptan sulfur removal rate and high mercaptan removal selectivity, and can be industrially popularized in the field of oil product desulfurization in a large scale.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a method for selectively removing mercaptan, which comprises the following steps:

According to a preferred embodiment of the present invention, the supported sulfided metal hydrogenation catalyst comprises a first carrier, and an active component a and an active metal component B supported on the first carrier, wherein the active metal component a is selected from at least one of group VIII metal elements, and the active metal component B is selected from at least one of group VIB metal elements.

According to the invention, preferably, the active component a is Co and/or Ni and the active component B is Mo and/or W. In this preferred case, the supported sulfided metal hydrogenation catalyst has a higher selectivity for mercaptan removal after activation treatment.

In the present invention, the atomic ratio of the active metal component a to the sum of the active metal component a and the active metal component B can be determined by an X-ray fluorescence method.

The present invention has a wide selection range of the atomic ratio of the active metal component a to the sum of the active metal component a and the active metal component B. According to the present invention, in the supported sulfided metal hydrogenation catalyst, the atomic ratio of the active metal component a to the sum of the active metal component a and the active metal component B is preferably 0.25 or more, preferably 0.3 to 0.4, as measured by X-ray fluorescence. In this preferred case, it is more advantageous to improve the catalytic performance of the catalyst.

According to a preferred embodiment of the present invention, the supported sulfided metal hydrogenation catalyst has a sulfidation degree of 70-99%, for example 70-90%, after activation treatment. The catalyst with the optimized vulcanization degree is more suitable for selective mercaptan removal reaction, and can better give consideration to high activity and high stability of the catalyst.

In the present invention, the degree of sulfidation of the catalyst means the proportion of the positive tetravalent active metal component B to the total active metal component B.

In the present invention, the degree of sulfidation of the catalyst is also determined by X-ray photoelectron spectroscopy (XPS), wherein the degree of sulfidation is obtained by processing XPS data, as described in Han et al, journal of Materials Chemistry 2012, 22.

In the present invention, preferably, the content of the type ii active phase a-B-S in the supported sulfidic metal hydrogenation catalyst measured by X-ray photoelectron spectroscopy is above 30%, preferably 35-70%, wherein the content of the type ii active phase a-B-S refers to the ratio of the amount of the active metal component a in the form of the type ii active phase a-B-S to the total amount of the active metal component a measured by X-ray photoelectron spectroscopy. A represents a VIII group metal element (such as Co and Ni), B represents a VIB group metal element (such as Mo and W), and S is a sulfur element. In the activated supported sulfurized metal hydrogenation catalyst, the VIII group metal elements exist in different forms, for example, co is used as Co in the sulfurized CoMo catalyst ²⁺ Co-Mo-S and Co ₉ S ₈ The Co existing in different forms corresponds to peaks at different positions in the XPS spectrogram, and the Co is calculated by unfolding the peaks ² ⁺ Co-Mo-S and Co ₉ S ₈ Corresponding peak area by Co-Mo-S corresponding peak area/(Co) ²⁺ Area of corresponding peak + area of Co-Mo-S corresponding peak + Co ₉ S ₈ Corresponding peak area) x 100%, the content of the II-type active phase Co-Mo-S is calculated, and the method is also suitable for NiW catalysts. The specific calculation method can be found in Qiuheim paper (X-ray photoelectron spectroscopy is used to study the chemical state of active elements in hydrodesulfurization catalyst [ J ]]And petroleum science and newspaper: petroleum processing, 2011, 27 (4): 638-642).

The carrier of the supported sulfided metal hydrogenation catalyst is not particularly limited in the present invention, and may be any of various carriers commonly used in the art, and may be a commercially available product or may be prepared by any method known in the art, and is preferably a porous oxide carrier. Further preferably, the first support is selected from one or more of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.

Preferably, the first support is present in an amount of from 50 to 90 wt%, preferably from 74 to 86 wt%, based on the total amount of the supported sulfided metal hydrogenation catalyst; the content of the active metal component A is 1 to 15% by weight, preferably 2 to 6% by weight, calculated as oxide; the content of the active metal component B is 5 to 45% by weight, preferably 8 to 20% by weight.

The catalyst component contents were measured by X-ray fluorescence spectroscopy RIPP 132-90 (petrochemical analysis (RIPP test), yangchini, kangying, wu Wenhui ed., first 9 months 1990 by scientific Press, pp 371-379).

The preparation method of the supported sulfurized metal hydrogenation catalyst is not particularly limited in the invention, as long as the supported sulfurized metal hydrogenation catalyst can be prepared. According to the present invention, preferably, the preparation method of the supported sulfided metal hydrogenation catalyst comprises:

(1) Impregnating the first support with a solution containing a precursor of active component a and a precursor of active component B, followed by a first drying and optionally a first calcination;

(2) Vulcanizing the solid product obtained in the step (1);

the step of vulcanizing comprises: contacting the solid product with a sulfur-containing medium.

In the invention, the supported oxidation state catalyst is obtained in the step (1), and the supported sulfidation state metal hydrogenation catalyst can be obtained by sulfiding the supported oxidation state catalyst.

The amounts of the precursor of the active component a, the precursor of the active component B and the first carrier can be selected according to the contents of the components in the supported sulfided metal hydrogenation catalyst.

The precursor of the active component a may be a soluble salt of the active component a, for example, at least one of nickel nitrate, cobalt nitrate, nickel acetate, cobalt acetate, basic nickel carbonate, basic cobalt carbonate, nickel chloride and cobalt chloride.

The precursor of the active component B can be soluble salt of the active component B, preferably at least one of molybdic acid, paramolybdic acid, molybdate, paramolybdate, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate and ethyl metatungstate.

According to the invention, in the preparation method of the supported sulfided metal hydrogenation catalyst, the solution in the step (1) optionally contains a complexing agent and/or a cosolvent. The type of complexing agent and/or co-solvent is well known to those skilled in the art, and the present invention is not particularly limited thereto.

The vulcanization mode is not particularly limited in the present invention, and the vulcanization process may be a wet vulcanization or a dry vulcanization. Preferably, the reaction conditions of the sulfurization include: the temperature is 140-400 deg.C, and the pressure is normal pressure-15 MPa.

According to a preferred embodiment of the present invention, the sulfur-containing medium is a mixed gas of a hydrogen-containing gas and hydrogen sulfide, the volume fraction of hydrogen sulfide in the mixed gas is 0.5-15%, and the volume space velocity of the mixed gas is 100-3000h ^-1 (ii) a And/or the sulfur-containing medium is a mixture of a sulfur-containing compound and a hydrocarbon oil, the mass fraction of the sulfur-containing compound in the mixture of the sulfur-containing compound and the hydrocarbon oil is 0.1-15% in terms of sulfur, and the liquid hourly space velocity of the mixture of the sulfur-containing compound and the hydrocarbon oil is 0.1-20h ^-1 。

More preferably, the reaction conditions for the sulfurization include: at a temperature of 140-400 ℃ and a pressure of-10 MPa, thereforThe sulfur-containing medium is a mixed gas of hydrogen-containing gas and hydrogen sulfide, the volume fraction of the hydrogen sulfide in the mixed gas is 3-10%, and the volume space velocity of the mixed gas is 300-1000h ^-1 (ii) a And/or the sulfur-containing medium is a mixture of a sulfur-containing compound and hydrocarbon oil, the mass fraction of the sulfur-containing compound in the mixture of the sulfur-containing compound and the hydrocarbon oil is 1-6% in terms of sulfur, and the liquid hourly space velocity of the mixture of the sulfur-containing compound and the hydrocarbon oil is 1-5h ^-1 。

Specifically, the mixed gas optionally contains an inert gas, and the content of the inert gas can be 0-85 vol%. In the present invention, the inert gas may be at least one of nitrogen, helium, neon and argon.

The sulfur-containing compound and hydrocarbon oil may be various sulfur-containing compounds and hydrocarbon oils conventionally used in the art for liquid phase sulfidation, for example, the sulfur-containing compound may be selected from CS ₂ At least one of dimethyl disulfide, dimethyl sulfide, t-butyl polysulfide and ethanethiol; the hydrocarbon oil may be organic hydrocarbon with 5-18 carbon atoms, gasoline fraction oil, aviation kerosene fraction oil, diesel oil fraction oil or their mixture.

In the present invention, preferably, the conditions of the first drying include: the temperature is 80-200 ℃, and the time is 1-20h.

The optional first calcination in the sense of the present invention means that calcination may or may not be carried out. The invention has wide selection range of the conditions of the first roasting, and preferably, the conditions of the first roasting comprise: the temperature is 300-550 ℃, and the time is 1-8h.

According to a preferred embodiment of the present invention, the supported zinc-containing catalyst comprises a second carrier and zinc oxide supported on the second carrier.

In the invention, the content of zinc oxide in the supported zinc-containing catalyst has a wide selection range. Preferably, the zinc oxide is present in an amount of 1 to 50 wt.%, preferably 10 to 40 wt.%, more preferably 20 to 35 wt.%, based on the total amount of the supported zinc-containing catalyst.

In a preferred case, the supported zinc-containing catalyst is a reduced supported zinc-containing catalyst. In this preferred case, the supported zinc containing catalyst has a higher selectivity for mercaptan removal.

The selection range of the second carrier is wider, and the specific selection range is preferably the same as that of the first carrier, which is not described herein again. Preferably, the second support is selected from at least one of alumina, silica and titania.

The method for producing the supported zinc-containing catalyst of the present invention is not particularly limited as long as the supported zinc-containing catalyst having the above composition can be obtained. According to the present invention, preferably, the preparation method of the supported zinc-containing catalyst comprises:

impregnating the second support with a solution containing a zinc-containing compound, followed by second drying and second calcining. In the present invention, the conditions of the second drying include: the temperature is 80-200 ℃, and the time is 1-20h.

Preferably, the conditions of the second firing include: the temperature is 250-450 ℃, and the time is 1-8h. The selection range of the zinc-containing compound is wide, and the selection range can be conventional in the field. Preferably, at least one selected from the group consisting of zinc nitrate, zinc sulfate, zinc chloride and basic zinc carbonate.

Preferably, the preparation method of the supported zinc-containing catalyst further comprises: and reducing the roasted product obtained by the second roasting.

The reduction treatment according to the present invention is preferably carried out under a hydrogen-containing atmosphere. The hydrogen-containing atmosphere may be provided by pure hydrogen or a mixed gas containing hydrogen and an inert gas (the content of hydrogen in the mixed gas is preferably 50 to 99 vol%). Preferably, the inert gas may be at least one of nitrogen, helium, neon, and argon.

Preferably, the conditions of the reduction treatment include: under the atmosphere containing hydrogen, the pressure is 0.1-15MPa, the reduction temperature is 200-550 ℃, and the gas volume space velocity is 100-3000h ^-1 The reduction time is 1-48 hours. Further preferably, the reduction treatment conditions include: under hydrogen-containing atmosphere, the pressure is 0.5-8MPa,the reduction temperature is 250-500 ℃, and the gas volume space velocity is 300-1000h ^-1 The reduction time is 2-24 hours.

According to a preferred embodiment of the present invention, the supported silver-containing catalyst comprises a third support and a silver-containing compound supported on the third support.

In the present invention, the content of the silver-containing compound in the supported silver-containing catalyst is selected from a wide range. Preferably, the supported silver-containing catalyst is used in the form of Ag ₂ The content of the silver-containing compound is 0.1 to 45% by weight, preferably 1 to 35% by weight, and more preferably 5 to 20% by weight, in terms of O.

In the present invention, the supported silver-containing catalyst has a wide range of selection of the kind of the silver-containing compound. Preferably, the silver-containing compound is selected from at least one of silver nitrate, silver oxide, silver hydroxide and silver chloride, more preferably silver nitrate.

The method for producing the supported silver-containing catalyst of the present invention is not particularly limited as long as the production of the supported silver-containing catalyst can be achieved. Preferably, the preparation method of the supported silver-containing catalyst comprises the following steps:

the third support is impregnated with a solution containing a silver-containing compound, followed by third drying. The method of the third drying in the present invention is not particularly limited, and may be selected conventionally in the art.

In the present invention, preferably, the third drying conditions include: under the condition of keeping out of the sun, the temperature is 70-150 ℃, and the time is 1-12h. Preferably, the third drying is performed under an inert atmosphere. The inert atmosphere is provided by an inert gas, which is selected as described above and will not be described in detail here. Specifically, the third drying may be performed in a stainless steel tube dried in the dark.

The selection range of the third carrier in the present invention is wider, and the specific selection range is preferably as described above for the first carrier, and will not be described herein again. Preferably, the third support is selected from at least one of alumina, silica and titania.

Further excellenceOptionally, the third carrier comprises alumina, and low temperature N is used ₂ The adsorption experiment is characterized in that the specific surface area of the alumina is 150-400m ² Per g, pore volume of 0.5-1.3cm ³ A pore size of 6 to 20nm, preferably 7 to 15nm.

More preferably, the third carrier further comprises 0.5 to 10 wt% silica, and even more preferably, the third carrier further comprises 1 to 5 wt% silica. When the catalyst prepared by the preferred embodiment is used in a mercaptan removal process, the mercaptan removal selectivity is higher, and the mercaptan in an oil product is selectively removed on the premise of smaller octane number loss, so that the total sulfur content in the oil product is effectively reduced.

When the third carrier contains alumina and silica, the method for producing the carrier is not particularly limited in the present invention, and the third carrier having the above-described characteristics is advantageous for further improving the effect of the present invention, and specifically, the silica may be introduced by an impregnation method and/or a kneading bar-extruding method, and preferably by an impregnation method. When the silica is introduced by an impregnation method, the support preparation method further comprises: the impregnated product is dried and/or calcined to convert the silica precursor to silica. In the present invention, the conditions for drying and calcining are not particularly limited, and for example, the drying temperature is from 80 to 150 ℃ and the calcining temperature is from 350 to 600 ℃. Specifically, when the amount of silicon to be incorporated is relatively large, the impregnation may be performed sequentially or may be performed a plurality of times (for example, 2 to 4 times), and the drying and/or firing may be performed after each impregnation.

The precursor of the silicon oxide can be any water-soluble silicon-containing compound and a silicon-containing compound which can be hydrolyzed in an aqueous medium to form silica gel and sol. Preferably, the precursor of the silicon oxide is selected from one or more of water glass, hydrosol and silicate ester.

According to a preferred embodiment of the present invention, the supported nickel-based catalyst comprises a fourth carrier and an active component nickel supported on the fourth carrier.

Preferably, the active component nickel is present in an amount of 1 to 50 wt.%, preferably 10 to 40 wt.%, and more preferably 20 to 35 wt.%, calculated as NiO, based on the total amount of the supported nickel-based catalyst.

In a preferred case, the supported nickel-based catalyst is a reduced supported nickel-based catalyst. The inventors of the present invention have found that when the supported nickel-based catalyst is subjected to a reduction treatment, it has a higher mercaptan selectivity when subjected to mercaptan removal.

The present invention is not particularly limited to the method for preparing the supported nickel-based catalyst, as long as it is capable of introducing nickel, which is an active component, into the fourth support. Preferably, the preparation method of the supported nickel-based catalyst comprises:

the fourth support is impregnated with a solution containing a nickel-containing compound, followed by fourth drying and fourth calcination.

The nickel-containing compound of the present invention is selected from a wide range, and is preferably at least one selected from the group consisting of nickel nitrate, nickel acetate, basic nickel carbonate and nickel chloride.

The selection range of the fourth carrier is wider, and the specific selection range is preferably as described in the first carrier, which is not described herein again. Preferably, the fourth support is selected from at least one of alumina, silica and titania.

In the present invention, preferably, the fourth drying condition includes: the temperature is 80-200 ℃, and the time is 1-20h.

The invention has wide selection range of the conditions of the fourth roasting, and preferably, the conditions of the fourth roasting comprise: the temperature is 300-500 ℃ and the time is 1-8h.

According to the present invention, preferably, the preparation method of the supported nickel-based catalyst further comprises: and reducing the roasted product obtained by the fourth roasting.

The reduction treatment of the supported nickel-based catalyst is preferably carried out under a hydrogen-containing atmosphere, which is as described above and will not be described herein.

Preferably, the conditions of the reduction treatment of the supported nickel-based catalyst include: under hydrogen-containing atmosphereThe pressure is 0.1-15MPa, the reduction temperature is 200-550 ℃, and the gas volume space velocity is 100-3000h ^-1 The reduction time is 1-48 hours. Further preferably, the conditions of the reduction treatment of the supported nickel-based catalyst include: under the atmosphere containing hydrogen, the pressure is 0.5-8MPa, the reduction temperature is 250-500 ℃, and the gas volume space velocity is 300-1000h ^-1 The reduction time is 1-24 hours.

According to the method for selectively removing mercaptan, the contact reaction in the step (1) can be carried out by mixing the supported zinc-containing catalyst and the supported sulfurized metal hydrogenation catalyst and/or the supported nickel-based catalyst and then filling the mixture into one bed layer for contact reaction, or can be carried out by filling the supported zinc-containing catalyst and the supported sulfurized metal hydrogenation catalyst and/or the supported nickel-based catalyst into different bed layers or different reactors for contact reaction. The supported zinc-containing catalyst and the supported sulfidic metal hydrogenation catalyst and/or the supported nickel-based catalyst are mixed and then filled in a bed layer for contact reaction, which is not described herein again, and a person skilled in the art can know how to operate on the basis of the above disclosure. Three different catalyst loadings, designated A, B and C, for step (1) are described in detail below.

According to a preferred embodiment A of the present invention, in the process for the selective sweetening,

the step (1) comprises a step (1-1) and a step (1-2);

the step (1-1) comprises: under the condition of first mercaptan removal, oil products are in first contact with a supported sulfurized metal hydrogenation catalyst and/or a supported nickel-based catalyst;

the step (1-2) comprises: and carrying out second contact on the stream obtained by the first contact and a supported zinc-containing catalyst under second mercaptan removal conditions to obtain the first stream. In this preferred embodiment, the catalyst in this combination exhibits a higher stability.

According to a preferred embodiment a of the present invention, the catalyst used in step (1-1) may be a supported sulfided metal hydrogenation catalyst or a supported nickel-based catalyst, or may be a mixture of a supported sulfided metal hydrogenation catalyst and a supported nickel-based catalyst, and when a supported sulfided metal hydrogenation catalyst or a supported nickel-based catalyst is used alone, the object of the present invention can be achieved, and it can be understood by those skilled in the art that when a mixture of a supported sulfided metal hydrogenation catalyst and a supported nickel-based catalyst is used, any ratio of the two is suitable for the present invention.

According to a preferred embodiment a of the present invention, the conditions of the first sweetening alcohol and the second sweetening alcohol each independently comprise: the temperature is 100-300 ℃, and the mass space velocity is 0.1-10h ^-1 Further preferably, the conditions of the first and second sweetening alcohols each independently comprise: the temperature is 100-220 ℃, and the mass space velocity is 0.5-6h ^-1 。

In this preferred embodiment a, the supported hydrogenation catalyst of the sulfided metal and/or the supported nickel-based catalyst may be loaded in one bed, or may be loaded in two different reactors or different beds of one reactor, which is not particularly limited in the present invention.

According to a preferred embodiment B of the present invention, in the process for the selective sweetening,

the step (1) comprises a step (1-A) and a step (1-B);

the step (1-A) comprises: under the third sweetening condition, the oil product is in third contact with a mixed catalyst containing a supported sulfurized metal hydrogenation catalyst and a supported zinc-containing catalyst;

the step (1-B) comprises: fourth contacting said third contacted stream with a supported nickel-based catalyst and optionally a supported zinc-containing catalyst under fourth mercaptan removal conditions to obtain said first stream. In this preferred embodiment, the catalyst in this combination has a higher mercaptan selectivity and a lower sulfur content in the resulting product.

In the mixed catalyst containing the supported sulfidic metal hydrogenation catalyst and the supported zinc-containing catalyst in the step (1-a), the loading ratio of the supported sulfidic metal hydrogenation catalyst and the supported zinc-containing catalyst can be selected in a wide range, which is not particularly limited in the present invention, for example, the loading mass ratio of the supported sulfidic metal hydrogenation catalyst and the supported zinc-containing catalyst is preferably 1 (0.1-10).

According to a preferred embodiment B of the present invention, the supported zinc-containing catalyst may or may not be incorporated in step (1-B), and the present invention is not particularly limited to this, and is preferably incorporated. When a mixture of the supported nickel-based catalyst and the supported zinc-containing catalyst is used in the step (1-B), the present invention has a wide selection range of the introduction ratio of the supported nickel-based catalyst and the supported zinc-containing catalyst, for example, the mass ratio of the supported nickel-based catalyst to the supported zinc-containing catalyst may be 1: (0.05-1).

According to a preferred embodiment B of the present invention, the conditions of the third sweetening step comprise: the temperature is 100-300 ℃, more preferably 160-220 ℃; the mass space velocity is 0.1-10h ^-1 More preferably 0.5 to 6 hours ^-1 。

According to a preferred embodiment B of the present invention, the fourth mercaptan removal conditions comprise: the temperature is 100-300 ℃, and more preferably 100-220 ℃; the mass space velocity is 0.1-10h ^-1 More preferably 0.5 to 6 hours ^-1 。

In this preferred embodiment B, the supported sulfided metal hydrogenation catalyst and the supported zinc-containing catalyst are packed in one bed. The supported nickel-based catalyst can be filled in different beds of one reactor with a supported sulfurized metal hydrogenation catalyst and a supported zinc-containing catalyst, and can also be filled in different reactors, preferably different reactors.

According to a preferred embodiment C of the present invention, in the process for the selective sweetening,

the step (1) comprises a step (1-I) and a step (1-II);

the step (1-I) comprises the following steps: under the condition of fifth mercaptan removal, oil products are in fifth contact with a supported sulfurized metal hydrogenation catalyst;

the step (1-II) comprises: and under a sixth mercaptan removal condition, sixth contacting the material flow obtained by the fifth contacting with a mixed catalyst containing a supported nickel-based catalyst and a supported zinc-containing catalyst to obtain the first material flow. In this preferred embodiment, the catalyst in this combination has a higher mercaptan selectivity and a lower sulfur content in the resulting product.

In the mixed catalyst containing the supported nickel-based catalyst and the supported zinc-containing catalyst in the step (1-II), the loading ratio of the supported nickel-based catalyst and the supported zinc-containing catalyst can be selected in a wide range, and the invention is not particularly limited thereto, for example, the loading mass ratio of the supported nickel-based hydrogenation catalyst and the supported zinc-containing catalyst is preferably 1 (0.1-10).

According to a preferred embodiment C of the invention, the conditions of the fifth sweetening step comprise: the temperature is 100-300 ℃, more preferably 160-220 ℃; the mass space velocity is 0.1-10h ^-1 More preferably 0.5 to 6 hours ^-1 。

According to a preferred embodiment C of the invention, the sixth sweetening condition comprises: the temperature is 100-300 ℃, and more preferably 100-220 ℃; the mass space velocity is 0.1-10h ^-1 More preferably 0.5 to 6 hours ^-1 。

In this preferred embodiment C, the supported nickel-based catalyst and the supported zinc-containing catalyst are packed in one bed, and the supported sulfidic metal hydrogenation catalyst may be packed in a different bed of one reactor than the supported nickel-based catalyst and the supported zinc-containing catalyst, or may be packed in a different reactor, preferably in a different reactor.

In the present invention, unless otherwise specified, the terms "first", "second", "third", "fourth", "fifth" and "sixth" do not limit the present invention, but are used for descriptive convenience and for distinguishing purposes.

According to the present invention, preferably, the conditions of the contact reaction of step (2) include: the temperature is 20-300 ℃, and the mass space velocity is 0.1-10h ^-1 (ii) a Further preferably, the conditions of the contact reaction in the step (2) include: the temperature is 20-220 ℃, and the mass space velocity is 2-6h ^-1 . The pressure of the contacting in the step (2) is not particularly limited in the present inventionIt can be carried out under normal pressure.

The method provided by the invention is suitable for the sweetening treatment of various oils, for example, the oils can be selected from at least one organic hydrocarbon material with the carbon number of 5-18, preferably from at least one organic hydrocarbon material with the carbon number of 6-12. Preferably, the oil is at least one of catalytically cracked gasoline, coker gasoline, steam cracked gasoline, thermally cracked gasoline, and kerosene.

Preferably, the oil product is petroleum hydrocarbon fraction with the distillation range of 10-230 ℃, more preferably 20-230 ℃, and more preferably hydrogenated gasoline fraction.

Preferably, the mercaptan content is 1-50ug/g and the olefin content is not less than 5 wt%, based on the total oil.

The present invention will be described in detail below by way of examples.

In the following examples, the industrial alumina supports were purchased from catalyst division, petrochemical company, inc; all the reagents are purchased from chemical reagents of national medicine group, inc., and are analytically pure. Industrial gamma-alumina-1 (specific surface area 256 m) ² /g、0.67cm ³ G, a few pore diameters of 7.5 nm); industrial gamma-alumina-2 (specific surface area 228 m) ² /g、0.88cm ³ A few pore sizes of 9.5 nm/g); industrial gamma-alumina-3 (specific surface area 289 m) ² /g、0.96cm ³ (ii)/g, several pore diameters of 11 nm).

Preparation example I-1

The preparation example is a preparation process of the supported sulfurized metal hydrogenation catalyst:

adopts industrial gamma-alumina-1 (the specific surface area is 256 m) ² /g、0.67cm ³ /g, can have a pore size of 7.5 nm) as the first support, and the catalyst is prepared by an impregnation method.

9.69 g of ethylene diamine tetraacetic acid, 2.32 g of trans-1, 2-cyclohexanediamine tetraacetic acid, 3.28 g of glyoxylic acid, 1.95 g of glycolic acid, 3.89 g of tartaric acid and 4.61 g of malic acid are weighed, added into water containing 30 ml of strong ammonia water, stirred and dissolved uniformly, then 17.42 g of cobalt nitrate hexahydrate and 23.36 g of ammonium heptamolybdate are added, the volume is determined to be 182 ml,200 g of the above alumina carrier was impregnated with this solution for 4 hours and dried at 120 ℃ for 3 hours. The resulting CoMo/Al ₂ O ₃ The metal loading of the catalyst was: 2.0 wt.% CoO and 8.4 wt.% MoO ₃ 。

(2) The catalyst was sulfided: crushing the catalyst into particles of 20-30 meshes, loading 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and adding the catalyst containing H ₂ S、N ₂ Ar and H ₂ The mixed gas (the volume contents of the four are respectively 3 percent, 50 percent, 22 percent and 25 percent) is introduced into the device, and the gas volume space velocity is 400h ^-1 Increasing the pressure to 1.6MPa, heating to 320 ℃, keeping the temperature for 4 hours, and then cooling to room temperature to obtain the vulcanized CoMo/Al ₂ O ₃ Catalyst I-1. The parameters of the properties of catalyst I-1 are given in Table 1.

Preparation example I-2

33.61 g of ethylene diamine tetraacetic acid, 3.45 g of trans-1, 2-cyclohexanediamine tetraacetic acid, 2.36 g of glyoxylic acid, 1.59 g of glucose, 3.15 g of tartaric acid and 3.58 g of glycerol are weighed, added into water containing 49 ml of concentrated ammonia water, stirred and dissolved uniformly, then 33.36 g of cobalt nitrate hexahydrate and 38.23 g of ammonium heptamolybdate are added, the volume is determined to be 182 ml, 200 g of the alumina carrier is soaked by the solution for 4 hours, and the alumina carrier is dried for 3 hours at 140 ℃. The obtained CoMo/Al ₂ O ₃ The metal loading of the catalyst was: 3.6 wt.% CoO and 12.9 wt.% MoO ₃ 。

(2) The catalyst was sulfided: crushing the catalyst into particles of 20-30 meshes, loading 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and adding the catalyst containing H ₂ S、N ₂ Ar and H ₂ The mixed gas (the volume contents of the four are respectively 5 percent, 12 percent, 55 percent and 28 percent) is introduced into the device, and the gas volume space velocity is 400h ^-1 Increasing the pressure to 1.6MPa, raising the temperature to 320 ℃, keeping the temperature for 4 hours, and then reducing the temperature to room temperature to obtain the vulcanized CoMo/Al ₂ O ₃ Catalyst I-2. Properties of catalyst I-2The parameters are listed in table 1.

Preparation example I-3

Adopts industrial gamma-alumina-1 (the specific surface area is 256 m) ² /g、0.67cm ³ /g, several pore diameters of 7.5 nm) as a first support, and the catalyst was prepared by an impregnation method.

54.06 g of ethylene diamine tetraacetic acid, 1.85 g of trans-1, 2-cyclohexanediamine tetraacetic acid, 3.36 g of glyoxylic acid, 2.59 g of sucrose, 2.65 g of glyoxylic acid, 1.58 g of tartaric acid and 5.62 g of ammonium citrate are weighed, added into water containing 60 ml of concentrated ammonia water, stirred and dissolved uniformly, then 50.25 g of cobalt nitrate hexahydrate and 48.36 g of ammonium heptamolybdate are added, the volume is determined to be 182 ml, 200 g of the alumina carrier is soaked by the solution for 4 hours, and the alumina carrier is dried for 3 hours at 140 ℃. The resulting CoMo/Al ₂ O ₃ The metal loading of the catalyst was: 5.1 wt% CoO and 15.5 wt% MoO ₃ 。

(2) Sulfurizing the catalyst: crushing the catalyst into particles of 20-30 meshes, loading 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and adding the catalyst containing H ₂ S、N ₂ Ar and H ₂ The mixed gas (the volume contents of the four are respectively 4 percent, 37 percent, 33 percent and 26 percent) is introduced into the device, and the gas volume space velocity is 400h ^-1 Increasing the pressure to 6.4MPa, raising the temperature to 320 ℃, keeping the temperature for 4 hours, and then reducing the temperature to room temperature to obtain the vulcanized CoMo/Al ₂ O ₃ Catalyst I-3. The parameters of the properties of catalyst I-3 are set forth in Table 1.

Preparation example I-4

6.89 g of trans-1, 2-cyclohexanediaminetetraacetic acid, 4.82 g of glyoxylic acid, 2.59 g of glycolic acid, 3.89 g of citric acid and 4.68 g of malic acid are weighed, added into water containing 30 ml of concentrated ammonia water, stirred and dissolved uniformly, then 17.42 g of cobalt nitrate hexahydrate and 23.36 g of ammonium heptamolybdate are added, the volume is determined to be 175 ml, 200 g of the alumina carrier is soaked by the solution for 4 hours, and the alumina carrier is dried for 3 hours at 120 ℃. The resulting CoMo/Al ₂ O ₃ Metallic negative of catalystThe loading capacity is as follows: 2.0 wt.% CoO and 8.4 wt.% MoO ₃ 。

(2) The catalyst was sulfided: crushing the catalyst into particles of 20-30 meshes, filling 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and adding H ₂ S、N ₂ Ar and H ₂ The mixed gas (the volume contents of the four are respectively 5 percent, 10 percent, 15 percent and 70 percent) is introduced into the device, and the gas volume space velocity is 400h ^-1 Increasing the pressure to 1.6MPa, raising the temperature to 320 ℃, keeping the temperature for 4 hours, and then reducing the temperature to room temperature to obtain the vulcanized CoMo/Al ₂ O ₃ Catalyst I-4. The properties of catalyst I-4 are given in Table 1.

Preparation example II-1

Adopts industrial gamma-alumina-2 (the specific surface area is 228 m) ² /g、0.88cm ³ A few pore diameters of 9.5 nm) as a carrier, and the catalyst is prepared by an impregnation method. The preparation method of the supported zinc-containing catalyst in an oxidation state comprises the following steps: 200 g of an industrial gamma-alumina carrier was weighed, the carrier was impregnated with 220 ml of an aqueous solution containing 87 g of zinc nitrate for 2 hours, dried at 120 ℃ for 4 hours and then calcined at 350 ℃ for 4 hours. Obtaining ZnO/Al in an oxidized state ₂ O ₃ Catalyst II-1 (ZnO loading 10.6 wt%).

Preparation example II-2

Adopts industrial gamma-alumina-3 (the specific surface area is 289 m) ² /g、0.96cm ³ A few pore diameters of 11 nm) as a carrier, and the catalyst is prepared by an impregnation method. The preparation method of the supported zinc-containing catalyst in an oxidation state comprises the following steps: 200 g of technical gamma-alumina-3 was weighed, the second support was impregnated with 240 ml of an aqueous solution containing 128 g of zinc nitrate for 2 hours, dried at 120 ℃ for 4 hours, and then calcined at 350 ℃ for 4 hours to obtain a first impregnated product. Then, 230 ml of an aqueous solution containing 118 g of zinc nitrate was used for impregnation to obtain a first-impregnated product for 2 hours, dried at 120 ℃ for 4 hours, and then calcined at 350 ℃ for 4 hours to obtain a second-impregnated product. The second impregnation was further impregnated with 223 ml of an aqueous solution containing 113 g of zinc nitrate to give a second impregnated product for 2 hours, dried at 120 ℃ for 4 hours, and then calcined at 350 ℃ for 4 hours. Obtaining ZnO/Al in an oxidized state ₂ O ₃ Catalyst II-2 (ZnO loading 32.9 wt%).

Reduction treatment: crushing the catalyst into particles of 20-30 meshes, loading 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and introducing N under 4MPa ₂ Ar and H ₂ The volume content of the mixed gas (the three are respectively 15 percent, 15 percent and 70 percent), and the gas volume space velocity is 800h ^-1 Raising the temperature to 400 ℃, keeping the temperature for 4 hours, and then cooling to room temperature. Obtaining the load type zinc-containing catalyst II-3 after reduction treatment.

Preparation example III-1

Adopts industrial gamma-alumina-3 (the specific surface area is 289 m) ² /g、0.96cm ³ A few pore diameters of 11 nm) as a third carrier, and the catalyst is prepared by an impregnation method.

The preparation method of the supported silver-containing catalyst comprises the following steps: 200 g of an industrial alumina carrier (third carrier) was weighed, the carrier was impregnated with 240 ml of an aqueous solution containing 65 g of silver nitrate for 2 hours, and the impregnated carrier was put into a dry stainless steel tube and dried at 100 ℃ for 4 hours under a nitrogen purge. To obtain AgNO ₃ /Al ₂ O ₃ Catalyst III-1, with Ag ₂ The content was 18.1% by weight in terms of O.

Preparation examples III-2, III-3 and III-4

Adopts industrial gamma-alumina-3 (the specific surface area is 289 m) ² /g、0.96cm ³ /g, several pore sizes 11 nm) as a third support.

The preparation method of the silicon-1 carrier comprises the following steps: soaking an industrial gamma-alumina-3 carrier for 4 hours by using 240 ml of absolute ethyl alcohol solution containing 10 g of tetraethoxysilane, drying for 4 hours at 120 ℃, and then roasting for 4 hours at 550 ℃; to obtain SiO ₂ A silicon-1 support in an amount of 1.4 wt%.

The preparation method of the silicon-2 carrier comprises the following steps: impregnating an industrial gamma-alumina-3 carrier with 240 ml of an absolute ethyl alcohol solution containing 10 g of tetraethoxysilane for 4 hours, drying at 120 ℃ for 4 hours, and then roasting at 550 ℃ for 4 hours; to obtain SiO ₂ A silicon-1 support in an amount of 1.4 wt%. Then 240 ml of absolute ethyl alcohol solution containing 9 g of tetraethoxysilane is used for soaking the silicon-1 carrier for 4 hours, the carrier is dried for 4 hours at the temperature of 120 ℃, and then the carrier is roasted for 4 hours at the temperature of 550 ℃; to obtain SiO ₂ Silicon-2 carrier with a content of 2.7 wt%And (3) a body.

The preparation method of the silicon-3 carrier comprises the following steps: soaking an industrial gamma-alumina-3 carrier for 4 hours by using 240 ml of absolute ethyl alcohol solution containing 36 g of tetraethoxysilane, drying for 4 hours at 120 ℃, and then roasting for 4 hours at 550 ℃; to obtain SiO ₂ A silicon-3 support in an amount of 4.9 wt.%.

The above silicon-1 carrier, silicon-2 carrier and silicon-3 carrier were impregnated with 240 ml of an aqueous solution containing 65 g of silver nitrate for 2 hours, respectively, and were charged into dry stainless steel tubes, respectively, and dried at 100 ℃ for 4 hours under nitrogen purging. Then sequentially get as Ag ₂ 18.1% by weight, calculated as O, of catalysts III-2, III-3 and III-4.

Preparation example III-5

The above silicon-2 carrier was impregnated with 240 ml of an aqueous solution containing 3.5 g of silver nitrate for 2 hours, and then dried in a dry stainless steel tube at 100 ℃ for 4 hours under a nitrogen purge. Catalyst III-5 (in Ag) is obtained ₂ Content 1.2 wt.% calculated as O).

Preparation example III-6

The above silicon-2 carrier was impregnated with 240 ml of an aqueous solution containing 15.9 g of silver nitrate for 2 hours, and then dried in a dry stainless steel tube at 100 ℃ for 4 hours under a nitrogen purge. Catalyst III-6 (in Ag) was obtained ₂ Content 5.1 wt.% calculated as O).

Preparation examples III to 7

The above silicon-2 carrier was impregnated with 240 ml of an aqueous solution containing 35.8 g of silver nitrate for 2 hours, and then dried in a dry stainless steel tube at 100 ℃ for 4 hours under a nitrogen purge. Catalyst III-7 (in Ag) is obtained ₂ Content 10.9 wt% calculated as O).

Preparation example IV-1

Adopts industrial gamma-alumina-1 (the specific surface area is 256 m) ² /g、0.67cm ³ Per g, several pore diameters of 7.5 nm) as a carrier, and the catalyst was prepared by an impregnation method. The preparation method of the supported nickel-containing catalyst in an oxidation state comprises the following steps: 200 g of technical gamma-alumina-1 support are weighed, impregnated with 182 ml of an aqueous solution containing 96 g of nickel nitrate for 2 hours, dried at 120 ℃ for 4 hours and then calcined at 350 ℃ for 4 hours. To obtain oxidationNiO/Al of state ₂ O ₃ Catalyst (NiO loading 10.9 wt%).

Reduction treatment: crushing the catalyst into particles of 20-30 meshes, loading 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and introducing N under normal pressure ₂ Ar and H ₂ The volume content of the mixed gas (three are respectively 2 percent, 3 percent and 95 percent), and the gas volume space velocity is 400h ^-1 Raising the temperature to 350 ℃, keeping the temperature for 4 hours, and then cooling to room temperature. Obtaining the reduced supported nickel-based catalyst IV-1.

Preparation example IV-2

Adopts industrial gamma-alumina-2 (the specific surface area is 228 m) ² /g、0.88cm ³ /g, several pore diameters of 9.5 nm) as a carrier, and preparing the catalyst by an impregnation method. The preparation method of the supported nickel-containing catalyst in an oxidation state comprises the following steps: 200 g of technical gamma-alumina-2 were weighed, the support was impregnated with 220 ml of an aqueous solution containing 112 g of nickel nitrate for 2 hours, dried at 120 ℃ for 4 hours and then calcined at 350 ℃ for 4 hours. A leaching product is obtained. The first-impregnated product was further impregnated with 215 ml of an aqueous solution containing 100 g of nickel nitrate for 2 hours, dried at 120 ℃ for 4 hours, and then calcined at 350 ℃ for 4 hours. Obtaining NiO/Al in an oxidation state ₂ O ₃ Catalyst (NiO loading 21.4 wt%).

Reduction treatment: crushing the catalyst into particles of 20-30 meshes, loading 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and introducing N-containing gas under normal pressure ₂ Ar and H ₂ The volume content of the mixed gas (the three are respectively 5 percent, 10 percent and 85 percent), and the gas volume space velocity is 400h ^-1 Raising the temperature to 350 ℃, keeping the temperature for 4 hours, and then cooling to room temperature. Obtaining the reduced supported nickel-based catalyst IV-2.

Preparation example IV-3

Adopts industrial gamma-alumina-3 (the specific surface area is 289 m) ² /g、0.96cm ³ A few pore diameters of 11 nm) as a carrier, and the catalyst is prepared by an impregnation method. The preparation method of the supported nickel-containing catalyst in an oxidation state comprises the following steps: 200 g of industrial gamma-alumina-3 are weighed, the second carrier is impregnated with 240 ml of aqueous solution containing 126 g of nickel nitrate for 2 hours,drying at 120 deg.C for 4 hours, and then calcining at 350 deg.C for 4 hours to obtain a first-leaching product. Then, the primary leaching product was impregnated with 230 ml of an aqueous solution containing 118 g of nickel nitrate for 2 hours, dried at 120 ℃ for 4 hours, and then calcined at 350 ℃ for 4 hours to obtain a secondary leaching product. The resultant second-impregnated product was further impregnated with 223 ml of an aqueous solution containing 109 g of nickel nitrate for 2 hours, dried at 120 ℃ for 4 hours, and then calcined at 350 ℃ for 4 hours. Obtaining NiO/Al in an oxidation state ₂ O ₃ Catalyst (NiO loading 31.2 wt%).

Reduction treatment: crushing the catalyst into particles of 20-30 meshes, loading 100 g of the crushed catalyst into a constant temperature area of a fixed bed hydrogenation reactor, and introducing N under normal pressure ₂ Ar and H ₂ The volume content of the mixed gas (12 percent, 33 percent and 55 percent) of the mixed gas and the gas volume space velocity of 400h ^-1 Raising the temperature to 350 ℃, keeping the temperature for 4 hours, and then cooling to room temperature. Obtaining the reduced supported nickel-based catalyst IV-3.

TABLE 1

Note: A/(A + B) means the atomic ratio of the active component A to the sum of the active metal component A and the active metal component B; the content of the component A and the content of the component B are calculated by oxide.

Example A-1

This example illustrates the selective sweetening process of the present invention. The method comprises the following steps:

(1-1) carrying out first contact on hydrogenated heavy gasoline (the mercaptan content is 28 mu g/g, the total sulfur content is 65 mu g/g, the olefin volume fraction is 25.6 percent, and the same is true below) and a supported sulfided metal hydrogenation catalyst I-1 under the first mercaptan removal condition. The conditions of the first contact include: the temperature is 180 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 。

(1-2) carrying out second contact on the material flow obtained by the first contact and a supported zinc-containing catalyst II-1 under a second mercaptan removal condition to obtain a first material flow. Condition package of second contactComprises the following steps: the temperature is 200 ℃, the pressure is normal pressure, and the mass space velocity is 2h ^-1 。

(2) And carrying out contact reaction on the first stream and the supported silver-containing catalyst III-1. The conditions of the contact reaction include: the temperature is 100 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 . After 100h of stabilization, the sample was analyzed, and the specific results are shown in Table 2.

Example A-2

The procedure of example A-1 was followed, except that in step (1-1), the supported sulfided metal hydrogenation catalyst I-1 was replaced with an equal mass of supported nickel-based catalyst IV-1. Specific results are shown in Table 2.

Example A-3

The procedure of example A-2 was followed, except that in the step (1-1), the supported nickel-based catalyst IV-1 was replaced with the supported nickel-based catalyst IV-3 of an equal mass. Specific results are shown in Table 2.

Example A-4

The procedure of example A-1 was followed except that, in step (1-1), 1/2 mass of the supported sulfided metal hydrogenation catalyst I-1 was replaced with the supported sulfided metal hydrogenation catalyst I-2, and the remaining 1/2 mass of the supported sulfided metal hydrogenation catalyst I-1 was replaced with the supported nickel-based catalyst IV-2 of equal mass. Specific results are shown in Table 2.

Example B-1

(1-A) under a third mercaptan removal condition, carrying out third contact on hydrogenated medium gasoline and a mixed catalyst (the mass ratio of the I-3 to the II-2 is 60) containing a supported sulfurized metal hydrogenation catalyst I-3 and a supported zinc-containing catalyst II-2 in a first fixed bed reactor. The conditions of the third contacting include: the temperature is 180 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 。

(1-B) carrying out fourth contact on the material flow obtained by the third contact and a supported nickel-based catalyst IV-3 in a second fixed bed reactor under the fourth mercaptan removal condition to obtain a first material flow. Strip of the fourth contactThe piece of equipment includes: the temperature is 175 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 。

(2) And carrying out contact reaction on the first stream and the supported silver-containing catalyst III-1. The conditions of the contact reaction include: the temperature is 120 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 . After 100h of stabilization, the sample was analyzed, and the specific results are shown in Table 2.

Examples B-2 to B-7

The procedure as in example B-1 was conducted except that the supported silver-containing catalyst III-1 in step (2) was replaced with a supported silver-containing catalyst III-2 to a supported silver-containing catalyst III-7, respectively.

Comparative example 1

The procedure of example B-1 was followed except that the supported zinc-containing catalyst II-2 was replaced with an equivalent mass of supported sulfidic metal hydrogenation catalyst I-3, i.e., no supported zinc-containing catalyst was used, and the specific results are set forth in Table 2.

Example B-8

The procedure of example B-1 was followed, except that the supported zinc-containing catalyst II-2 was replaced with an equal mass of the supported zinc-containing catalyst II-3 (subjected to reduction treatment). Specific results are shown in Table 2.

Example B-9

The procedure of example B-1 was followed, except that the supported sulfided metal hydrogenation catalyst I-3 was replaced with an equivalent mass of supported sulfided metal hydrogenation catalyst I-4. Specific results are shown in Table 2.

Example B-10

The procedure of example B-1 was followed, except that the supported nickel-based catalyst IV-3 was replaced with a mixed catalyst of the supported nickel-based catalyst IV-3 and the supported zinc-containing catalyst II-3 (the mass ratio of IV-3 and II-3 was 85; meanwhile, the supported silver-containing catalyst III-1 is replaced by a supported silver-containing catalyst III-3. Specific results are shown in Table 2.

Example C-1

(1-I) in the fifthAnd (3) carrying out fifth contact on the hydrogenated heavy gasoline and the supported sulfurized metal hydrogenation catalyst I-1 under the mercaptan removal condition. The conditions of the fifth contacting include: the temperature is 180 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 。

(1-II) subjecting the stream obtained by the fifth contact to sixth contact with a mixed catalyst (the mass ratio of IV-3 to II-3 is 80) containing a supported nickel-based catalyst IV-3 and a supported zinc-containing catalyst II-3) under sixth mercaptan removal conditions to obtain a first stream. The conditions of the sixth contact include: the temperature is 180 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 。

(2) And carrying out contact reaction on the first stream and the supported silver-containing catalyst III-2. The conditions of the contact reaction include: the temperature is 180 ℃, the pressure is normal pressure, and the mass space velocity is 4h ^-1 . After 100h of stabilization, the sample was analyzed, and the specific results are shown in Table 2.

TABLE 2

The results in Table 2 show that the method provided by the invention can show higher mercaptan removal selectivity and activity, and can effectively reduce the total sulfur content in the product while selectively removing mercaptan sulfur in the oil product, thereby realizing the aim of producing low-sulfur gasoline.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A process for the selective sweetening of mercaptans, the process comprising:

the step (1) and the step (2) are carried out under the non-hydrogen condition;

wherein the first catalyst comprises a supported zinc-containing catalyst and a supported sulfided metal hydrogenation catalyst and/or a supported nickel-based catalyst;

the supported sulfidation metal hydrogenation catalyst comprises a first carrier, and an active metal component A and an active metal component B which are loaded on the first carrier, wherein the active metal component A is selected from at least one of VIII group metal elements, and the active metal component B is selected from at least one of VIB group metal elements;

the supported zinc-containing catalyst comprises a second carrier and zinc oxide supported on the second carrier; based on the total amount of the supported zinc-containing catalyst, the content of zinc oxide is 1-50 wt%;

the supported silver-containing catalyst comprises a third carrier and a silver-containing compound supported on the third carrier; based on the total amount of the supported silver-containing catalyst, ag ₂ Calculated by O, the content of the silver-containing compound is 0.1 to 45 weight percent; the preparation method of the supported silver-containing catalyst comprises the following steps: impregnating the third carrier with a solution containing a silver-containing compound, followed by third drying;

the supported nickel-based catalyst comprises a fourth carrier and an active component nickel loaded on the fourth carrier; based on the total amount of the supported nickel-based catalyst, the content of an active component nickel is 1-50 wt% calculated by NiO, and the supported nickel-based catalyst is a reduced supported nickel-based catalyst.

2. The method of claim 1, wherein,

the active metal component A is Co and/or Ni, and the active metal component B is Mo and/or W.

3. The method of claim 1, wherein,

in the supported sulfidic metal hydrogenation catalyst, the atomic ratio of the active metal component A to the sum of the active metal component A and the active metal component B is above 0.25 as measured by an X-ray fluorescence method.

4. The method of claim 3, wherein,

in the supported sulfurized metal hydrogenation catalyst, the atomic ratio of the active metal component A to the sum of the active metal component A and the active metal component B is 0.3-0.4 measured by an X-ray fluorescence method.

5. The method of claim 1, wherein,

the degree of sulfidation of the supported sulfided metal hydrogenation catalyst is 70-99% as measured by X-ray photoelectron spectroscopy.

6. The method of claim 1, wherein,

in the supported sulfidation metal hydrogenation catalyst measured by X-ray photoelectron spectroscopy, the content of the II active phase A-B-S is more than 30 percent, wherein the content of the II active phase A-B-S refers to the ratio of the amount of the active metal component A existing in the form of the II active phase A-B-S to the total amount of the active metal component A measured by the X-ray photoelectron spectroscopy.

7. The process of claim 6, wherein the supported sulfided metal hydrogenation catalyst has a class II active phase, A-B-S, content of from 35 to 70% as measured by X-ray photoelectron spectroscopy.

8. The process of claim 6 wherein the supported sulfided metal hydrogenation catalyst has a group II active phase A-B-S content of from 40 to 70% as measured by X-ray photoelectron spectroscopy.

9. The process of claim 1, wherein the first support is selected from one or more of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.

10. The method of claim 1 or 2,

the content of the first carrier is 50-90 wt% based on the total amount of the supported sulfidic metal hydrogenation catalyst; the content of the active metal component A is 1-15 wt% calculated by oxide; the content of the active metal component B is 5 to 45% by weight.

11. The method of claim 10, wherein,

the content of the first carrier is 74-86 wt% based on the total amount of the supported sulfidic metal hydrogenation catalyst; the content of the active metal component A is 2-6 wt% calculated by oxide; the content of the active metal component B is 8 to 20% by weight.

12. The process of any of claims 1-9, wherein the supported sulfided metal hydrogenation catalyst is prepared by a process comprising:

(1) Impregnating the first support with a solution containing a precursor of an active metal component a and a precursor of an active metal component B, followed by a first drying and optionally a first calcination;

(2) Vulcanizing the solid product obtained in the step (1);

13. The method of claim 12, wherein,

the reaction conditions for the sulfurization include: the temperature is 140-400 deg.C, and the pressure is normal pressure-15 MPa.

14. The method of claim 12, wherein,

the sulfur-containing medium is a mixed gas of hydrogen-containing gas and hydrogen sulfide, the volume fraction of the hydrogen sulfide in the mixed gas is 0.5-15%, and the volume space velocity of the mixed gas is 100-3000h ^-1 (ii) a And/or the sulfur-containing medium is a mixture of a sulfur-containing compound and a hydrocarbon oil, the mass fraction of the sulfur-containing compound in the mixture of the sulfur-containing compound and the hydrocarbon oil is 0.1-15% in terms of sulfur, and the liquid hourly space velocity of the mixture of the sulfur-containing compound and the hydrocarbon oil is 0.1-20h ^-1 。

15. The process according to claim 1, wherein the zinc oxide is present in an amount of 10 to 40 wt.%, based on the total amount of the supported zinc-containing catalyst.

16. The process of claim 1, wherein the supported zinc-containing catalyst is a reduced-treated supported zinc-containing catalyst.

17. The method of claim 1, wherein,

the preparation method of the supported zinc-containing catalyst comprises the following steps:

and impregnating the second carrier with a solution containing a zinc-containing compound, and then performing second drying and second calcination.

18. The method of claim 17, wherein,

the preparation method of the zinc-containing catalyst further comprises the following steps: and reducing the roasted product obtained by the second roasting.

19. The method of claim 18, wherein,

the reduction treatment conditions include: under hydrogen-containing atmosphere, the pressure is 0.1-15MPa, the reduction temperature is 200-550 ℃, and the gas volume space velocity is 100-3000h ^-1 The reduction time is 1-48 hours.

20. The method of any one of claims 1 and 15-19,

the second support is selected from one or more of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.

21. The method of claim 1, wherein,

based on the total amount of the supported silver-containing catalyst, ag is used ₂ Calculated by O, the content of the silver-containing compound is 1 to 35 weight percent.

22. The method of claim 1, wherein,

the silver-containing compound is selected from silver nitrate and/or silver chloride.

23. The method of claim 1, wherein,

the third carrier is selected from at least one of alumina, silica and titania.

24. The method of claim 1, wherein,

the third carrier comprises alumina and adopts low-temperature N ₂ Adsorption characterization, wherein the specific surface area of the alumina is 150-400m ² Per g, pore volume of 0.5-1.3cm ³ A few pores of 6-20nm in diameter/g.

25. The method of claim 24, wherein,

the third support also contains 0.5 to 10 weight percent silica.

26. The method of claim 24, wherein,

the third support further comprises 1-5 wt% silica.

27. The method of claim 1, wherein,

based on the total amount of the supported nickel-based catalyst, the content of the active component nickel is 10-40 wt% calculated by NiO.

28. The method of claim 1, wherein,

the preparation method of the supported nickel-based catalyst comprises the following steps:

and (3) impregnating the fourth carrier by adopting a solution containing a nickel-containing compound, then carrying out fourth drying and fourth roasting, and reducing a roasted product obtained by the fourth roasting.

29. The method of claim 28, wherein,

the reduction treatment conditions include: under the atmosphere containing hydrogen, the pressure is 0.1-4MPa, the reduction temperature is 200-550 ℃, and the gas volume space velocity is 100-3000h ^-1 The reduction time is 1-48 hours.

30. The method of any one of claims 1, 27-29,

the fourth support is selected from one or more of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.

31. The method of claim 1, wherein,

the step (1) comprises a step (1-1) and a step (1-2);

the step (1-2) comprises: and carrying out second contact on the stream obtained by the first contact and a supported zinc-containing catalyst under second mercaptan removal conditions to obtain the first stream.

32. The method of claim 31, wherein,

the conditions for the first and second mercaptans and for the second sweetening step each independently include: the temperature is 100-300 ℃, and the mass space velocity is 0.1-10h ^-1 。

33. The method of claim 31, wherein,

the first sweetening alcohol and the second sweetening conditions each independently comprise: the temperature is 100-220 ℃, and the mass space velocity is 0.5-6h ^-1 。

34. The method of claim 1, wherein,

the step (1) comprises a step (1-A) and a step (1-B);

the step (1-B) comprises: fourth contacting said third contacted stream with a supported nickel-based catalyst and optionally a supported zinc-containing catalyst under fourth mercaptan removal conditions to obtain said first stream.

35. The method of claim 34, wherein,

the third mercaptan removal conditions comprise: the temperature is 100-300 ℃; the mass space velocity is 0.1-10h ^-1 ；

The fourth mercaptan removal conditions comprise: the temperature is 100-300 ℃; the mass space velocity is 0.1-10h ^-1 。

36. The method of claim 34, wherein,

the third mercaptan removal conditions comprise: the temperature is 160-220 ℃; the mass space velocity is 0.5-6h ^-1 ；

The fourth mercaptan removal conditions comprise: the temperature is 100-220 ℃; the mass space velocity is 0.5-6h ^-1 。

37. The method of claim 1, wherein,

the step (1) comprises a step (1-I) and a step (1-II);

the step (1-I) comprises the following steps: under the condition of fifth sweetening, the oil product is in fifth contact with a supported sulfurized metal hydrogenation catalyst;

the step (1-II) comprises: and under sixth mercaptan removal conditions, sixth contacting the stream obtained by the fifth contacting with a mixed catalyst containing a supported nickel-based catalyst and a supported zinc-containing catalyst to obtain the first stream.

38. The method of claim 37, wherein,

the fifth sweetening condition comprises: the temperature is 100-300 ℃; the mass space velocity is 0.1-10h ^-1 ；

The sixth mercaptan removal conditions comprise: the temperature is 100-300 ℃; the mass space velocity is 0.1-10h ^-1 。

39. The method of claim 38, wherein,

the fifth sweetening condition comprises: the temperature is 160-220 ℃; the mass space velocity is 0.5-6h ^-1 ；

The sixth mercaptan removal conditions comprise: the temperature is 100-220 ℃; the mass space velocity is 0.5-6h ^-1 。

40. The method of claim 1, wherein the conditions of the contact reaction of step (2) comprise: the temperature is 20-300 ℃; quality ofThe space velocity is 0.1-10h ^-1 。

41. The method of claim 40, wherein the conditions of the contact reaction of step (2) comprise: the temperature is 20-220 ℃; the mass space velocity is 2-6h ^-1 。