A desulfurization filler and its preparation and application

Abstract

The present invention discloses a desulfurization filler and a preparation method and application thereof. The desulfurization filler comprises a filler, a silane layer, a first modified layer and a second modified layer from the inside to the outside; the first modified layer contains a phenyl group; the second modified layer contains a secondary amine group and a primary amine group. The preparation method of the desulfurization filler comprises: performing a silanization treatment on the filler to obtain a silanized filler; then performing a first modification treatment, a second modification treatment and an activation treatment on the silanized filler in sequence to obtain the desulfurization filler. The desulfurization filler of the present invention is suitable for deep removal of sulfur-containing impurities in raw dry gas that affect the activity of ethylbenzene alkylation catalyst.

Description

Technical Field

[0001] The invention relates to the technical field of preparing ethylbenzene from dry gas, and relates to a desulfurization filler and a preparation method thereof, as well as application in deep removal of impurities (especially sulfur-containing impurities) in dry gas. Background Art

[0002] Dry gas refers to the tail gas that cannot be liquefied in the process of oil refining. It mainly comes from the secondary processing of crude oil and is generally used as fuel. In order to make full use of the dilute ethylene in dry gas, improve the utilization rate of oil resources, and solve the current shortage of ethylbenzene / styrene market, various countries have developed the process of producing ethylbenzene from dry gas. Dry gas to produce ethylbenzene is generally carried out under the action of a catalyst at a reaction temperature of 200℃ to 500℃, so that the ethylene and a small amount of propylene and butene in the dry gas react with benzene to produce ethylbenzene, propylbenzene, butylbenzene and polyalkylbenzenes.

[0003] Ethylbenzene alkylation catalysts generally use acidic molecular sieves. Due to the presence of high levels of sulfur-containing impurities in dry gas, they are easily adsorbed on the active centers on the catalyst surface due to their strong polarity, causing catalyst deactivation and significantly shortening the operation cycle of the ethylbenzene alkylation catalyst. Therefore, the dry gas needs to be desulfurized before entering the ethylene-based ethylbenzene unit to control the H2S content. However, when the desulfurization unit fluctuates, the H2S volume fraction in the catalytic dry gas will exceed 100×10 -6 , even up to 20000×10 -6 .

[0004] The article "Summary of pilot tests on the selective removal of H2S by aqueous methyldiethanolamine solution under pressure" (Petroleum and Natural Gas Chemical Industry, Issue 2, 1987) discloses a method for removing hydrogen sulfide from natural gas using an absorption tower using aqueous methyldiethanolamine solution. The hydrogen sulfide content in the purified gas was reduced to 10 mg / m 3 This method significantly reduces the hydrogen sulfide content in natural gas, but the conventional absorption tower operation results in a low elasticity in hydrogen sulfide removal and a general depth of hydrogen sulfide removal, which makes it difficult to meet the requirements of working conditions that are sensitive to hydrogen sulfide content.

[0005] The article "Industrial Application of Supergravity Complex Iron Method for Removing H2S" (Chemical Industry and Engineering Technology, Vol. 35, No. 2, 2014) discloses a method for removing hydrogen sulfide-containing oil field associated gas using complex iron and a supergravity machine. After desulfurization, the hydrogen sulfide concentration of the associated gas is less than 20 mg / m 2 The depth of hydrogen sulfide removal by this method is not as good as the research results published in "Summary of Intermediate Tests on Selective H2S Removal from Methyldiethanolamine Aqueous Solution under Pressure" (Petroleum and Natural Gas Chemical Industry, Issue 2, 1987), and it is still difficult to apply to working conditions that are more sensitive to hydrogen sulfide content.

[0006] Patent CN103756743A discloses a method for removing hydrogen sulfide from low-content hydrogen sulfide raw gas on an offshore platform, wherein the hydrogen sulfide content in the hydrogen sulfide raw gas is ≤300ppm, and the outlet hydrogen sulfide concentration is about 0ppm (undetectable). This method has a high depth of hydrogen sulfide removal, but is generally only applicable to occasions where the hydrogen sulfide content in the raw material is low. When the hydrogen sulfide content in the raw material is high, the depth of hydrogen sulfide removal cannot be guaranteed.

[0007] Patent CN102151476A discloses a method for oxidative removal of hydrogen sulfide in the gas phase under a hypergravity field, which involves contacting a desulfurizer and a hydrogen sulfide-containing gas in a countercurrent or crosscurrent manner in a desulfurization hypergravity machine to remove hydrogen sulfide from catalytic cracking dry gas, thereby reducing the concentration of hydrogen sulfide from 10,000 ppm to 20 ppm. The depth of hydrogen sulfide removal by this method is still inferior to the research results disclosed in "Summary of Intermediate Tests on Selective Removal of H2S from Methyldiethanolamine Aqueous Solution under Pressure" (Petroleum and Natural Gas Chemical Industry, Issue 2, 1987), and is difficult to apply to working conditions that are sensitive to hydrogen sulfide content.

[0008] In summary, the existing technologies for removing sulfur-containing impurities mainly have the following problems: low operational flexibility and insufficient removal depth, which in turn lead to continuous slow deactivation or rapid deactivation of the alkylation catalyst. Therefore, continuous deep and stable removal of sulfur-containing impurities in dry gas is one of the important issues to be solved in ethylbenzene units related to high-sulfur crude oil refining. Summary of the invention

[0009] The technical problem to be solved by the present invention is that the content of sulfur-containing impurities in dry gas is high and difficult to remove in the prior art, and a desulfurization filler and a preparation method and application thereof are provided. The desulfurization filler of the present invention is used to separate sulfur-containing impurities in dry gas that affect the activity of ethylbenzene alkylation catalyst, effectively eliminate the cumulative effect of trace sulfur-containing impurities on the catalyst, and is conducive to extending the operating cycle of the alkylation catalyst, and realizing low-cost and continuous production of ethylbenzene.

[0010] The first aspect of the present invention provides a desulfurization filler, wherein the desulfurization filler comprises a filler, a silane layer, a first modified layer and a second modified layer from the inside to the outside; the first modified layer contains a phenyl group; and the second modified layer contains a secondary amine group and a primary amine group.

[0011] In the above technical solution, in the silane layer, the molar ratio of silicon ether group to silicon carbon group is 0.8-1.2, and the thickness of the silane layer is 150-250 microns.

[0012] In the above technical solution, the phenyl content in the first modified layer is 0.15 to 0.33 mol / m 2 , the thickness of the first modified layer is 42 to 85 microns.

[0013] In the above technical solution, the content of secondary amine groups in the second modified layer is 0.32 to 0.75 mol / m 2 The content of primary amine groups is 0.10~0.32mol / m 2 Preferably, the second modified layer further contains tertiary amine groups, and the content of the tertiary amine groups is 0.08 to 0.21 mol / m 2 .

[0014] In the above technical solution, the outer surface of the second modified layer of the desulfurization filler further includes a third modified layer. Preferably, the content of secondary amine groups in the third modified layer is 110 to 320 mmol / m 2 The imine content is 46~138mmol / m 2 The content of methoxyl group is 143~448mmol / m 2 .

[0015] In the above technical solution, the filler can be at least one of a grid structured filler and a corrugated structured filler, and the corrugated structured filler can be at least one of a plate corrugated structured filler, a mesh corrugated structured filler, etc., such as a corrugated plate structured filler, a calendered perforated plate corrugated structured filler, a mesh grid structured filler, or a corrugated wire mesh structured filler. The specific surface area of ​​the filler is preferably 800 to 2300 m 2 / m 3 The filler is preferably made of metal, and more preferably 304, 304L, 316, 316L. The filler is preferably a metal corrugated plate structured filler, and the porosity of the filler is 81% to 93%.

[0016] In the above technical solution, the silanization agent used for the silane layer is selected from at least one of γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like.

[0017] In the above technical scheme, the first modifier used in the first modified layer includes a first modifying component (the first modifying component is selected from at least one of 3-(3,5-dichlorophenyl)-1-propylene, 1-(3-butene-1-yl)-2,4-dichlorobenzene, and 3-(3,4-dichlorophenyl)-1-propylene, preferably 1-(3-butene-1-yl)-2,4-dichlorobenzene), dibenzoyl peroxide and a solvent; the solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene.

[0018] In the above technical scheme, the second modifier used in the second modified layer includes a second modifying component (the second modifying component is selected from at least one of N1-(2-aminoethyl)-N1-(2-aminophenyl)-1,2-phenylenediamine, N,N-bis(4-aminophenyl)-1,4-phenylenediamine, and 3,5-diamino-N-(4-aminophenyl)benzamide, preferably N,N-bis(4-aminophenyl)-1,4-phenylenediamine), a catalyst and a solvent; the catalyst is selected from one of Lewis acids or Lewis bases, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride, and anhydrous aluminum chloride; the solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene.

[0019] In the above technical scheme, the third modifier used in the third modified layer includes a third modifying component (the third modifying component is selected from at least one of 2-[2-(2,6-dichlorophenyl)ethyl]hydrazinecarboxamidine, N-amidino-2-(2,6-dichlorophenyl)acetamide, N1,N2-di(4-chlorophenyl)acetamide, preferably N-amidino-2-(2,6-dichlorophenyl)acetamide), a diluent, 3,5-dichloro-2-methoxyaniline and a catalyst; the diluent is at least one of tetrahydrofuran, dichloromethane, dichloroethane, chloroform and trichloroethane; the catalyst is selected from one of a Lewis acid or a Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride.

[0020] In the above technical solution, the contents of phenyl in the first modified layer, secondary amine, primary amino and tertiary amine in the second modified layer, and secondary amine, imine and methoxy in the third modified layer are based on the surface area of ​​filler per square meter.

[0021] The second aspect of the present invention provides a method for preparing the above-mentioned desulfurization filler, comprising:

[0022] (11) performing silanization treatment on the filler to obtain a silanized filler;

[0023] (21) performing a first modification treatment on the silanized filler obtained in step (11);

[0024] (31) performing a second modification treatment on the filler obtained in step (21);

[0025] (41) Activating the filler obtained in step (31) to obtain a desulfurization filler.

[0026] In the above technical solution, the filler in step (11) can be at least one of a grid structured filler and a corrugated structured filler, and the corrugated structured filler can be at least one of a plate corrugated structured filler, a mesh corrugated structured filler, etc., such as a corrugated plate structured filler, a calendered perforated plate corrugated structured filler, a mesh grid structured filler, or a corrugated wire mesh structured filler. The specific surface area of ​​the filler is preferably 800 to 2300 m 2 / m 3 The filler is preferably made of metal, and more preferably 304, 304L, 316, 316L. The filler is preferably a metal corrugated plate structured filler, and the porosity of the filler is 81% to 93%.

[0027] In the above technical solution, the silanized filler obtained in step (11) is a filler covered with a silane film with a thickness of 150 to 250 microns.

[0028] In the above technical scheme, the silanization treatment described in step (11) can be carried out by a conventional dipping method in the art. For example, the filler can be firstly ultrasonically polished with a suspended grinding liquid (such as silicon carbide), and the polishing ultrasonic frequency is preferably 20-40 kHz, and then ultrasonic cleaning with desalted water (the cleaning ultrasonic frequency is 30-70 kHz, the temperature is 60-80°C, and the cleaning time is 30-40 minutes), ultrasonic cleaning with acetone (the cleaning ultrasonic frequency is 40-80 kHz, the cleaning temperature is 20-40°C, and the cleaning time is 20-30 minutes), ultrasonic cleaning with alkali solution (wherein the composition of the alkali solution, by mass content, is 5%-7% sodium hydroxide and 0.5%-1% sodium phosphate, the ultrasonic frequency is 50-90 kHz, the alkali washing temperature is 60-90°C, and the alkali washing time is 20-30 minutes), rinsing with desalted water (for example, 4-6 times), and drying with nitrogen (the temperature can be 20-40°C). Subsequently, the film is dipped in a silane reagent (selected from at least one of γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc.) solution (the composition of the silane reagent solution, by volume, is silane reagent: desalted water: anhydrous ethanol = (5.4-12): (16-20): (74-89), the pH value is 7.5-8.5, and the preparation method of the silanization reagent solution is to mix the silanization reagent, desalted water and anhydrous ethanol according to a ratio and pre-hydrolyze them, and the pre-hydrolysis time is 20-40 hours) (the dipping time is 20-30 minutes), and then dried and cured to obtain a silane film with a thickness of 150-250 microns. The drying and curing temperature is 110-130°C, the drying time is 30-50 minutes, and the drying atmosphere is nitrogen. The silanization reagent solution is continuously dipped and dried and cured 5-7 times.

[0029] In the above technical scheme, the first modifier used in the first modification treatment described in step (21) is a first modifying component (the first modifying component is selected from at least one of 3-(3,5-dichlorophenyl)-1-propylene, 1-(3-butene-1-yl)-2,4-dichlorobenzene, and 3-(3,4-dichlorophenyl)-1-propylene, preferably 1-(3-butene-1-yl)-2,4-dichlorobenzene), dibenzoyl peroxide and a solvent; the solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene. Preferably, the first modifying component, dibenzoyl peroxide and the solvent are calculated by weight, and the first modifying component: dibenzoyl peroxide: solvent = (23-35): (1-3): (190-280).

[0030] In the above technical scheme, the treatment conditions of the first modification treatment described in step (21) are as follows: the volume ratio (liquid-to-solid volume ratio) of the first modifier to the filler obtained in step (11) is 2 to 6, the immersion treatment temperature is 40° C. to 70° C., and the immersion treatment time is 2.5 to 5 hours. After the filler is treated with the first modifier, a first modified silanized filler intermediate is obtained.

[0031] In the above technical solution, preferably, in step (21), the filler obtained in step (11) is subjected to a first modification treatment and then to a first post-modification treatment to obtain a first post-modification silanized filler intermediate.

[0032] In the above technical solution, the first modification post-treatment agent used in the first modification post-treatment described in step (21) can be one or more of anhydrous methanol, anhydrous ethanol, and anhydrous acetone, and the preferred first modification post-treatment agent is anhydrous ethanol.

[0033] In the above technical scheme, in step (21), the first post-modification treatment can be carried out by immersion method, and the conditions of the first post-modification treatment are as follows: the volume ratio (liquid-to-solid volume ratio) of the first post-modification treatment agent to the first modified silanized filler intermediate is 1 to 4, the temperature is 60°C to 80°C, the treatment time for each treatment is 0.5 to 1.0 hour, the number of treatments is 2 to 3 times, and after the first post-modification treatment, it is dried at 110°C to 130°C for 0.5 to 1.0 hour in an inert atmosphere (such as nitrogen).

[0034] In the above technical solution, in step (31), the filler (the first modified silanized filler intermediate and / or the first modified post-treated silanized filler intermediate) obtained in step (21) is subjected to a second modification treatment to obtain a second modified silanized filler intermediate.

[0035] In the above technical solution, preferably, in step (31), the content of secondary amine groups introduced into the desulfurization filler by the second modification treatment is 0.32-0.75 mol / m 2The content of primary amine groups is 0.10~0.32mol / m 2 Preferably, the second modified layer further contains tertiary amine groups, and the content of the tertiary amine groups is 0.08 to 0.21 mol / m 2 .

[0036] In the above technical scheme, in step (31), the second modifier is a second modifying component (the second modifying component is selected from at least one of N1-(2-aminoethyl)-N1-(2-aminophenyl)-1,2-phenylenediamine, N,N-bis(4-aminophenyl)-1,4-phenylenediamine, 3,5-diamino-N-(4-aminophenyl)benzamide, preferably N,N-bis(4-aminophenyl)-1,4-phenylenediamine), a catalyst and a solvent; the catalyst is selected from one of Lewis acids or Lewis bases, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride, and anhydrous aluminum chloride; the solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene. Preferably, the second modifying component, the catalyst and the solvent, by mass fraction, second modifying component: catalyst: solvent = (28-46): (15-25): (200-300).

[0037] In the above technical scheme, the second modification treatment described in step (31) has the following treatment conditions: the volume ratio (liquid-to-solid volume ratio) of the second modifier to the filler obtained in step (21) is 2 to 6, the treatment temperature is 60°C to 80°C, the treatment time is 3 to 6 hours, and the treatment pressure (gauge pressure) is 500 to 1000 kPa.

[0038] In the above technical solution, preferably, in step (31), the filler obtained in step (21) is subjected to a second modification treatment and then to a third modification treatment; the content of secondary amine groups introduced into the desulfurized filler by the third modification treatment is 110 to 320 mmol / m 2 The imine content is 46~138mmol / m 2 The content of methoxyl group is 143~448mmol / m 2 .

[0039] In the above technical solution, preferably, in step (31), the second modified silanized filler intermediate is subjected to a third modification treatment to obtain a third modified silanized filler intermediate.

[0040] In the above technical scheme, preferably, in step (31), the third modifier used for the third modification treatment is a third modifying component (the third modifying component is selected from at least one of 2-[2-(2,6-dichlorophenyl)ethyl]hydrazinecarboxamidine, N-amidino-2-(2,6-dichlorophenyl)acetamide, N1,N2-di(4-chlorophenyl)acetamide, preferably N-amidino-2-(2,6-dichlorophenyl)acetamide), a diluent, 3,5-dichloro-2-methoxyaniline and a catalyst; the diluent is at least one of tetrahydrofuran, dichloromethane, dichloroethane, chloroform and trichloroethane; the catalyst is selected from one of a Lewis acid or a Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride. Preferably, the third modifying component, diluent, 3,5-dichloro-2-methoxyaniline and catalyst, by mass parts, are as follows: third modifying component: diluent: 3,5-dichloro-2-methoxyaniline: catalyst = (32-45): (200-300): (45-90): (15-28).

[0041] In the above technical scheme, preferably, in step (31), the third modification treatment can be carried out by immersion method, and the treatment conditions of the third modification treatment are as follows: the volume ratio (liquid-to-solid volume ratio) of the third modifier to the filler obtained in step (31) is 2 to 4, the treatment temperature is 70°C to 85°C, the treatment time is 6 to 8 hours, and the treatment pressure (gauge pressure) is 500 to 900 kPa.

[0042] In the above technical solution, preferably, in step (31), after the second modification treatment or the third modification treatment, a third post-modification treatment is performed to obtain a pre-activated modified silanized filler intermediate.

[0043] In the above technical solution, preferably, in step (31), the pre-activating agent used in the third modification post-treatment is anhydrous ethanol.

[0044] In the above technical scheme, preferably, in step (31), the third modification post-treatment conditions are as follows: the volume ratio of the preactivator to the third modified silanized filler intermediate (liquid-to-solid volume ratio) is 2 to 6, the temperature is 65°C to 90°C, the treatment time for each treatment is 0.5 to 1.0 hour, the number of treatments is 3 to 6 times, and after the third modification post-treatment, it is dried at 110°C to 130°C in an inert atmosphere (such as nitrogen) for 0.5 to 1.0 hour.

[0045] In the above technical scheme, in step (41), after the activation treatment, it is preferred to further include desalted water treatment to obtain a modified filler, i.e., a desulfurized filler. The activator is an alkaline aqueous solution of 2% to 10% (mass concentration); the alkaline aqueous solution is an inorganic alkaline solution, and / or an organic alkaline solution, preferably at least one of an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. The treatment conditions of the activator treatment are as follows: the volume ratio (liquid-to-solid volume ratio) of the activator to the filler obtained in step (31) is 4 to 11, the treatment temperature is 40°C to 60°C, and the treatment time is 2 to 3 hours. The desalted water treatment can be treated 4 to 6 times by an equal volume immersion method at a treatment temperature of 40°C to 60°C.

[0046] The third aspect of the present invention provides an application of the desulfurization filler provided in the first aspect or the desulfurization filler prepared by the method described in the second aspect in dry gas desulfurization.

[0047] In the above technical solution, the application includes: raw dry gas contacts with desulfurization filler to obtain desulfurized purified dry gas.

[0048] In the above technical scheme, preferably, in the application, a desulfurization refiner is used, in which a desulfurization filler bed is provided, a stationary regeneration agent central axis distributor is provided at the axial center position of the desulfurization refiner, a gas collecting pipe is provided on the outside of the regeneration agent central axis distributor, a raw material dry gas feed port is provided on the side wall of the desulfurization refiner, a regeneration agent feed port is provided on the upper part and communicated with the regeneration agent central axis distributor, a regeneration agent discharge port is provided on the lower part, a purified dry gas discharge port is provided on the top, and the dry gas discharge port is communicated with the gas collecting pipe.

[0049] In the above technical scheme, preferably, when the desulfurization refiner is started, the raw dry gas enters the desulfurization refiner through the raw dry gas feed port, and flows from the near wall side of the desulfurization filler bed to the axial center of the desulfurization filler bed. The sulfur-containing impurities in the dry gas are selectively adsorbed by the desulfurization filler. At the same time, the regeneration agent enters the desulfurization refiner from the regeneration agent feed port and passes through the regeneration agent central axis distributor. On the one hand, part of the regeneration agent flows to the desulfurization filler under the action of power to regenerate the desulfurization filler that adsorbs the sulfur-containing impurities. On the other hand, part of the regeneration agent directly reacts with the sulfur-containing impurities in the dry gas. The reacted regeneration agent is discharged from the regeneration agent discharge port. The obtained purified dry gas is collected by the gas collecting pipe and then discharged from the top of the desulfurization refiner.

[0050] In the above technical scheme, the raw dry gas flows from the wall side through the desulfurization packing bed to the axis center, and the regeneration agent flows to the desulfurization packing bed under the action of power through the regeneration agent central axis distributor, realizing adsorption and regeneration at the same time, thereby obtaining purified dry gas and working regeneration agent solution.

[0051] In the above technical scheme, the desulfurization filler is loaded in the desulfurization refiner to form a desulfurization filler bed. Under the action of power, the liquid is accelerated to turbulently move. It is an adsorption refining bed integrating adsorption and regeneration. It adopts online in-situ real-time continuous adsorption and regeneration, that is, it adsorbs and regenerates in situ in the desulfurization refiner. The high-speed turbulent regeneration agent realizes the regeneration of the adsorption center by contacting and mass transferring with the adsorption center.

[0052] In the above technical solution, the power is gas driving force, liquid throw-off inertia force, preferably liquid throw-off inertia force. The liquid throw-off inertia force comes from liquid high pressure injection, and / or the motor drives the desulfurization packing bed to move axially or radially.

[0053] In the above technical solution, the dry gas desulfurization conditions are as follows: the volume feed space velocity of the raw dry gas is 300-1500h -1 The adsorption temperature is 20-50°C, the adsorption pressure (gauge pressure) is 500-1200 kPa, and the feed volume ratio of raw dry gas to regeneration agent solution is 400-600.

[0054] In the above technical solution, the regeneration agent is selected from at least one of diethanolamine, N-methyldiethanolamine and potassium carbonate. Preferably, the regeneration agent solution is composed of 20% to 40% N-methyldiethanolamine, 3% to 5% diethanolamine, 3% to 5% potassium carbonate, and the rest is desalted water, based on the mass composition percentage.

[0055] In the above technical solution, preferably, after the dry gas raw material contacts the desulfurization, it is subjected to gas-liquid separation and defoaming. The gas-liquid separation and defoaming can be performed by a conventional wire mesh demister in the art, with a separation accuracy of 3 to 5 microns and a thickness of 80 to 200 mm.

[0056] In the above technical scheme, the raw material dry gas is derived from catalytic cracking, thermal cracking, delayed coking and hydrocracking in the refinery. The raw material dry gas includes but is not limited to ethylene, methane, ethane, propane, propylene, isobutane, n-butane, trans-butene, n-butene, isobutene, cis-butene, oxygen, nitrogen, hydrogen, carbon monoxide, carbon dioxide, acetylene, 1,3-butadiene, alkanes or alkenes with carbon content of more than five, and sulfur-containing impurities. The sulfur-containing impurities include but are not limited to the following substances: at least one of hydrogen sulfide, carbon oxysulfide and carbon disulfide, which are derived from sulfur-containing impurities in crude oil and sulfur-containing components generated by reactions during the refining process. In the raw material dry gas, the volume content of ethylene is 5% to 40%, preferably 10% to 20%. The volume content of the impurities calculated as total sulfur element is not less than 500 ppm, preferably not less than 50,000 ppm, more preferably not less than 100,000 ppm, and the volume content calculated as total sulfur element is not higher than 200,000 ppm, preferably not higher than 150,000 ppm.

[0057] In the above technical scheme, preferably, after the dry gas raw material contacts the desulfurization filler, it is washed with water, and the operating conditions of the water washing are as follows: the temperature is 20-50°C, the pressure is, by gauge pressure, 500-1200kPa, the theoretical plate number of the water washing tower is 6-10, and the ratio of the desulfurization purified dry gas to water (preferably desalted water) is, by volume, 50-80.

[0058] In the above technical scheme, according to the requirements for the propylene content in the product dry gas, the desulfurized purified dry gas can be contacted with a depropylene agent to obtain a depropylene purified dry gas. Wherein, the depropylene agent is a conventional depropylene agent in the art, preferably at least one of benzene and diethylbenzene. The conditions for the contact between the dry gas and the depropylene agent are as follows: the temperature is 10 to 25°C, the pressure is, by gauge pressure, 700 to 1500 kPa, and the theoretical plate number of the depropylene contact tower is 8 to 15. The amount ratio of dry gas to depropylene agent is, by volume, 60 to 90.

[0059] In the above technical solution, preferably, the total sulfur volume content in the obtained purified dry gas is not higher than 10 ppm, preferably not higher than 5 ppm, and more preferably not higher than 3 ppm.

[0060] In the above technical solution, preferably, the obtained purified dry gas can meet the requirements of long-term operation of the ethylbenzene alkylation catalyst.

[0061] A fourth aspect of the present invention provides a separation system for removing impurities from dry gas, comprising:

[0062] 1) Desulfurization refining bed, used to remove sulfur-containing impurities in dry gas raw materials;

[0063] 2) Water scrubber, used to remove trace nitrogen impurities in the desulfurized and purified dry gas;

[0064] 3) Propylene removal contact tower, used to remove propylene from the water-washed purified dry gas.

[0065] In the above technical solution, a desulfurization refining feed buffer tank is provided before the desulfurization refining bed, which is used to separate free colloids entrained in the dry gas raw material.

[0066] In the above technical scheme, preferably, the desulfurization refining bed is provided with a desulfurization filler bed layer, a regeneration agent central axis distributor is provided at the axial center, a raw dry gas feed port is provided on the side wall of the desulfurization refining bed, a regeneration agent feed port is provided at the upper part and communicated with the regeneration agent central axis distributor, a regeneration agent discharge port is provided at the lower part, and a purified dry gas discharge port is provided at the top.

[0067] In the above technical solution, a gas-liquid separation and demisting combined tank is provided after the desulfurization refining bed, which is used to grade and remove trace alkaline mist entrained in the dry gas at the outlet of the desulfurization refining bed.

[0068] In the above technical solution, the desulfurization refining bed is provided with a regeneration agent inlet and a regeneration agent outlet, which are used to introduce and lead out the regeneration agent into and out of the desulfurization refining bed when the desulfurization filler is adsorbed and saturated and regenerated online in situ.

[0069] In the above technical solution, a regeneration agent storage tank is provided to buffer the regeneration agent, including the recycled regeneration agent and the fresh regeneration agent.

[0070] In the above technical solution, preferably, the desulfurization refining bed regeneration agent storage tank is provided with a fresh regeneration agent or a regeneration agent lean solution inlet and a regeneration agent rich solution outlet for replacing the regeneration agent when the regeneration agent utilization rate reaches the process value (such as ≥80%).

[0071] In the above technical solution, a high-pressure pump is provided for pressurized delivery of the regeneration agent.

[0072] Compared with the prior art, the present invention has the following advantages:

[0073] 1. The inventor of the present invention has found through research that there are sulfur-containing impurities in the dry gas raw material that have a significant impact on the ethylbenzene alkylation catalyst, and these impurities will continue to accumulate in the catalyst, resulting in a decrease in the activity of the ethylbenzene catalyst and a shortened operating cycle. Due to the increase in the specific gravity of sulfur-containing crude oil refining and the volatility and limitations of the existing conventional desulfurization process, the sulfur-containing impurities in the dry gas raw material continue to fluctuate significantly. If only conventional adsorbents (such as ion exchange resins, activated carbon, etc.) are used for fixed bed adsorption, the adsorbent is easily saturated, conventional regeneration operations are frequent, and the amount of wastewater discharged is large. The inventor has further found that by modifying the filler, the highly active groups on the filler are used to deeply adsorb the sulfur-containing impurities in the raw dry gas, and then a preferred regeneration agent with low corrosiveness but desorption function is used to utilize the inertial throw-off force of the liquid, the gas-liquid co-current driving force and other dynamic displacement adsorption micro-interfaces, which not only solves the problem that the adsorbent is difficult to continuously regenerate in situ online, but also achieves the good effect of continuous adsorption and regeneration at the same time. At the same time, since the regeneration agent is used to continuously regenerate the active centers of the desulfurization filler with high-frequency pulses, there are sufficient fresh active centers for continuous adsorption, which solves the problem of low elasticity of conventional distillation desulfurization operations.

[0074] 2. In the process of modifying the filler of the present invention, a silanization layer is first formed on the surface of the filler, and then the filler is subjected to the first modification treatment, so that the strong support and dispersion effect of the filler can be fully exerted, the filler is protected from corrosion, and the service life is extended. Then, the filler is subjected to the second modification treatment, so that a modified layer with an adsorption active center having a suitable adsorption strength can be formed on the surface of the silanization layer, and good adsorption and regeneration effects can be achieved during continuous adsorption and regeneration operations. Preferably, the filler subjected to the third modification treatment can reduce the air film resistance when the dry gas contacts the modified layer formed by the second modification treatment, and improve the mass transfer rate. The modified layer formed by the third modification treatment has a certain absorption effect on each component in the dry gas, forming a dry gas concentration zone of a certain thickness, which is in dynamic equilibrium with the main dry gas zone, and the sulfur-containing impurity components are continuously exchanged to the modified layer formed by the second modification treatment, thereby achieving deep removal of sulfur-containing impurities in the dry gas. At the same time, the regeneration agent of the present invention preferably has good permeability, and in particular can effectively desorb the sulfur impurities adsorbed in the modified layer formed by the second modification treatment to restore the active centers of the desulfurization filler, so as to achieve a good balance between continuous adsorption and regeneration.

[0075] 3. The present invention solves the problems of high content of trace sulfur-containing impurities in the existing dry gas raw materials that affect the ethylbenzene alkylation catalyst and short operating cycle of the alkylation catalyst. By deeply and continuously adsorbing the sulfur-containing impurities in the dry gas raw materials, the operating cycle of the alkylation catalyst is greatly improved, thereby reducing the production cost of ethylbenzene. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 This is a schematic diagram of a separation system for removing impurities from dry gas according to the present invention;

[0077] The reference numerals are described as follows:

[0078] 0101 is a water washing tower, 0102 is a depropylene contact tower, 1101 is a desulfurization refining feed buffer tank, 1102 is a desulfurization refiner, 1103 is a motor, 1104 is a regeneration agent high-pressure pump, 1105 is a gas-liquid separation and demisting combination tank, 1106 is an integrated demisting layer, 0201 is a raw material dry gas inlet of the desulfurization refining feed buffer tank, 0202 is a water washing water inlet, 0203 is a water washing water rich liquid outlet, 0204 is a depropylene agent inlet, 0205 is a depropylene purified dry gas outlet, 0206 is a depropylene agent rich liquid outlet, 1201 is a fresh regeneration agent or a regeneration agent lean liquid inlet, 1202 is a regeneration agent rich liquid outlet;

[0079] Figure 2 It is a schematic diagram of the structure of the desulfurization refiner of the present invention;

[0080] The reference numerals are described as follows:

[0081] 1131 is a desulfurization packing bed, 1132 is a regeneration agent central axis distributor, 1133 is a gas collecting pipe, 1134 is a raw dry gas feed port, 1135 is a purified dry gas discharge port, 1136 is a regeneration agent feed port, and 1137 is a regeneration agent discharge port. DETAILED DESCRIPTION

[0082] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the protection scope of the present invention.

[0083] In the present invention, the specific surface area of ​​a filler refers to the surface area per unit volume of the filler.

[0084] In the present invention, the analysis of low-carbon hydrocarbon components uses a gas chromatograph Agilent 7890A GC (Agilent, USA), equipped with an HP-PLOT Al2O3 KCl (50m×0.53mm×15μm) capillary chromatographic column, and the column temperature is maintained at 100°C for 10 minutes, then increased to 120°C at 30°C per minute, and maintained for 3 minutes. The carrier gas He flow rate is 3mL / min, the injection volume is 0.1mL (quantitative loop), the split ratio is 5:1, the injection port temperature is 250°C, and the detector (FID) temperature is 250°C.

[0085] In the present invention, the sulfur content in the dry gas material is tested by Mitsubishi sulfur and nitrogen analyzer NSX-2100V, and the analysis method is argon flow rate 200ml / min, oxygen flow rate 400ml / min, and combustion temperature is 1000-1050℃.

[0086] A separation system for deeply removing impurities from dry gas according to the present invention (such as Figure 1As shown), it includes: 0101 is a water washing tower, 0102 is a depropylene contact tower, 1101 is a desulfurization refining feed buffer tank, 1102 is a desulfurization refiner, 1103 is a motor, 1104 is a regeneration agent high-pressure pump, 1105 is a gas-liquid separation and demisting combination tank, and 1106 is an integrated demisting layer. The separation process is as follows: dry gas raw materials (for example, those from catalytic cracking, thermal cracking, delayed coking, and hydrocracking in refineries) enter the desulfurization refining feed buffer tank 1101 through the raw material dry gas inlet 0201 of the desulfurization refining feed buffer tank, and the free colloids entrained in the dry gas raw materials are separated and removed. Then, the gas phase at the top of the desulfurization refining feed buffer tank 1101 enters the circumferential shell side of the desulfurization refiner 1102, and flows toward the axis through the desulfurization packing bed. The sulfur-containing impurities in the dry gas raw material are adsorbed by the active groups on the desulfurization packing. At the same time, the regeneration agent in the gas-liquid separation and demisting combination tank 1105 is pressurized and transported to the regeneration agent central axis distributor in the desulfurization refiner 1102 by the regeneration agent high-pressure pump 1104. Under the driving force of the dry gas or the liquid Under the action of the inertial force of the shake-off, the adsorption surface is contacted, mass transferred and regenerated by high-frequency pulses. The dry gas at the outlet of the desulfurization refiner 1102 enters the gas-liquid separation and demisting combination tank 1105, and after being expanded and decelerated to settle large droplets, it enters the integrated demisting layer 1106 to remove trace alkaline mist larger than 5 microns, and then enters the water washing tower 0101 to remove trace nitrogen-containing impurities that may exist in the desulfurization purified dry gas. Then, it passes through conventional boosting equipment or directly enters the depropylene contact tower 0102 to countercurrently contact with the depropylene agent entering from the depropylene agent inlet 0204 to remove propylene in the dry gas. The depropylene purified dry gas is discharged through the depropylene purified dry gas outlet 0205, and the depropylene agent rich liquid is discharged through the depropylene agent rich liquid outlet 0206. The regenerant in the gas-liquid separation and demisting combination tank 1105 is continuously circulated through the regenerant high-pressure pump 1104. When the regenerant utilization rate reaches the process value (≥80%), the liquid level in the gas-liquid separation and demisting combination tank 1105 is discharged to 1% to 5% through the regenerant rich liquid outlet 1202, and then fresh regenerant or regenerant lean liquid regenerated by the regenerant regeneration unit is added through the fresh regenerant or regenerant lean liquid inlet 1201.

[0087] The structural schematic diagram of the desulfurization refiner of the present invention is as follows Figure 2As shown. A desulfurization filler bed 1131 is provided in the desulfurization refiner 1102, a static regeneration agent central axis distributor 1132 is provided at the axial center of the desulfurization refiner 1102, a gas collecting pipe 1133 is provided outside the regeneration agent central axis distributor 1132, a raw material dry gas feed port 1134 is provided on the side wall of the desulfurization refiner 1102, a regeneration agent feed port 1136 is provided at the top and communicates with the regeneration agent central axis distributor 1132, a regeneration agent discharge port 1137 is provided at the bottom, a purified dry gas discharge port 1135 is provided at the top, and the purified dry gas discharge port 1135 is communicated with the gas collecting pipe 1133, the lower end of the gas collecting pipe 1133 is connected to the motor through a shaft, and a sealing ring is provided at the connection between the upper section of the gas collecting pipe 1133 and the flange. When the desulfurization refiner is started, the raw dry gas enters the desulfurization refiner 1102 through the raw dry gas feed port 1134, and flows from the near wall side of the desulfurization filler bed 1131 to the axis of the desulfurization filler bed 1131. The sulfur-containing impurities in the dry gas are selectively adsorbed by the desulfurization filler. At the same time, the regeneration agent enters the desulfurization refiner 1102 from the regeneration agent feed port 1136 and passes through the regeneration agent central axis distributor 1132. On the one hand, part of the regeneration agent flows to the desulfurization filler under the action of power to regenerate the desulfurization filler that adsorbs the sulfur-containing impurities. On the other hand, part of the regeneration agent directly reacts with the sulfur-containing impurities in the dry gas. The reacted regeneration agent is discharged from the regeneration agent discharge port 1137. The obtained purified dry gas is collected by the gas collecting pipe and then discharged from the purified dry gas discharge port 1135 at the top of the desulfurization refiner.

[0088] [Example 1]

[0089] The dry gas raw material described in this embodiment is derived from catalytic cracking in a refinery. The dry gas composition, by volume ratio, includes: methane 16.3840%, ethane 9.1091%, ethylene 16.9379%, hydrogen sulfide 6.4433%, propane 0.1937%, propylene 0.9112%, isobutane 0.0901%, n-butane 0.0145%, trans-butene 0.0057%, cis-butene 0.0001%, oxygen 0.146 8%, nitrogen 14.3707%, carbon oxysulfide 0.0958%, n-butene 0.0177%, isobutylene 0.0376%, carbon disulfide 0.0104%, hydrogen 28.6812%, carbon monoxide 1.5062%, carbon dioxide 2.9757%, acetylene 0.0049%, 1,3-butadiene 0.0001%, alkanes or alkenes with carbon 5 or above 1.2428%, and other components 0.8204%. The volume content of sulfur-containing impurities based on total sulfur element is 67000ppm.

[0090] The separation process of this embodiment is the same as Figure 1 As shown, the schematic diagram of the desulfurization refiner is as follows Figure 2 shown.

[0091] The desulfurization packing bed is filled with desulfurization packing, which accelerates the turbulence of liquid under the action of forced power and integrates adsorption and regeneration. The forced power is the inertial force of liquid throwing off, which comes from the high-pressure injection of liquid and the circular motion of packing driven by the motor.

[0092] The preparation method of desulfurization filler includes: the filler is first treated with a silane reagent to obtain a silanized filler, and then sequentially subjected to a first modification treatment, a first post-modification treatment, a second modification treatment, a third modification treatment, a third post-modification treatment, an activation treatment and desalted water to obtain a desulfurization filler, namely, a desulfurization filler.

[0093] The filler has a specific surface area of ​​1500m 2 / m 3 (Model 1500Y, porosity 87%) metal corrugated plate structured packing. The packing metal is 316 material. The silanization treatment adopts the dip coating method. First, the packing is ultrasonically polished with silicon carbide suspension grinding liquid, and then ultrasonically cleaned with desalted water, ultrasonically cleaned with acetone, ultrasonically cleaned with alkaline solution, rinsed with desalted water, dried with nitrogen, and then dipped in a silane reagent (γ-methacryloxypropylmethyldimethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 1.0 and a thickness of 202 microns. Among them, the silane treatment conditions are as follows: the ultrasonic frequency of silicon carbide polishing is 30kHz; the ultrasonic cleaning conditions of desalted water are as follows: the ultrasonic frequency is 50kHz, the cleaning temperature is 70℃, and the cleaning time is 35 minutes; the cleaning conditions of acetone ultrasonic cleaning are as follows: the ultrasonic frequency is 60kHz, the ultrasonic cleaning temperature is 30℃, and the cleaning time is 25 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 6%, sodium phosphate is 0.7%, the ultrasonic frequency of alkali cleaning is 70kHz, the alkali cleaning temperature is 75℃, and the alkali cleaning time is 25 minutes; the filler after alkali washing is rinsed with desalted water for 5 times and blown dry with nitrogen at 30℃. The composition of the silane reagent solution, by volume, is silane reagent: desalted water: anhydrous ethanol = 8.5:18:81, the pH value is 8, and the pre-hydrolysis time is 30 hours. The dipping time is 25 minutes, the drying and curing temperature is 120℃, the drying time is 40 minutes, the drying atmosphere is nitrogen, and the dipping and drying are repeated 6 times.

[0094] The first modifier described in this embodiment is 1-(3-butene-1-yl)-2,4-dichlorobenzene, dibenzoyl peroxide and toluene. By mass, 1-(3-butene-1-yl)-2,4-dichlorobenzene: dibenzoyl peroxide: toluene = 29:2:235. The treatment conditions of the first modifier treatment are as follows: the volume ratio of the first modifier to the filler is 4, the immersion treatment temperature is 55°C, and the immersion treatment time is 3.7 hours. After being treated with the first modifier and introduced into the desulfurization filler, the phenyl content is 0.24 mol / m 2, with a thickness of 64 microns. After treating the filler with the first modifier, a first modified silanized filler intermediate is obtained. The first modified post-treatment agent used for the post-modification treatment is anhydrous ethanol. The first modified post-treatment adopts an immersion method, and the conditions are as follows: the volume ratio of the first modified post-treatment agent to the first modified silanized filler intermediate is 2.6, the temperature is 70°C, the treatment time is 0.7 hours each time, the number of treatments is 2 times, and after the ethanol treatment, it is dried at 120°C in nitrogen for 0.7 hours.

[0095] After the first modification, the silanized filler intermediate is subjected to a second modification treatment to obtain a second modified silanized filler intermediate. The second modifier is N,N-bis(4-aminophenyl)-1,4-phenylenediamine, zinc chloride and toluene, and by mass, N,N-bis(4-aminophenyl)-1,4-phenylenediamine: zinc chloride: toluene = 37:20:250. The zinc chloride is anhydrous zinc chloride. The treatment conditions of the second modifier treatment are as follows: the liquid-to-solid volume ratio of the second modifier to the filler is 4, the treatment temperature is 70°C, the treatment time is 4.5 hours, and the treatment pressure (gauge pressure) is 750kPa. After being treated with the second modifier, it is introduced into the desulfurized filler, and the content of secondary amine groups is 0.53mol / m 2 The content of primary amine groups is 0.21 mol / m 2 The content of tertiary amine is 0.15 mol / m 2 .

[0096] The second modified silanized filler intermediate is subjected to a third modification treatment to obtain a third modified silanized filler intermediate. The third modifier is N-amidino-2-(2,6-dichlorophenyl)acetamide, tetrahydrofuran, 3,5-dichloro-2-methoxyaniline and zinc chloride. By mass, N-amidino-2-(2,6-dichlorophenyl)acetamide: tetrahydrofuran: 3,5-dichloro-2-methoxyaniline: zinc chloride = 38:250:68:21. The treatment conditions of the third modifier treatment are as follows: the third modifier is used in an immersion method, the liquid-to-solid volume ratio of the third modifier to the filler is 3, the treatment temperature is 77°C, the treatment time is 7 hours, and the treatment pressure (gauge pressure) is 700kPa. After being treated with the third modifier, it is introduced into the desulfurized filler, and the content of secondary amine groups is 215mmol / m 2 The imine content is 92mmol / m 2 The methoxy content is 296mmol / m 2 .

[0097] The third modified silanized filler intermediate is subjected to a third modification post-treatment to obtain a preactivated modified silanized filler intermediate. The preactivating agent used in the third modification post-treatment is anhydrous ethanol. The third modification post-treatment conditions are as follows: the volume ratio of the preactivating agent to the third modified silanized filler intermediate is 4, the temperature is 77° C., the treatment time for each treatment is 0.7 hours, the number of treatments is 4 times, and after the third modification post-treatment, it is dried in nitrogen at 120° C. for 0.7 hours.

[0098] The pre-activated modified silanized filler intermediate is subjected to activation treatment and desalted water treatment to obtain a modified filler, i.e., a desulfurized filler. The activator is a 5% (mass concentration) sodium hydroxide aqueous solution. The treatment conditions of the activator treatment are as follows: the liquid-to-solid volume ratio of the activator to the filler is 7.5, the treatment temperature is 50° C., and the treatment time is 2.5 hours. The desalted water treatment is treated 5 times by an equal volume immersion method at a treatment temperature of 50° C.

[0099] In this embodiment, the dry gas raw material volume feed space velocity is 1000h -1 , the adsorption temperature is 35℃, and the adsorption pressure (gauge pressure) is 850kPa. The demisting component in the gas-liquid separation demisting combination tank is a wire mesh demisting device with a separation accuracy of 4 microns and a thickness of 100 mm. The regeneration agent solution includes diethanolamine, N-methyldiethanolamine, potassium carbonate, and desalted water. In terms of mass composition percentage, N-methyldiethanolamine is 30%, diethanolamine is 4%, potassium carbonate is 4%, and the rest is desalted water. Among them, the feed ratio of dry gas raw material to regeneration agent solution is, by volume, 500.

[0100] The operating conditions of the desulfurized purified dry gas in the water scrubber are as follows: the temperature is 35°C, the pressure is, by gauge pressure, 840 kPa, and the theoretical plate number of the water scrubber is 8. The usage ratio of the desulfurized purified dry gas to the desalted water is, by volume, 65.

[0101] The depropylene agent is benzene. The contact conditions between the raw material dry gas and the depropylene agent are as follows: the temperature is 18°C, the pressure is, by gauge pressure, 1100 kPa, and the theoretical plate number of the depropylene contact tower is 11. The amount ratio of the raw material dry gas to the depropylene agent is, by volume, 75.

[0102] The total sulfur content in the propylene-free purified dry gas obtained in this example is 6 ppm by volume.

[0103] [Example 2]

[0104] The dry gas raw material described in this embodiment is the same as that in Example 1. The separation process of this embodiment is the same as that in Example 1. Figure 1 As shown, the schematic diagram of the desulfurization refiner is as follows Figure 2 shown.

[0105] The desulfurization packing bed is filled with desulfurization packing, which accelerates the turbulence of liquid under the action of forced power and integrates adsorption and regeneration. The forced power is the inertial force of liquid throwing off, which comes from the high-pressure injection of liquid and the circular motion of packing driven by the motor.

[0106] The preparation method of desulfurization filler comprises: the filler is first treated with a silane reagent to obtain a silanized filler, and then sequentially subjected to a first modification treatment, a first post-modification treatment, a second modification treatment, a third modification treatment, a third post-modification treatment, an activation treatment and a desalted water treatment to obtain the desulfurization filler.

[0107] The filler has a specific surface area of ​​2200m 2 / m 3 (Model 2200Y, porosity 82%) metal corrugated plate structured packing. The packing metal is 316 material. The silanization treatment adopts the dip coating method. First, the packing is ultrasonically polished with silicon carbide suspension grinding liquid, and then ultrasonically cleaned with desalted water, ultrasonically cleaned with acetone, ultrasonically cleaned with alkali solution, rinsed with desalted water, dried with nitrogen, and then dipped in a silane reagent (γ-methacryloxypropylmethyldiethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 1.1 and a thickness of 242 microns. Among them, the silanization treatment conditions are as follows: the ultrasonic frequency of silicon carbide polishing is 25kHz; the ultrasonic cleaning conditions of desalted water are as follows: the ultrasonic cleaning frequency is 35kHz, the cleaning temperature is 78℃, and the cleaning time is 39 minutes; the conditions of acetone ultrasonic cleaning are as follows: the ultrasonic cleaning frequency is 45kHz, the ultrasonic cleaning temperature is 35℃, and the cleaning time is 28 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 6%, sodium phosphate is 0.9%, the ultrasonic cleaning frequency of alkali is 55kHz, the alkali cleaning temperature is 85℃, and the alkali cleaning time is 27 minutes. The filler after alkali cleaning is rinsed with desalted water for 6 times and blown dry with nitrogen at 40℃. The composition of the silane reagent solution, by volume, is silane reagent: desalted water: anhydrous ethanol = 11.3: 19.5: 76, the pH value is 8.3, and the pre-hydrolysis time is 39 hours. The dipping time is 29 minutes, the drying curing temperature is 127℃, the drying time is 46 minutes, the drying atmosphere is nitrogen, and the dipping and drying are repeated 7 times.

[0108] The first modifier described in this embodiment is 1-(3-butene-1-yl)-2,4-dichlorobenzene, dibenzoyl peroxide and toluene. By mass, 1-(3-butene-1-yl)-2,4-dichlorobenzene: dibenzoyl peroxide: toluene = 34:2.7:200. The treatment conditions of the first modifier treatment are as follows: the liquid-to-solid volume ratio of the first modifier to the filler is 5, the immersion treatment temperature is 68°C, and the immersion treatment time is 4.8 hours. After being treated with the first modifier and introduced into the desulfurization filler, the phenyl content is 0.28 mol / m 2, with a thickness of 75 microns. After treating the filler with the first modifier, a first modified silanized filler intermediate is obtained. The first modified post-treatment agent used for the post-modification treatment is anhydrous ethanol. The first modified post-treatment adopts an immersion method, and the conditions are as follows: the volume ratio of the first modified post-treatment agent to the first modified silanized filler intermediate is 3.8, the temperature is 78°C, the treatment time is 1.0 hour each time, the number of treatments is 3 times, and after the ethanol treatment, it is dried at 125°C in nitrogen for 1.0 hour.

[0109] After the first modification, the silanized filler intermediate is subjected to a second modification treatment to obtain a second modified silanized filler intermediate. The second modifier is N,N-bis(4-aminophenyl)-1,4-phenylenediamine, zinc chloride and toluene, and by mass, N,N-bis(4-aminophenyl)-1,4-phenylenediamine: zinc chloride: toluene = 45:23:210. The zinc chloride is anhydrous zinc chloride. The treatment conditions of the second modifier treatment are as follows: the liquid-to-solid volume ratio of the second modifier to the filler is 5.2, the treatment temperature is 77°C, the treatment time is 5.8 hours, and the treatment pressure (gauge pressure) is 960kPa. After being treated with the second modifier, it is introduced into the desulfurized filler, and the content of secondary amine groups is 0.72mol / m 2 The content of primary amine groups is 0.28 mol / m 2 The content of tertiary amine is 0.18 mol / m 2 .

[0110] The second modified silanized filler intermediate is subjected to a third modification treatment to obtain a third modified silanized filler intermediate. The third modifier is N-amidino-2-(2,6-dichlorophenyl)acetamide, tetrahydrofuran, 3,5-dichloro-2-methoxyaniline and zinc chloride. By mass, N-amidino-2-(2,6-dichlorophenyl)acetamide: tetrahydrofuran: 3,5-dichloro-2-methoxyaniline: zinc chloride = 43:205:87:26. The treatment conditions of the third modifier treatment are as follows: the third modifier and the filler liquid-to-solid volume ratio are 3.6 by immersion method, the treatment temperature is 83°C, the treatment time is 7.6 hours, and the treatment pressure (gauge pressure) is 870kPa. After being treated with the third modifier and introduced into the desulfurized filler, the content of secondary amine groups is 275mmol / m 2 The imine content is 131mmol / m 2 The methoxy content is 411mmol / m 2 .

[0111] The third modified silanized filler intermediate is subjected to a third modification post-treatment to obtain a preactivated modified silanized filler intermediate. The preactivating agent used in the third modification post-treatment is anhydrous ethanol. The third modification post-treatment conditions are as follows: the volume ratio of the preactivating agent to the third modified silanized filler intermediate is 5.6, the temperature is 85°C, the treatment time for each treatment is 0.9 hours, the number of treatments is 6 times, and after the third modification post-treatment, it is dried in nitrogen at 127°C for 0.9 hours.

[0112] The pre-activated modified silanized filler intermediate is subjected to activation treatment and desalted water treatment to obtain a modified filler, i.e., a desulfurized filler. The activator is a 5.7% (mass concentration) sodium hydroxide aqueous solution. The treatment conditions of the activator treatment are as follows: the liquid-to-solid volume ratio of the activator to the filler is 10, the treatment temperature is 57° C., and the treatment time is 2.8 hours. The desalted water treatment is treated 6 times by an equal volume immersion method at a treatment temperature of 57° C.

[0113] In this embodiment, the dry gas raw material volume feed space velocity is 500h -1 , the adsorption temperature is 25°C, and the adsorption pressure (gauge pressure) is 1000kPa. The demisting component in the gas-liquid separation demisting combination tank is a conventional wire mesh demisting device in the field, with a separation accuracy of 3 microns and a thickness of 150 mm. The regeneration agent includes diethanolamine, N-methyldiethanolamine, potassium carbonate, and desalted water. In terms of mass composition percentage, N-methyldiethanolamine is 36%, diethanolamine is 4.5%, potassium carbonate is 4.2%, and the rest is desalted water. Among them, the feed ratio of dry gas raw material to regeneration agent solution is, by volume, 450.

[0114] The operating conditions of the desulfurized purified dry gas in the water scrubber are as follows: the temperature is 30°C, the pressure is, by gauge pressure, 900 kPa, and the theoretical plate number of the water scrubber is 9. The usage ratio of the desulfurized purified dry gas to the desalted water is, by volume, 55.

[0115] The depropylene agent is diethylbenzene. The contact conditions between the raw material dry gas and the depropylene agent are as follows: the temperature is 15°C, the pressure is, by gauge pressure, 1400 kPa, and the theoretical plate number of the depropylene contact tower is 14. The dosage ratio of the raw material dry gas to the depropylene agent is, by volume, 65.

[0116] The total sulfur content in the propylene-free purified dry gas obtained in this example is 1.2 ppm by volume.

[0117] [Example 3]

[0118] The dry gas raw material described in this embodiment is the same as that in Example 1. The separation process of this embodiment is the same as that in Example 1. Figure 1 As shown, the schematic diagram of the desulfurization refiner is as follows Figure 2 shown.

[0119] The desulfurization packing bed is filled with desulfurization packing, which accelerates the turbulence of liquid under the action of forced power and integrates adsorption and regeneration. The forced power is the inertial force of liquid throwing off, which comes from the high-pressure injection of liquid and the circular motion of packing driven by the motor.

[0120] The preparation method of desulfurization filler comprises: the filler is first treated with a silane reagent to obtain a silanized filler, and then sequentially subjected to a first modification treatment, a first post-modification treatment, a second modification treatment, a third modification treatment, a third post-modification treatment, an activation treatment and desalted water to obtain the desulfurization filler.

[0121] The filler has a specific surface area of ​​900m 2 / m 3 (Model 900Y, porosity 92%) metal corrugated plate structured packing. The packing metal is 316 material. The silanization treatment adopts the dip coating method. First, the packing is ultrasonically polished with silicon carbide suspension grinding liquid, and then ultrasonically cleaned with desalted water, ultrasonically cleaned with acetone, ultrasonically cleaned with alkaline solution, rinsed with desalted water, dried with nitrogen, and then dipped in a silane reagent (γ-methacryloxypropylmethyldimethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 0.9 and a thickness of 162 microns. Among them, the silane treatment conditions are as follows: the ultrasonic frequency of silicon carbide polishing is 35kHz; the ultrasonic cleaning conditions of desalted water are as follows: the ultrasonic frequency is 65kHz, the cleaning temperature is 65℃, and the cleaning time is 35 minutes; the conditions of acetone ultrasonic cleaning are as follows: the cleaning ultrasonic frequency is 75kHz, the ultrasonic cleaning temperature is 25℃, and the cleaning time is 23 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 5.5%, sodium phosphate is 0.6%, the ultrasonic frequency is 80kHz, the alkali cleaning temperature is 65℃, the alkali cleaning time is 23 minutes, and the filler after alkali cleaning is rinsed with desalted water 4 times and blown dry with nitrogen at 25℃. The composition of the silane reagent solution, by volume, is silane reagent: desalted water: anhydrous ethanol = 6.1:16.5:76, the pH value is 7.7, and the pre-hydrolysis time is 26 hours. The dipping time is 21 minutes, the drying and curing temperature is 115℃, the drying time is 35 minutes, the drying atmosphere is nitrogen, and the dipping and drying are repeated 5 times.

[0122] The first modifier described in this embodiment is 1-(3-butene-1-yl)-2,4-dichlorobenzene, dibenzoyl peroxide and toluene. By mass, 1-(3-butene-1-yl)-2,4-dichlorobenzene: dibenzoyl peroxide: toluene = 24:1.1:275. The treatment conditions of the first modifier treatment are as follows: the volume ratio of the first modifier to the filler is 3, the immersion treatment temperature is 45°C, and the immersion treatment time is 2.6 hours. After being treated with the first modifier and introduced into the desulfurization filler, the phenyl content is 0.16 mol / m 2, with a thickness of 50 microns. After treating the filler with the first modifier, a first modified silanized filler intermediate is obtained. The first modified post-treatment agent used for the post-modification treatment is anhydrous ethanol. The first modified post-treatment adopts an immersion method, and the conditions are as follows: the volume ratio of the first modified post-treatment agent to the first modified silanized filler intermediate is 1.6, the temperature is 65°C, the treatment time is 0.6 hours each time, the number of treatments is 2 times, and after the ethanol treatment, it is dried at 115°C in nitrogen for 0.6 hours.

[0123] After the first modification, the silanized filler intermediate is subjected to a second modification treatment to obtain a second modified silanized filler intermediate. The second modifier is N,N-bis(4-aminophenyl)-1,4-phenylenediamine, zinc chloride and toluene, and by mass, N,N-bis(4-aminophenyl)-1,4-phenylenediamine: zinc chloride: toluene = 29:16:290. The zinc chloride is anhydrous zinc chloride. The treatment conditions of the second modifier treatment are as follows: the liquid-to-solid volume ratio of the second modifier to the filler is 3, the treatment temperature is 62°C, the treatment time is 3.5 hours, and the treatment pressure (gauge pressure) is 550kPa. After being treated with the second modifier, it is introduced into the desulfurized filler, and the content of secondary amine groups is 0.39mol / m 2 The content of primary amine groups is 0.13 mol / m 2 The content of tertiary amine is 0.12 mol / m 2 .

[0124] The second modified silanized filler intermediate is subjected to a third modification treatment to obtain a third modified silanized filler intermediate. The third modifier is N-amidino-2-(2,6-dichlorophenyl)acetamide, tetrahydrofuran, 3,5-dichloro-2-methoxyaniline and zinc chloride. By mass, N-amidino-2-(2,6-dichlorophenyl)acetamide: tetrahydrofuran: 3,5-dichloro-2-methoxyaniline: zinc chloride = 33:290:46:17. The treatment conditions of the third modifier treatment are as follows: the third modifier is used in an immersion method, the liquid-to-solid volume ratio of the third modifier to the filler is 3, the treatment temperature is 72°C, the treatment time is 6.3 hours, and the treatment pressure (gauge pressure) is 520 kPa. After being treated with the third modifier and introduced into the desulfurized filler, the content of the secondary amine group is 163 mmol / m 2 The imine content is 48mmol / m 2 The methoxy content is 155mmol / m 2 .

[0125] The third modified silanized filler intermediate is subjected to a third modification post-treatment to obtain a preactivated modified silanized filler intermediate. The preactivating agent used in the third modification post-treatment is anhydrous ethanol. The third modification post-treatment conditions are as follows: the volume ratio of the preactivating agent to the third modified silanized filler intermediate is 3, the temperature is 72°C, the treatment time for each treatment is 0.6 hours, the number of treatments is 4 times, and after the third modification post-treatment, it is dried in nitrogen at 117°C for 0.6 hours.

[0126] The pre-activated modified silanized filler intermediate is subjected to activation treatment and desalted water treatment to obtain a modified filler, i.e., a desulfurized filler. The activator is a 4.5% (mass concentration) sodium hydroxide aqueous solution. The treatment conditions of the activator treatment are as follows: the liquid-to-solid volume ratio of the activator to the filler is 5, the treatment temperature is 42° C., and the treatment time is 2.2 hours. The desalted water treatment is treated 4 times by an equal volume immersion method at a temperature of 43° C.

[0127] In this embodiment, the dry gas raw material volume feed space velocity is 1300h -1 , the adsorption temperature is 45°C, and the adsorption pressure (gauge pressure) is 600kPa. The demisting component in the gas-liquid separation demisting combination tank is a conventional wire mesh demisting device in the art, with a separation accuracy of 5 microns and a thickness of 100 mm. The regeneration agent includes diethanolamine, N-methyldiethanolamine, potassium carbonate, and desalted water. In terms of mass composition percentage, N-methyldiethanolamine is 25%, diethanolamine is 3.2%, potassium carbonate is 3.5%, and the rest is desalted water. Among them, the dosage ratio of dry gas raw material to regeneration agent solution is, by volume, 550.

[0128] The operating conditions of the desulfurized purified dry gas in the water scrubber are as follows: the temperature is 45°C, the pressure is, by gauge pressure, 600 kPa, and the theoretical plate number of the water scrubber is 7. The usage ratio of the desulfurized purified dry gas to the desalted water is, by volume, 75.

[0129] The depropylene agent is diethylbenzene. The contact conditions between the raw material dry gas and the depropylene agent are as follows: the temperature is 22°C, the pressure is, by gauge pressure, 900 kPa, and the theoretical plate number of the depropylene contact tower is 9. The dosage ratio of the raw material dry gas to the depropylene agent is, by volume, 85.

[0130] The total sulfur content in the propylene-free purified dry gas obtained in this example is 8.4 ppm by volume.

[0131] [Example 4]

[0132] The desulfurization filler used in this embodiment is the same as that in Example 2.

[0133] The separation process for the dry gas raw material in this embodiment is the same as that in embodiment 2. The only difference between this embodiment and embodiment 2 is the dry gas raw material used. The dry gas composition, by volume, includes: methane 16.6244%, ethane 7.5433%, carbon oxysulfide 0.2577%, ethylene 14.8774%, propane 0.1729%, propylene 0.7825%, isobutane 0.0754%, carbon disulfide 0.1309%, n-butane 0.0146%, trans-butene 0.0062%, n-butene 0.0172%, isobutene 0.0354%, cis-butene 0.0002%, oxygen 0.1274%, nitrogen 12.5934%, hydrogen sulfide 12.8866%, hydrogen 27.3889%, carbon monoxide 1.3922%, carbon dioxide 3.0938%, acetylene 0.0049%, 1,3-butadiene 0.0001%, alkanes or alkenes with carbon content of more than five carbon atoms 1.1101%, and other components 0.8644%. The volume content of sulfur-containing impurities based on total sulfur element is 124,000 ppm.

[0134] The total sulfur content in the propylene-free purified dry gas obtained in this example is 4.5 ppm by volume.

[0135] [Example 5]

[0136] The desulfurization filler used in this embodiment is the same as that in Example 2.

[0137] The separation process for the dry gas raw material in this embodiment is the same as that in embodiment 2. The only difference between this embodiment and embodiment 2 is the dry gas raw material used. The dry gas composition, by volume, includes: methane 19.1554%, ethane 8.6917%, ethylene 17.1423%, propane 0.1992%, propylene 0.9017%, isobutane 0.0869%, n-butane 0.0168%, trans-butene 0.0071%, hydrogen sulfide 0.0699%, n-butene 0.0198%, isobutene 0.0408%, cis-butene 0.0002%, oxygen 0.1468%, carbon disulfide 0.0007%, nitrogen 14.5107%, hydrogen 31.5587%, carbon monoxide 1.6041%, carbon dioxide 3.5648%, carbon oxysulfide 0.0014%, acetylene 0.0057%, 1,3-butadiene 0.0001%, alkanes or alkenes with carbon content of more than five carbon atoms 1.2791%, and other components 0.9960%. The volume content of sulfur-containing impurities based on total sulfur element is 730 ppm.

[0138] The total sulfur volume content in the propylene-removed purified dry gas obtained in this example is 0.12 ppm.

[0139] [Example 6]

[0140] The dry gas raw material described in this embodiment is the same as that in Example 1. The separation process of this embodiment is the same as that in Example 1. Figure 1 As shown, the schematic diagram of the desulfurization refiner is as follows Figure 2 shown.

[0141] The desulfurization packing bed is filled with desulfurization packing, which accelerates the turbulence of liquid under the action of forced power and integrates adsorption and regeneration. The forced power is the inertial force of liquid throwing off, which comes from the high-pressure injection of liquid and the circular motion of packing driven by the motor.

[0142] The preparation method of desulfurization filler comprises: the filler is first treated with a silane reagent to obtain a silanized filler, and then sequentially subjected to a first modification treatment, a second modification treatment, a third modification treatment, and an activation treatment to obtain the desulfurization filler.

[0143] The filler has a specific surface area of ​​900m 2 / m 3 (Model 900Y, porosity 92%) metal corrugated plate structured packing. The packing metal is 316 material. The silanization treatment adopts the dip coating method. First, the packing is ultrasonically polished with silicon carbide suspension grinding liquid, and then ultrasonically cleaned with desalted water, ultrasonically cleaned with acetone, ultrasonically cleaned with alkaline solution, rinsed with desalted water, dried with nitrogen, and then dipped in a silane reagent (γ-methacryloxypropylmethyldimethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 0.9 and a thickness of 162 microns. Among them, the silane treatment conditions are as follows: the ultrasonic frequency of silicon carbide polishing is 35kHz; the ultrasonic cleaning conditions of desalted water are as follows: the ultrasonic frequency is 65kHz, the cleaning temperature is 65℃, and the cleaning time is 35 minutes; the conditions of acetone ultrasonic cleaning are as follows: the cleaning ultrasonic frequency is 75kHz, the ultrasonic cleaning temperature is 25℃, and the cleaning time is 23 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 5.5%, sodium phosphate is 0.6%, the ultrasonic frequency is 80kHz, the alkali cleaning temperature is 65℃, the alkali cleaning time is 23 minutes, and the filler after alkali cleaning is rinsed with desalted water 4 times and blown dry with nitrogen at 25℃. The composition of the silane reagent solution, by volume, is silane reagent: desalted water: anhydrous ethanol = 6.1:16.5:76, the pH value is 7.7, and the pre-hydrolysis time is 26 hours. The dipping time is 21 minutes, the drying and curing temperature is 115℃, the drying time is 35 minutes, the drying atmosphere is nitrogen, and the dipping and drying are repeated 5 times.

[0144] The first modifier described in this embodiment is 1-(3-butene-1-yl)-2,4-dichlorobenzene, dibenzoyl peroxide and toluene. By mass, 1-(3-butene-1-yl)-2,4-dichlorobenzene: dibenzoyl peroxide: toluene = 24:1.1:275. The treatment conditions of the first modifier treatment are as follows: the volume ratio of the first modifier to the filler is 3, the immersion treatment temperature is 45°C, and the immersion treatment time is 2.6 hours. After being treated with the first modifier and introduced into the desulfurization filler, the phenyl content is 0.16 mol / m 2 , with a thickness of 50 microns. After the filler is treated with the first modifier, a first modified silanized filler intermediate is obtained.

[0145] After the first modification, the silanized filler intermediate is subjected to a second modification treatment to obtain a second modified silanized filler intermediate. The second modifier is N,N-bis(4-aminophenyl)-1,4-phenylenediamine, zinc chloride and toluene, and by mass, N,N-bis(4-aminophenyl)-1,4-phenylenediamine: zinc chloride: toluene = 29:16:290. The zinc chloride is anhydrous zinc chloride. The treatment conditions of the second modifier treatment are as follows: the liquid-to-solid volume ratio of the second modifier to the filler is 3, the treatment temperature is 62°C, the treatment time is 3.5 hours, and the treatment pressure (gauge pressure) is 550kPa. After being treated with the second modifier, it is introduced into the desulfurized filler, and the content of secondary amine groups is 0.37mol / m 2 The content of primary amine groups is 0.12 mol / m 2 The content of tertiary amine is 0.11 mol / m 2 .

[0146] The second modified silanized filler intermediate is subjected to a third modification treatment to obtain a third modified silanized filler intermediate. The third modifier is N-amidino-2-(2,6-dichlorophenyl)acetamide, tetrahydrofuran, 3,5-dichloro-2-methoxyaniline and zinc chloride. By mass, N-amidino-2-(2,6-dichlorophenyl)acetamide: tetrahydrofuran: 3,5-dichloro-2-methoxyaniline: zinc chloride = 33:290:46:17. The treatment conditions of the third modifier treatment are as follows: the third modifier is used in an immersion method, the liquid-to-solid volume ratio of the third modifier to the filler is 3, the treatment temperature is 72°C, the treatment time is 6.3 hours, and the treatment pressure (gauge pressure) is 520 kPa. After being treated with the third modifier and introduced into the desulfurized filler, the content of the secondary amine group is 155 mmol / m 2 The imine content is 47mmol / m 2 The methoxy content is 148mmol / m 2 .

[0147] The third modified silanized filler intermediate is activated to obtain a modified filler, i.e., a desulfurized filler. The activator is a 4.5% (mass concentration) sodium hydroxide aqueous solution. The treatment conditions of the activator treatment are as follows: the liquid-to-solid volume ratio of the activator to the filler is 5, the treatment temperature is 42° C., and the treatment time is 2.2 hours.

[0148] In this embodiment, the dry gas raw material volume feed space velocity is 1300h -1 , the adsorption temperature is 45°C, and the adsorption pressure (gauge pressure) is 600kPa. The demisting component in the gas-liquid separation demisting combination tank is a conventional wire mesh demisting device in the art, with a separation accuracy of 5 microns and a thickness of 100 mm. The regeneration agent includes diethanolamine, N-methyldiethanolamine, potassium carbonate, and desalted water. In terms of mass composition percentage, N-methyldiethanolamine is 25%, diethanolamine is 3.2%, potassium carbonate is 3.5%, and the rest is desalted water. Among them, the dosage ratio of dry gas raw material to regeneration agent solution is, by volume, 550.

[0149] The operating conditions of the desulfurized purified dry gas in the water scrubber are as follows: the temperature is 45°C, the pressure is, by gauge pressure, 600 kPa, and the theoretical plate number of the water scrubber is 7. The usage ratio of the desulfurized purified dry gas to the desalted water is, by volume, 75.

[0150] The depropylene agent is diethylbenzene. The contact conditions between the raw material dry gas and the depropylene agent are as follows: the temperature is 22°C, the pressure is, by gauge pressure, 900 kPa, and the theoretical plate number of the depropylene contact tower is 9. The dosage ratio of the raw material dry gas to the depropylene agent is, by volume, 85.

[0151] The total sulfur volume content in the propylene-removed purified dry gas obtained in this example is 11.6 ppm.

[0152] [Example 7]

[0153] The dry gas raw material described in this embodiment is derived from catalytic cracking in a refinery. The dry gas composition, by volume ratio, includes: methane 19.1554%, ethane 8.6917%, ethylene 17.1423%, propane 0.1992%, propylene 0.9017%, isobutane 0.0869%, normal butane 0.0168%, trans-butene 0.0071%, hydrogen sulfide 0.0699%, normal butene 0.0198%, isobutene 0.04 08%, cis-butylene 0.0002%, oxygen 0.1468%, carbon disulfide 0.0007%, nitrogen 14.5107%, hydrogen 31.5587%, carbon monoxide 1.6041%, carbon dioxide 3.5648%, carbon oxysulfide 0.0014%, acetylene 0.0057%, 1,3-butadiene 0.0001%, alkanes or alkenes with carbon 5 or above 1.2791%, and other components 0.9960%. The volume content of sulfur-containing impurities based on total sulfur element is 730ppm.

[0154] The separation process of this embodiment is the same as Figure 1 As shown, the schematic diagram of the desulfurization refiner is as follows Figure 2 shown.

[0155] The desulfurization packing bed is filled with desulfurization packing, which accelerates the turbulence of liquid under the action of forced power and integrates adsorption and regeneration. The forced power is the inertial force of liquid throwing off, which comes from the high-pressure injection of liquid and the circular motion of packing driven by the motor.

[0156] The preparation method of the desulfurization filler comprises: the filler is first treated with a silane reagent to obtain a silanized filler, and then sequentially subjected to a first modification treatment, a second modification treatment and an activation treatment to obtain the desulfurization filler.

[0157] The filler has a specific surface area of ​​900m 2 / m 3 (Model 900Y, porosity 92%) metal corrugated plate structured packing. The packing metal is 316 material. The silanization treatment adopts the dip coating method. First, the packing is ultrasonically polished with silicon carbide suspension grinding liquid, and then ultrasonically cleaned with desalted water, ultrasonically cleaned with acetone, ultrasonically cleaned with alkali solution, rinsed with desalted water, dried with nitrogen, and then dipped in a silane reagent (γ-methacryloxypropylmethyldiethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 0.9 and a thickness of 162 microns. Among them, the silane treatment conditions are as follows: the ultrasonic frequency of silicon carbide polishing is 35kHz; the ultrasonic cleaning conditions of desalted water are as follows: the ultrasonic frequency is 65kHz, the cleaning temperature is 65℃, and the cleaning time is 35 minutes; the conditions of acetone ultrasonic cleaning are as follows: the cleaning ultrasonic frequency is 75kHz, the ultrasonic cleaning temperature is 25℃, and the cleaning time is 23 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 5.5%, sodium phosphate is 0.6%, the ultrasonic frequency is 80kHz, the alkali cleaning temperature is 65℃, the alkali cleaning time is 23 minutes, and the filler after alkali cleaning is rinsed with desalted water 4 times and blown dry with nitrogen at 25℃. The composition of the silane reagent solution, by volume, is silane reagent: desalted water: anhydrous ethanol = 6.1:16.5:76, the pH value is 7.7, and the pre-hydrolysis time is 26 hours. The dipping time is 21 minutes, the drying and curing temperature is 115℃, the drying time is 35 minutes, the drying atmosphere is nitrogen, and the dipping and drying are repeated 5 times.

[0158] The first modifier described in this embodiment is 1-(3-butene-1-yl)-2,4-dichlorobenzene, dibenzoyl peroxide and toluene. By mass, 1-(3-butene-1-yl)-2,4-dichlorobenzene: dibenzoyl peroxide: toluene = 24:1.1:275. The treatment conditions of the first modifier treatment are as follows: the liquid-to-solid volume ratio of the first modifier to the filler is 3, the immersion treatment temperature is 45°C, and the immersion treatment time is 2.6 hours. After being treated with the first modifier and introduced into the desulfurization filler, the phenyl content is 0.16 mol / m 2 , with a thickness of 50 microns. After the filler is treated with the first modifier, a first modified silanized filler intermediate is obtained.

[0159] After the first modification, the silanized filler intermediate is subjected to a second modification treatment to obtain a second modified silanized filler intermediate. The second modifier is N,N-bis(4-aminophenyl)-1,4-phenylenediamine, zinc chloride and toluene, and by mass, N,N-bis(4-aminophenyl)-1,4-phenylenediamine: zinc chloride: toluene = 29:16:290. The zinc chloride is anhydrous zinc chloride. The treatment conditions for the second modifier treatment are as follows: the volume ratio of the second modifier to the filler obtained in step (21) is 3, the treatment temperature is 62°C, the treatment time is 3.5 hours, and the treatment pressure (gauge pressure) is 550kPa. After being treated with the second modifier, it is introduced into the desulfurized filler, and the content of secondary amine groups is 0.37mol / m 2 The content of primary amine groups is 0.12 mol / m 2 The content of tertiary amine is 0.11 mol / m 2 .

[0160] The second modified silanized filler intermediate is activated to obtain a modified filler, i.e., a desulfurized filler. The activator is a 4.5% (mass concentration) sodium hydroxide aqueous solution. The treatment conditions of the activator treatment are as follows: the liquid-to-solid volume ratio of the activator to the filler is 5, the treatment temperature is 42° C., and the treatment time is 2.2 hours.

[0161] In this embodiment, the dry gas raw material volume feed space velocity is 1300h -1 , the adsorption temperature is 45°C, and the adsorption pressure (gauge pressure) is 600kPa. The demisting component in the gas-liquid separation demisting combination tank is a conventional wire mesh demisting device in the art, with a separation accuracy of 5 microns and a thickness of 100 mm. The regeneration agent includes diethanolamine, N-methyldiethanolamine, potassium carbonate, and desalted water. In terms of mass composition percentage, N-methyldiethanolamine is 25%, diethanolamine is 3.2%, potassium carbonate is 3.5%, and the rest is desalted water. Among them, the dosage ratio of dry gas raw material to regeneration agent solution is, by volume, 550.

[0162] The operating conditions of the desulfurized purified dry gas in the water scrubber are as follows: the temperature is 45°C, the pressure is, by gauge pressure, 600 kPa, and the theoretical plate number of the water scrubber is 7. The usage ratio of the desulfurized purified dry gas to the desalted water is, by volume, 75.

[0163] The depropylene agent is diethylbenzene. The contact conditions between the raw material dry gas and the depropylene agent are as follows: the temperature is 22°C, the pressure is, by gauge pressure, 900 kPa, and the theoretical plate number of the depropylene contact tower is 9. The dosage ratio of the raw material dry gas to the depropylene agent is, by volume, 85.

[0164] The total sulfur content in the propylene-free purified dry gas obtained in this example is 5.1 ppm by volume.

[0165] [Comparative Example 1]

[0166] The preparation of the desulfurization filler in this comparative example is different from that in Example 3 in that a commercially available desulfurization filler with a specific surface area of ​​1000 m 2 / m 3 (Model 900Y, porosity 92%) metal corrugated plate structured packing. The packing metal is 316 material.

[0167] The dry gas raw material used in this comparative example is the same as that in Example 3, and the separation process for the dry gas raw material is the same as that in Example 3.

[0168] The total sulfur content of the obtained depropylene purified dry gas was 314 ppm by volume.

[0169] [Comparative Example 2]

[0170] The dry gas raw material used in this comparative example is the same as that in Example 3. Compared with Example 3, the only difference is that a packed tower water washing is used to remove sulfur impurities. The water washing tower equipment (packing model 250Y, porosity 98%) and process operating conditions are as follows: temperature 35°C, pressure (gauge pressure) 1000kPa theoretical plate number 18, mass concentration 30% diethanolamine aqueous solution, gas-liquid volume ratio 40.

[0171] The total sulfur content of the obtained depropylene purified dry gas was 3115 ppm by volume.

[0172] [Comparative Example 3]

[0173] This comparative example uses commercial 201×7OH resin as the adsorbent and adopts a conventional fixed bed adsorption process. The adsorption conditions are as follows: the resin filling volume is 60 cubic meters, the adsorption temperature is 30°C, and the volume space velocity is 30h -1 .

[0174] The dry gas raw material is the same as that in Example 3. In the initial stage of operation, the total sulfur content in the obtained propylene-removed purified dry gas is 3 ppm, and the adsorbent breaks through in about 7 minutes. Regeneration requires 4% to 6% sodium hydroxide, and the volume consumption of the regeneration liquid per unit volume of the adsorbent is 4 to 5 times.

[0175] The above describes the specific implementation of the present invention in detail, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A desulfurization filler, characterized in that: The desulfurization filler includes filler, silane layer, first modified layer and second modified layer from inside to outside; the first modified layer contains phenyl group; the second modified layer contains secondary amine group and primary amine group; In the silane layer, the molar ratio of silane ether group to silicon carbon group is 0.8 to 1.2, and the thickness of the silane layer is 150 to 250 microns; In the first modified layer, the phenyl content is 0.15 to 0.33 mol / m 2 , the thickness of the first modified layer is 42 to 85 microns; In the second modified layer, the content of secondary amine groups is 0.32 to 0.75 mol / m 2 The content of primary amine groups is 0.10~0.32mol / m 2 .

2. The desulfurization filler according to claim 1, characterized in that: The second modified layer also contains tertiary amine groups, and the content of the tertiary amine groups is 0.08-0.21 mol / m 2 .

3. The desulfurization filler according to claim 1, characterized in that: The filler is at least one of a grid structured filler or a corrugated structured filler.

4. The desulfurization filler according to claim 3, characterized in that: The filler is a metal corrugated wire mesh structured filler.

5. The desulfurization filler according to claim 3, characterized in that: The specific surface area of ​​the filler is 800 to 2300 m 2 / m 3 , the porosity is 81% to 93%.

6. The desulfurization filler according to any one of claims 1 to 5, characterized in that: The outer surface of the second modified layer of the desulfurization filler further includes a third modified layer; in the third modified layer, the content of secondary amine groups is 110 to 320 mmol / m 2 The imine content is 46~138mmol / m 2 The content of methoxyl group is 143~448mmol / m 2 .

7. The method for preparing the desulfurization filler according to any one of claims 1 to 5, comprising: (11) performing silanization treatment on the filler to obtain a silanized filler; (21) performing a first modification treatment on the silanized filler obtained in step (11); (31) performing a second modification treatment on the filler obtained in step (21); (41) The filler obtained in step (31) is activated to obtain a desulfurization filler.

8. The preparation method according to claim 7, characterized in that: The first modifier used in the first modification treatment in step (21) is a first modifying component, dibenzoyl peroxide and a solvent; the first modifying component is selected from at least one of 3-(3,5-dichlorophenyl)-1-propylene, 1-(3-butene-1-yl)-2,4-dichlorobenzene and 3-(3,4-dichlorophenyl)-1-propylene; and the solvent is selected from at least one of toluene, p-xylene, m-xylene and o-xylene.

9. The preparation method according to claim 8, characterized in that: In the first modifying agent used in the first modification treatment described in step (21), the first modifying component is 1-(3-butene-1-yl)-2,4-dichlorobenzene.

10. The preparation method according to claim 8, characterized in that: In the first modifying agent used in the first modification treatment described in step (21), the first modifying component, dibenzoyl peroxide and toluene are calculated by weight as follows: first modifying component: dibenzoyl peroxide: solvent = (23-35): (1-3): (190-280).

11. The preparation method according to claim 8, characterized in that: The treatment conditions of the first modification treatment described in step (21) are as follows: liquid-to-solid volume ratio is 2 to 6, immersion treatment temperature is 40° C. to 70° C., and immersion treatment time is 2.5 to 5 hours.

12. The preparation method according to claim 7, characterized in that: In step (31), the second modifier is a second modifying component, a catalyst and a solvent; the second modifying component is selected from at least one of N1-(2-aminoethyl)-N1-(2-aminophenyl)-1,2-phenylenediamine, N,N-bis(4-aminophenyl)-1,4-phenylenediamine, and 3,5-diamino-N-(4-aminophenyl)benzamide; the catalyst is selected from one of a Lewis acid or a Lewis base; and the solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene.

13. The preparation method according to claim 12, characterized in that: In step (31), in the second modifier, the second modifying component is N,N-bis(4-aminophenyl)-1,4-phenylenediamine.

14. The preparation method according to claim 12, characterized in that: In step (31), in the second modifier, the catalyst is at least one of anhydrous zinc chloride, anhydrous tin tetrachloride, and anhydrous aluminum chloride.

15. The preparation method according to claim 12, characterized in that: In step (31), in the second modifier, the second modification component: catalyst: solvent = (28-46): (15-25): (200-300) by weight.

16. The preparation method according to claim 12, characterized in that: The treatment conditions of the second modification treatment described in step (31) are as follows: liquid-to-solid volume ratio is 2 to 6, treatment temperature is 60° C. to 80° C., treatment time is 3 to 6 hours, and treatment pressure gauge pressure is 500 to 1000 kPa.

17. The preparation method according to claim 7, characterized in that: In step (31), the filler obtained in step (21) is subjected to a second modification treatment and then to a third modification treatment; the content of the secondary amine groups introduced into the desulfurized filler after the third modification treatment is 110 to 320 mmol / m 2 The imine content is 46~138mmol / m 2 The content of methoxyl group is 143~448mmol / m 2 .

18. The preparation method according to claim 17, characterized in that: The third modifier used in the third modification treatment is a third modification component, a diluent, 3,5-dichloro-2-methoxyaniline and a catalyst; the third modification component is selected from at least one of 2-[2-(2,6-dichlorophenyl)ethyl]hydrazinecarboxamidine, N-amidino-2-(2,6-dichlorophenyl)acetamide, and N1,N2-di(4-chlorophenyl)acetamide; the diluent is at least one of tetrahydrofuran, dichloromethane, dichloroethane, chloroform, and trichloroethane; the catalyst is selected from one of a Lewis acid or a Lewis base.

19. The preparation method according to claim 18, characterized in that: In the third modifying agent used in the third modification treatment, the third modifying components, calculated by mass percentage, are: diluent: 3,5-dichloro-2-methoxyaniline: catalyst = (32-45): (200-300): (45-90): (15-28).

20. The preparation method according to claim 18, characterized in that: In the third modifier used in the third modification treatment, the catalyst is at least one of anhydrous zinc chloride, anhydrous tin tetrachloride, and anhydrous aluminum chloride.

21. The preparation method according to claim 18, characterized in that: The third modification treatment adopts the immersion method, and the treatment conditions of the third modification treatment are as follows: liquid-to-solid volume ratio is 2-4, treatment temperature is 70°C-85°C, treatment time is 6-8 hours, and treatment pressure gauge pressure is 500-900 kPa.

22. The preparation method according to claim 7 or 17, characterized in that: In step (41), the activator is an alkaline aqueous solution with a mass concentration of 2% to 10%; the alkaline aqueous solution is an inorganic alkaline solution and / or an organic alkaline solution; the activator treatment is carried out by immersion, and the treatment conditions are as follows: liquid-to-solid volume ratio is 4 to 11, the treatment temperature is 40°C to 60°C, and the treatment time is 2 to 3 hours.

23. The preparation method according to claim 22, characterized in that: In step (41), the alkaline aqueous solution is at least one of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution.

24. The preparation method according to claim 22, characterized in that: In step (41), the activation treatment further includes desalted water treatment, wherein the desalted water treatment is carried out by an equal volume immersion method for 4 to 6 times at a treatment temperature of 40° C. to 60° C.

25. Use of the desulfurization filler according to any one of claims 1 to 6 or the desulfurization filler prepared by the preparation method according to any one of claims 7 to 24 in dry gas desulfurization, wherein: The raw dry gas contacts the desulfurization filler to obtain desulfurized purified dry gas.

26. The use according to claim 25, characterized in that The application adopts a desulfurization refiner, in which a desulfurization filler bed is provided, a stationary regeneration agent central axis distributor is provided at the axial center position of the desulfurization refiner, a gas collecting pipe is provided on the outside of the regeneration agent central axis distributor, a raw dry gas feed port is provided on the side wall of the desulfurization refiner, a regeneration agent feed port is provided on the upper part and communicated with the regeneration agent central axis distributor, a regeneration agent discharge port is provided on the lower part, and a purified dry gas discharge port is provided on the top, and the dry gas discharge port is communicated with the gas collecting pipe; wherein, the raw dry gas flows from the wall side to the axis center through the desulfurization filler bed, and at the same time, the regeneration agent flows to the desulfurization filler bed through the regeneration agent central axis distributor under the action of power, and adsorption and regeneration are realized at the same time, thereby obtaining purified dry gas and regeneration agent solution after working.

27. The use according to claim 25, characterized in that The dry gas desulfurization conditions are as follows: the volume feed space velocity of the raw dry gas is 300-1500h -1 The adsorption temperature is 20-50°C, the adsorption pressure gauge pressure is 500-1200 kPa, and the feed volume ratio of raw dry gas to regeneration agent solution is 400-600.

28. The use according to claim 26, characterized in that The regeneration agent is selected from at least one of diethanolamine, N-methyldiethanolamine and potassium carbonate.

29. The use according to claim 28, characterized in that The regeneration agent solution is composed of 20% to 40% N-methyldiethanolamine, 3% to 5% diethanolamine, 3% to 5% potassium carbonate, and the rest is desalted water.

30. The use according to claim 25, characterized in that The volume content of the raw material dry gas calculated as total sulfur element is not less than 500 ppm, and the volume content of the total sulfur element is not more than 200,000 ppm.

31. The use according to claim 30, characterized in that The volume content of the raw material dry gas calculated as total sulfur element is not less than 50,000 ppm, and the volume content of the total sulfur element is not more than 150,000 ppm.

32. The use according to claim 30, characterized in that The volume content of the raw material dry gas in terms of total sulfur element is not less than 100,000 ppm.

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