A kind of dealkalizing refining agent and its preparation and application

Abstract

The present invention discloses a dealkalizing refining agent and its preparation and application. The dealkalizing refining agent comprises a filler, a silane film and a modified layer from the inside to the outside, wherein the modified layer contains a sulfonic acid group and a secondary amine group. The preparation method of the dealkalizing refining agent comprises: preparing a filler covered with a silane film; and then treating the filler covered with the silane film with a modifier to obtain the dealkalizing refining agent. The method of the present invention can efficiently remove alkaline impurities that affect the activity of ethylbenzene alkylation catalyst, reduce the accumulation of alkaline impurities in the catalytic system, effectively extend the service life of the ethylbenzene alkylation catalyst, and reduce the production cost of ethylbenzene, and can be used in the industrial production of dry gas to ethylbenzene devices.

Description

Technical Field

[0001] The invention relates to the technical field of preparing ethylbenzene from dry gas, and relates to a dealkalizing refining agent and its preparation, as well as application in efficiently removing alkaline impurities (especially alkaline impurities) from dry gas. Background Art

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

[0003] Ethylbenzene alkylation catalysts generally use acidic molecular sieves. Due to the complexity of impurities in dry gas, especially the presence of certain alkaline impurities, the operating cycle of ethylbenzene alkylation catalysts is significantly shortened.

[0004] Patent CN109574780A discloses a method for adsorbing ammonia in dry gas using modified activated carbon. Since the ammonia content in the dry gas is unstable and generally fluctuates greatly between 1 and 500 ppm, the adsorbent is easily saturated when the ammonia content is high, resulting in frequent loading and unloading of the adsorbent.

[0005] Patent CN111450662A discloses a combined deammoniation process of a water washing tower, a cyclone separator, a coalescer, and an adsorption tower, wherein the water washing liquid is selected from industrial water or an acidic aqueous solution, and the adsorbent is formed activated carbon, silicon dioxide, alumina, formed molecular sieves, and strongly acidic cation exchange resins loaded with inorganic or organic acids. In this process, due to the limited operational flexibility of the water washing distillation tower, it is difficult to effectively remove ammonia from the dry gas when the ammonia content in the raw material fluctuates greatly. Even if an adsorption tower is set up later, the adsorbent in the adsorption tower is quickly saturated due to the excessively high ammonia content in the dry gas.

[0006] "Study on the absorption of ammonia in phosphate fertilizer tail gas by rotating packed bed" (Chemical Intermediates, Issue 7, 2009) discloses a process for absorbing ammonia in phosphate fertilizer tail gas by using phosphoric acid wastewater. Compared with traditional tower equipment, the absorption efficiency of this process is improved to a certain extent, but the deep deammoniation effect is average.

[0007] In summary, the existing deamination technology has the main problems of low operational flexibility and low removal depth, which leads to continuous slow deactivation or rapid deactivation of the alkylation catalyst. Therefore, continuous, efficient and stable removal of alkaline impurities in dry gas is one of the important issues that ethylbenzene units need to solve in the context of crude oil degradation. Summary of the invention

[0008] The technical problem to be solved by the present invention is that the alkaline impurity content in dry gas is high and it is difficult to remove it continuously and efficiently in the prior art, and a dealkalizing refining agent and a preparation method thereof and an application in removing alkaline impurities in dry gas are provided. The dealkalizing refining agent of the present invention is particularly suitable for separating alkaline impurities in dry gas that significantly affect the activity of ethylbenzene alkylation catalyst, effectively eliminating the cumulative effect of alkaline impurities on the catalyst, and can significantly extend the operation cycle of the alkylation catalyst, thereby realizing low-cost and continuous production of ethylbenzene.

[0009] The first aspect of the present invention provides a dealkalizing refining agent, wherein the dealkalizing refining agent comprises a filler, a silane film and a modified layer from the inside to the outside, and the modified layer contains a sulfonic acid group and a secondary amine group.

[0010] In the above technical solution, in the silane film, the molar ratio of silicon ether group to silicon carbon group is 0.9-1.3, and the thickness of the silane film is 50-300 microns.

[0011] In the above technical solution, the content of sulfonic acid groups in the modified layer is 0.42 to 0.83 mol / m 2 The content of secondary amine groups is 0.17~0.59mol / m 2 .

[0012] In the above technical solution, preferably, the outer surface of the modified layer further includes a surface treatment layer; the content of sulfonic acid groups in the surface treatment layer is 12 to 56 mmol / m 2 The content of secondary amine groups is 19 to 101 mmol / m 2 The content of methoxyl group is 47~303mmol / m 2 .

[0013] In the above technical solution, the filler can be at least one of grid structured filler and corrugated structured filler, and the corrugated structured filler can be at least one of plate corrugated structured filler and mesh corrugated structured filler. The specific surface area of ​​the filler is preferably 1000-2600m 2 / m 3 The porosity of the filler is preferably 74% to 85%. The filler can be made of metal, plastic or ceramic, wherein the metal material is preferably 304, 304L, 316, 316L. The filler is preferably a metal corrugated wire mesh structured filler.

[0014] In the above technical solution, the silanization agent used for the silane film is selected from at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and the like.

[0015] In the above technical solution, the modifier used in the modified layer includes a pretreatment agent, a catalyst and a solvent; the catalyst is selected from one of Lewis acid or Lewis base, 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. The pretreatment agent is selected from at least one of 4,4'-dichlorodiphenylmethanol, p-chlorodiphenylmethyl chloride, and 4-chlorodiphenylmethane (preferably p-chlorodiphenylmethyl chloride) further treated with fuming sulfuric acid.

[0016] In the above technical scheme, the surface treatment agent used for the surface treatment layer preferably includes N-(carbamoylmethyl)-2-aminoethanesulfonic acid, 3,5-dichloro-2-methoxyaniline, 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.

[0017] In the above technical solution, the contents of sulfonic acid groups and secondary amine groups in the modified layer and sulfonic acid groups, secondary amine groups and methoxy groups in the surface treatment layer are based on the surface area of ​​filler per square meter.

[0018] The second aspect of the present invention provides a method for preparing the above-mentioned dealkalized refined preparation, comprising:

[0019] (11) preparing a filler covered with a silane film;

[0020] (21) Treating the filler coated with the silane film described in step (11) with a modifier to obtain a dealkalized refined preparation.

[0021] In the above technical solution, the filler described in step (11) can be at least one of a grid structured filler or 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 1000 to 2600 m 2 / m 3 The porosity of the filler is preferably 74% to 85%. The filler can be made of metal, plastic or ceramic, wherein the metal material is preferably 304, 304L, 316, 316L. The filler is preferably a metal corrugated wire mesh structured filler.

[0022] In the above technical solution, the filler covered with a silane film in step (11) is a filler covered with a silane film with a thickness of 50 to 300 microns.

[0023] In the above technical solution, in step (11), the filler covered with the silane film can be prepared by conventional electrodeposition methods 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 to 40 kHz, and then ultrasonic cleaning with desalted water (the cleaning ultrasonic frequency is 30 to 70 kHz, the temperature is 60 to 80°C, and the cleaning time is 30 to 40 minutes), ultrasonic cleaning with acetone (the cleaning ultrasonic frequency is 40 to 80 kHz, the temperature is 20 to 40°C, and the cleaning time is 20 to 30 minutes), ultrasonic cleaning with alkali solution (wherein the alkali solution is composed of, by mass content, sodium hydroxide) and sodium hydroxide. The present invention relates to a method for preparing the silane film of the present invention. The method comprises the following steps: the first step is to prepare the silane film of the present invention; the first step is to prepare the silane film of the present invention; the second step is to prepare the silane film of the present invention; ... Generally, the silanization treatment conditions are preferably as follows: the electrodeposition voltage is 7V to 13V, the electrodeposition time is 40 to 60 minutes, the drying and curing temperature is 100 to 120° C., and the drying atmosphere can be nitrogen.

[0024] In the above technical scheme, in the dealkalization refining agent described in step (21), the filler covered with silane film is treated with a modifier, and the amount of sulfonic acid groups introduced into the dealkalization refining agent is 0.42-0.83 mol / m 2 The content of secondary amine groups is 0.17~0.59mol / m 2 .

[0025] In the above technical scheme, the modifier described in step (21) includes a pretreatment agent, a catalyst and a solvent; the catalyst is selected from one of Lewis acid or Lewis base, 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. The preparation method of the pretreatment agent is as follows: a pretreatment raw material (selected from at least one of 4,4'-dichlorodiphenylmethanol, p-chlorodiphenylmethyl chloride, and 4-chlorodiphenylmethane, preferably p-chlorodiphenylmethyl chloride) and fuming sulfuric acid react to obtain a pretreatment agent. The reaction conditions are as follows: pretreatment raw material and fuming sulfuric acid, by mass parts, pretreatment raw material: fuming sulfuric acid = (20-40): (50-80), reaction temperature is 60°C-90°C, and reaction time is 3-6 hours. The reaction product obtained by the reaction can be extracted by ether (preferably diethyl ether), wherein the process conditions of the ether extraction are as follows: by volume, reaction product: ether = 1: (10-20), extraction temperature is 20-30°C, continuous extraction time is 2-3 hours, the extracts are combined, and then the ether is evaporated at 50-70°C to obtain a pretreatment agent.

[0026] In the above technical solution, the modifier composition described in step (21) includes, by weight, pretreatment agent: catalyst: solvent = (22-34): (13-24): (180-320).

[0027] In the above technical scheme, the process of treating the filler covered with silane film in step (11) with a modifier in step (21) is as follows: the volume ratio (liquid-to-solid volume ratio) of the modifier to the filler covered with silane film obtained in step (11) is 1 to 6, the immersion treatment temperature is 45° C. to 65° C., and the immersion treatment time is 4 to 8 hours. After treating the filler covered with silane film in step (11) with a modifier, a modified filler intermediate is obtained.

[0028] In the above technical solution, in step (21), preferably, the modified filler intermediate is further surface treated with a surface treatment agent. After the surface treatment, the amount of sulfonic acid groups introduced into the dealkalizing agent is 12 to 56 mmol / m 2 The content of secondary amine groups is 19 to 101 mmol / m 2 The content of methoxyl group is 47~303mmol / m 2 .

[0029] In the above technical scheme, in step (21), the surface treatment agent preferably includes N-(carbamoylmethyl)-2-aminoethanesulfonic acid, 3,5-dichloro-2-methoxyaniline, 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; in terms of mass fractions, N-(carbamoylmethyl)-2-aminoethanesulfonic acid: 3,5-dichloro-2-methoxyaniline: catalyst: solvent = (12-23): (33-54): (16-32): (190-290).

[0030] In the above technical scheme, in step (21), the treatment conditions for treating the modified filler intermediate with the surface treatment agent are as follows: the volume ratio (liquid-to-solid volume ratio) of the surface treatment agent to the modified filler intermediate is 1.5 to 2.5, the immersion treatment temperature is 35°C to 55°C, and the immersion treatment time is 30 to 60 minutes.

[0031] In the above technical scheme, in step (21), after treatment with a modifier or a surface treatment agent, a post-modification treatment is preferably performed, wherein the solvent used for the post-modification treatment is at least one of anhydrous ethanol, anhydrous methanol, and anhydrous acetone, and preferably, the solvent used for the post-modification treatment is anhydrous ethanol.

[0032] In the above technical scheme, in step (21), the post-modification treatment conditions are as follows: the volume ratio (liquid-to-solid volume ratio) of the post-modification treatment agent to the filler (modified filler intermediate or surface-treated modified filler intermediate) is 2 to 6, the temperature is 65°C to 100°C, the pressure (gauge pressure) is 200 to 400 kPa, the treatment time for each treatment is 2.0 to 4.0 hours, the number of treatments is 2 to 3 times, and after the active post-treatment, it is dried at 100°C to 120°C for 0.5 to 1.0 hour in an inert atmosphere (such as nitrogen).

[0033] The third aspect of the present invention provides a use of the dealkalized refined agent provided in the first aspect or the dealkalized refined agent prepared by the method provided in the second aspect in dealkalizing impurities in dry gas.

[0034] In the above technical solution, the application includes: the raw dry gas is contacted with the dealkalizing refining agent to obtain the purified dry gas with dealkalizing impurities.

[0035] In the above technical scheme, preferably, in the application, a dealkalizing refiner is adopted, in which a dealkalizing refining agent bed is provided, a gas collecting pipe with sealed ends is provided at the axial center position of the dealkalizing refiner, a static regeneration agent central axis distributor is provided on the inner side of the gas collecting pipe, a regeneration agent feed port is provided at the upper part of the dealkalizing refiner and is communicated with the regeneration agent central axis distributor, a regeneration agent discharge port is provided at the lower part, a raw material dry gas feed port is provided on the side wall, a purified dry gas discharge port is provided on the top, and the dry gas discharge port is communicated with the gas collecting pipe.

[0036] In the above technical scheme, preferably, in the application, when the dealkalization refiner is started, the raw dry gas enters the dealkalization refiner through the raw dry gas feed port, and flows from the side near the wall of the dealkalization refining agent bed around the dealkalization refining agent bed to the axial center of the dealkalization refining agent bed, and the alkaline impurities in the dry gas are selectively adsorbed by the active layer on the dealkalization refining agent. At the same time, the regeneration agent enters the dealkalization 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 directly reacts with the alkaline impurities in the dry gas, and on the other hand, part of the regeneration agent flows to the dealkalization refining agent under the action of power to regenerate the dealkalization refining agent that adsorbs the alkaline impurities. The regeneration agent after reaction or regeneration is discharged from the regeneration agent discharge port, and the obtained purified dry gas enters the gas collecting pipe for collection and is then discharged from the top of the dealkalization refiner.

[0037] In the above technical scheme, in the application, the dealkalizing refining agent is loaded in the dealkalizing refiner to form a dealkalizing refining agent bed, and the liquid is accelerated to turbulent under the action of power. It is an adsorption refining bed integrating adsorption and regeneration, and adopts online in-situ real-time continuous adsorption and regeneration, that is, adsorption and in-situ regeneration are carried out in the dealkalizing refiner, and the high-speed turbulent regeneration agent realizes the regeneration of the adsorption center through mass transfer through contact with the adsorption center.

[0038] In the above technical solution, in the application, the power is gas driving force, liquid throw-off inertial force, preferably liquid throw-off inertial force. The liquid throw-off inertial force comes from liquid high-pressure injection, and / or the motor drives the dealkalization refining agent bed to move axially or radially in a circular motion.

[0039] In the above technical solution, in the application, the conditions of the dealkalization refining are preferably as follows: the temperature is 20-50°C, the pressure is, according to the gauge pressure, 500-1200 kPa, and the dry gas feed volume space velocity is 300-1500 h -1 The feed ratio of dry gas to regeneration agent solution is 400 to 600 by volume.

[0040] In the above technical solution, in the application, the regeneration agent is selected from at least one of citric acid, tartaric acid, acetoxysuccinic acid, methanesulfonic acid, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, and acetic acid. Preferably, the regeneration agent solution is composed of 10% to 30% tartaric acid, 2% to 4% acetoxysuccinic acid, 1% to 3% methanesulfonic acid, and the rest is desalted water, based on the mass composition percentage.

[0041] In the above technical solution, in the application, the material after dealkalization and refining is preferably subjected to a demisting treatment to remove trace mist entrained in the dry gas after dealkalization and refining. The demisting treatment can be carried out 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.

[0042] In the above technical scheme, the raw material dry gas is derived from catalytic cracking, thermal cracking, delayed coking and hydrocracking in refineries. 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 alkaline impurities, wherein the alkaline impurities include at least one of chain or cyclic nitrogen-containing impurities, which are derived from nitrogen-containing impurities in crude oil and their degradation components, amine-based desulfurizers and their degradation components. In the raw material dry gas, the volume content of ethylene is 5% to 40%, preferably 10% to 20%. In the raw material dry gas, the volume content of total nitrogen element is not less than 5ppm, preferably not less than 50ppm, more preferably not less than 500ppm, and the volume content of total nitrogen element is not higher than 2000ppm, preferably not higher than 1000ppm.

[0043] In the above technical scheme, the alkaline impurities include but are not limited to at least one of the following substances: ammonia, aminomethane, N-methylmethylamine, cyclopropanemethylamine, N-dimethylmethylamine, monoethanolamine, diethanolamine, aminocyclobutane, diisopropanolamine, N-methyldiethanolamine, etc.

[0044] In the above technical scheme, the raw dry gas also includes sulfides (such as hydrogen sulfide, etc.). According to the requirements for the sulfide content in the product dry gas, the raw dry gas can be contacted with a desulfurizer to remove the sulfides before contacting the dealkalizing refining agent to obtain a desulfurized purified dry gas. The desulfurizer is a conventional desulfurizer in the art, preferably an alcohol amine, such as at least one of diethanolamine and N-methyldiethanolamine. The conditions for the raw dry gas to contact the desulfurizer are as follows: the temperature is 15 to 45°C, the pressure is, according to the gauge pressure, 500 to 1200 kPa, and the theoretical plate number of the desulfurization contact tower is 5 to 10. The dosage ratio of the raw dry gas to the desulfurizer is, by volume, 50 to 100, and the mass concentration of the desulfurizer solution used is 20% to 40%.

[0045] In the above technical scheme, according to the requirements for the propylene content in the product dry gas, the purified dry gas free of alkaline impurities can be contacted with a depropylene agent to obtain a purified dry gas free of propylene. 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 dosage ratio of the dry gas to the depropylene agent is, by volume, 60 to 90.

[0046] In the above technical solution, preferably, the total nitrogen volume content in the obtained purified dry gas is not higher than 5 ppm, preferably not higher than 3 ppm, and more preferably not higher than 1 ppm.

[0047] In the above technical solution, preferably, the obtained purified dry gas can meet the requirements of long-term operation of the ethylbenzene alkylation catalyst.

[0048] A fourth aspect of the present invention provides a separation system for removing impurities from dry gas, comprising:

[0049] 1) Desulfurization contact tower, used to remove hydrogen sulfide from dry gas raw materials;

[0050] 2) The dealkalization refining system is used to remove alkaline impurities from the dry gas after desulfurization purification;

[0051] 3) Demister, used to remove trace mist entrained in the dry gas after dealkalization and refining;

[0052] 4) A propylene removal contact tower is used to remove propylene from the dry gas after de-alkali purification.

[0053] In the above technical solution, a dealkalization refining feed buffer tank is provided to separate free liquid entrained in the dry gas after desulfurization and purification.

[0054] In the above technical solution, the dealkalization refining system includes a dealkalization refiner, in which a dealkalization refining agent bed is arranged to remove alkaline impurities in the dry gas.

[0055] In the above technical scheme, preferably, the dealkalization refiner is provided with a dealkalization refining agent bed, a regeneration agent central axis distributor is provided at the axial center, a raw material dry gas feed port is provided on the side wall of the dealkalization refiner, 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.

[0056] In the above technical solution, preferably, a demister or a cyclone is arranged downstream of the dealkalization refiner in the dealkalization refining system to remove trace mist entrained in the dry gas after dealkalization refining.

[0057] In the above technical solution, preferably, a regeneration agent storage tank is provided to buffer the regeneration agent, and the regeneration agent is introduced into and led out of the dealkalization refiner through a liquid conveying device.

[0058] In the above technical solution, preferably, the regenerant storage tank is provided with a fresh regenerant or a regenerant lean solution inlet and a regenerant rich solution outlet for replacing the regenerant when the regenerant utilization rate reaches the process value (eg ≥95%).

[0059] In the above technical solution, a high-pressure pump is provided for pressurized delivery of the regeneration agent.

[0060] Compared with the prior art, the present invention has the following advantages:

[0061] 1. The inventor of the present invention has found through research that there are alkaline 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 volatility of crude oil raw materials and the volatility of the desulfurization process, the alkaline 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 found through further research that the use of dealkalizing refining agents, the use of highly active groups on modified structured fillers to efficiently adsorb the alkaline impurities in the raw dry gas, and the use of a preferred regenerant solution with low corrosiveness but desorption function to quickly flow through the adsorption micro-interface of the dealkalizing refining agent under the action of power, contact and transfer mass with the adsorption active center, and achieve the regeneration of the saturated adsorption center, 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 solution is used through dynamic injection or stripping, continuous random high-speed turbulence is used to achieve regeneration of active centers. Even if the content of alkaline impurities in the dry gas raw material fluctuates greatly, there are sufficient active centers for continuous adsorption, which solves the problem of low elasticity of conventional distillation dealkalization operation.

[0062] 2. In the process of filler modification of the present invention, a silanized layer is first formed on the surface of the filler, so that the original function of the filler can be fully exerted, and the filler can be protected from corrosion to extend the service life. Then, the filler is modified with a modifier, so that a modified layer with an adsorption active center of suitable adsorption strength can be formed on the surface of the silanized layer, and a good adsorption and regeneration effect can be achieved during continuous adsorption and regeneration operations. Preferably, further treatment with a surface treatment agent can reduce the air film resistance when the dry gas contacts the modified layer formed by the modifier treatment, and improve the mass transfer rate. The modified layer formed by the surface treatment has a certain absorption effect on each component in the dry gas, forming a dry gas concentration area of ​​a certain thickness, which is in dynamic equilibrium with the main area of ​​the dry gas, and the alkaline impurity components are continuously exchanged to the modified layer formed by the modifier treatment, thereby achieving deep removal of alkaline impurities in the dry gas. At the same time, it is preferred that the regeneration agent of the present invention has good permeability, especially can effectively desorb the alkaline impurities adsorbed in the modified layer formed by the modifier treatment, so as to restore the active center of the modified dealkalization refining agent, so as to achieve a good balance between continuous adsorption and regeneration.

[0063] 3. The present invention solves the problems of high content of trace alkaline impurities in the existing dry gas raw materials that affect the ethylbenzene alkylation catalyst and short operating cycle of the alkylation catalyst. By efficiently and continuously adsorbing the alkaline 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

[0064] Figure 1 This is a schematic diagram of a separation system for removing impurities from dry gas according to the present invention;

[0065] The reference numerals are described as follows:

[0066] 0101 is a desulfurization contact tower, 0102 is a depropylene contact tower, 1101 is a dealkalization refining feed buffer tank, 1102 is a dealkalization refiner, 1103 is a demister, 1104 is a motor, 1105 is a regeneration agent storage tank, 1106 is a regeneration agent high-pressure pump, 0201 is a desulfurization agent lean liquid inlet, 0202 is a raw material dry gas inlet, 0203 is a desulfurization agent 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 dealkalization refining feed buffer tank condensate outlet, 1202 is a fresh regeneration agent or regeneration agent lean liquid inlet, 1203 is a regeneration agent rich liquid outlet;

[0067] Figure 2 It is a schematic diagram of the structure of the dealkalization refiner of the present invention;

[0068] The reference numerals are described as follows:

[0069] 1131 is a dealkalizing refining agent 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

[0070] 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.

[0071] In the present invention, the specific surface area of ​​a filler refers to the surface area per unit volume of the filler.

[0072] In the present invention, the low-carbon hydrocarbon component analysis adopts gas chromatography Agilent 7890A GC (Agilent, USA), equipped with HP-PLOT Al 2 O 3 KCl (50m×0.53mm×15μm) capillary column, column temperature was maintained at 100℃ for 10 minutes, then increased to 120℃ at 30℃min and maintained for 3 minutes. Carrier gas He flow rate was 3mL / min, injection volume was 0.1mL (quantitative loop), split ratio was 5:1, injection port temperature was 250℃, and detector (FID) temperature was 250℃.

[0073] In the present invention, the nitrogen content in the dry gas material is tested by Mitsubishi sulfur nitrogen analyzer NSX-2100V analyzer, and the analysis method is argon flow rate 200ml / min, oxygen flow rate 400ml / min, and combustion temperature is 1000-1050℃.

[0074] A separation system for removing impurities from dry gas according to the present invention (such as Figure 1As shown), it includes: 0101 is a desulfurization contact tower, 0102 is a depropylene contact tower, 1101 is a dealkalization refining feed buffer tank, 1102 is a dealkalization refiner, 1103 is a demister, 1104 is a motor, 1105 is a regeneration agent storage tank, and 1106 is a regeneration agent high-pressure pump. The separation process is as follows: dry gas raw material (for example, from catalytic cracking, thermal cracking, delayed coking, and hydrocracking in a refinery) enters the desulfurization contact tower 0101 from the middle and lower raw material dry gas inlet 0202 of the desulfurization contact tower 0101, and is countercurrently contacted with the amine desulfurizer coming in from the desulfurizer lean liquid inlet 0201 to remove hydrogen sulfide in the dry gas. The desulfurizer rich liquid is drawn out from the desulfurizer rich liquid outlet 0203 at the bottom of the desulfurization contact tower 0101 to the desulfurizer regeneration unit. The dry gas coming out of the top of the desulfurization contact tower 0101 then enters the dealkalization refining feed buffer tank 1101 to remove free liquid entrained in the dry gas. The condensate in the dealkalization refining feed buffer tank 1101 is discharged from the dealkalization refining feed buffer tank condensate outlet 1201 to the desulfurizer regeneration unit. The gas phase at the top of the dealkalization refining feed buffer tank 1101 then enters a desulfurizer bed provided with a dealkalization refining agent. On the circumferential shell side of the dealkalization refiner 1102, the alkaline impurities in the dry gas flow toward the axis through the dealkalization refining agent layer, and the alkaline impurities in the dry gas are selectively adsorbed by the active groups on the dealkalization refining agent. At the same time, the regeneration agent in the regeneration agent storage tank 1105 is pressurized and transported to the central axis distributor in the dealkalization refiner 1102 by the regeneration agent high-pressure pump 1106. Under the action of liquid high-pressure injection or liquid throw-off inertial force, the adsorption interface is contacted, mass transferred, and regenerated by high-frequency pulses. A demister 1103 is arranged at the outlet of the dealkalization refiner 1102 to remove trace mist entrained in the dry gas after dealkalization refining. The mist is passed through conventional booster equipment or directly into the depropylene contact tower 0102 to countercurrently contact with the depropylene agent 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 regenerant storage tank 1105 is continuously circulated by the regenerant high-pressure pump 1106. When the regenerant utilization rate reaches the process value (≥95%), the liquid level in the regenerant storage tank 1105 is discharged to 1% to 5% through the regenerant rich liquid outlet 1203, 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 1202.

[0075] The structural schematic diagram of the filler refiner of the present invention is as follows Figure 2As shown. Among them, a dealkalizing refining agent bed 1131 is arranged in the dealkalizing refiner 1102, a stationary regeneration agent central axis distributor 1132 is arranged at the axial center position of the dealkalizing refiner 1102, a gas collecting pipe 1133 is arranged outside the regeneration agent central axis distributor 1132, a raw material dry gas feed port 1134 is arranged on the side wall of the dealkalizing refiner 1102, a regeneration agent feed port 1136 is arranged at the upper part and communicated with the regeneration agent central axis distributor 1132, a regeneration agent discharge port 1137 is arranged at the lower part, and a purified dry gas discharge port 1135 is arranged 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 1104 through a shaft, and a sealing ring is arranged at the connection between the upper section of the gas collecting pipe 1033 and the flange. When the dealkalization refiner is started, the raw dry gas enters the dealkalization refiner 1102 through the raw dry gas feed port 1134, and flows from the side near the wall of the dealkalization refining agent bed 1131 around the dealkalization refining agent bed 1131 to the axis of the dealkalization refining agent bed 1131, and the alkaline impurities in the dry gas are selectively adsorbed by the dealkalization refining agent. At the same time, the regeneration agent enters the dealkalization 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 dealkalization refining agent under the action of power to regenerate the dealkalization refining agent that adsorbs the alkaline impurities. On the other hand, part of the regeneration agent directly reacts with the alkaline impurities in the dry gas, and 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 dealkalization refiner.

[0076] [Example 1]

[0077] The dry gas raw material described in this embodiment comes from the catalytic cracking unit of the refinery. The dry gas composition, by volume fraction, includes: methane 17.8769%, ethane 8.1116%, aminocyclobutane 0.0038%, ethylene 15.9982%, N-methylmethylamine 0.0024%, propane 0.1859%, propylene 0.8415%, isobutane 0.0811%, n-butane 0.0157%, cyclopropanemethylamine 0.0034%, N,N-dimethylmethylamine 0.0019%, trans-butene 0.0067%, Isobutylene 0.0381%, cis-butylene 0.0002%, N-methyldiethanolamine 0.0019%, oxygen 0.1370%, aminomethane 0.0034%, nitrogen 13.5422%, hydrogen 29.4523%, ammonia 0.0312%, carbon monoxide 1.4971%, carbon dioxide 3.3268%, acetylene 0.0053%, 1,3-butadiene 0.0001%, hydrogen sulfide 6.6733%, alkanes or alkenes with carbon 5 or above 1.1937%, and other components 0.9499%. The volume content of basic impurities based on total nitrogen element is 350ppm.

[0078] The separation process of this embodiment is as follows Figure 1As shown, the schematic diagram of the dealkalization refiner structure is as follows Figure 2 shown.

[0079] The desulfurizing agent in the desulfurizing contact tower is N-methyldiethanolamine. The contact conditions between the raw dry gas and the desulfurizing agent are as follows: the temperature is 30°C, the pressure is, by gauge pressure, 850 kPa, and the number of theoretical plates of the desulfurizing contact tower is 7. The dosage ratio of the raw dry gas to the desulfurizing agent is, by volume, 75, and the mass concentration of the desulfurizing agent solution is 27%.

[0080] The filler refiner is a dynamic adsorption bed which is provided with a modified filler with adsorption function, namely a dealkalizing refiner, and which promotes the turbulence of the liquid through dynamic action and promotes the continuous regeneration of the adsorption active center.

[0081] The preparation method of the modified filler comprises: firstly subjecting the filler to silanization treatment to obtain a filler covered with a silane film, then treating the filler covered with the silane film with a modifier, treating it with a surface treatment agent, and then subjecting it to post-modification treatment to obtain a dealkalization refined preparation.

[0082] The filler has a specific surface area of ​​1700m 2 / m 3 The metal corrugated wire mesh structured packing (model 1700Y, porosity 80%) is used. The metal is made of 304L material. The silanization treatment adopts the electrodeposition method. First, the filler 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, and dried with nitrogen. Then, cathode electrodeposition is carried out in a silanization agent (γ-aminopropyltriethoxysilane) 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 177 microns. Among them, the silanization 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 75℃, and the cleaning time is 35 minutes; the cleaning conditions of acetone ultrasonic cleaning are as follows: the ultrasonic frequency is 60kHz, the 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 cleaning is rinsed with desalted water 5 times and blown dry with nitrogen at 30℃. The composition of the silanization agent solution, by volume, is silanization agent: desalted water: anhydrous ethanol = 5.6:15:85, the pH value is 9, and the pre-hydrolysis time is 11 hours; the electrodeposition voltage is 10V, and the electrodeposition time is 50 minutes; the drying and curing temperature is 110℃, and the drying atmosphere is nitrogen.

[0083] The modifiers are pretreatment agent, toluene and zinc chloride. The preparation process of the pretreatment agent is as follows: p-chlorobenzhydryl chloride and oleum are reacted to obtain a reaction product, and the reaction product is extracted with ether. The reaction conditions of p-chlorobenzhydryl chloride and oleum are as follows: p-chlorobenzhydryl chloride and oleum, by mass fraction, p-chlorobenzhydryl chloride: oleum = 30:65, the reaction temperature is 75°C, and the treatment time is 4.5 hours. The process conditions of ether extraction are as follows: reaction product and ether, by volume, reaction product: ether = 1:15, the extraction temperature is 25°C, the extraction is continuous for 2.5 hours, the extracts are combined, and then the ether is evaporated at 60°C to obtain the pretreatment agent.

[0084] The composition of the modifier is, by weight, pretreatment agent: zinc chloride: toluene = 28:18.5:250. Zinc chloride uses anhydrous zinc chloride. The process of treating the filler covered with silane film with the modifier is as follows: the volume ratio of the modifier to the filler covered with silane film is 3.5, the immersion treatment temperature is 55°C, and the immersion treatment time is 6 hours. After treating the filler covered with silane film with the modifier, a modified filler intermediate is obtained. After the filler covered with silane film is treated with the modifier, the content of sulfonic acid groups introduced into the modified filler is 0.62 mol / m 2 The content of secondary amine groups is 0.38 mol / m 2 .

[0085] The modified filler intermediate is further surface treated with a surface treatment agent. The surface treatment agent includes N-(carbamoylmethyl)-2-aminoethanesulfonic acid, 3,5-dichloro-2-methoxyaniline, zinc chloride and toluene. By mass, N-(carbamoylmethyl)-2-aminoethanesulfonic acid: 3,5-dichloro-2-methoxyaniline: zinc chloride: toluene = 17:43:24:240. The surface treatment conditions are as follows: the volume ratio of the surface treatment agent to the modified filler intermediate is 2, the immersion treatment temperature is 45°C, and the immersion treatment time is 45 minutes. After treatment with the surface treatment agent, the sulfonic acid group content introduced into the modified filler by the surface treatment agent is 34mmol / m 2 The secondary amine content is 60mmol / m 2 , the methoxy content is 175mmol / m 2 .

[0086] The modified filler intermediate is subjected to modification post-treatment to obtain a modified filler. The solvent used for the modification post-treatment is anhydrous ethanol. The modification post-treatment conditions are as follows: the volume ratio of the modification post-treatment agent to the filler is 4, the temperature is 82.5°C, the pressure (gauge pressure) is 300 kPa, each treatment time is 3 hours, the number of treatments is 3 times, and after the active post-treatment, it is dried in nitrogen at 110°C for 0.7 hours.

[0087] The desulfurization purified dry gas feed volume space velocity of the dealkalization refining bed is 1000h-1 , the dealkalization refining agent, the adsorption temperature is 35℃, and the adsorption pressure (gauge pressure) is 800kPa. The liquid power in the dealkalization refining bed is the liquid throw-off inertia force, which comes from the high-pressure liquid injection and the circular motion of the filler driven by the motor. The dealkalization refining bed regeneration agent solution is composed of 20% tartaric acid, 3% acetoxysuccinic acid, 2% methanesulfonic acid, and the rest is desalted water in terms of mass composition percentage. Among them, the feed ratio of desulfurized purified dry gas to regeneration agent solution is 500 by volume.

[0088] The de-alkali refining bed demister is a wire mesh demister with a separation accuracy of 4 microns and a thickness of 100 mm.

[0089] The depropylene agent in the depropylene contact tower is benzene. The contact conditions between the raw dry gas and the depropylene agent are as follows: the temperature is 17°C, the pressure is, by gauge pressure, 1100 kPa, and the theoretical plate number of the depropylene contact tower is 11. The dosage ratio of the raw dry gas to the depropylene agent is, by volume, 75.

[0090] The total nitrogen volume content in the propylene-removed purified dry gas obtained in this example is 4.4 ppm.

[0091] [Example 2]

[0092] The dry gas raw material described in this embodiment is the same as that in Example 1. The separation process of this embodiment is as follows: Figure 1 As shown, the schematic diagram of the dealkalization refiner structure is as follows Figure 2 shown.

[0093] The desulfurizing agent in the desulfurizing contact tower is N-methyldiethanolamine. The contact conditions between the raw dry gas and the desulfurizing agent are as follows: the temperature is 44°C, the pressure is, by gauge pressure, 1100 kPa, and the theoretical plate number of the desulfurizing contact tower is 9. The dosage ratio of the raw dry gas to the desulfurizing agent is, by volume, 58, and the mass concentration of the desulfurizing agent is 33%.

[0094] The filler refiner is a dynamic adsorption bed which is provided with a modified filler with adsorption function, namely a dealkalizing refiner, and which promotes the turbulence of the liquid through dynamic action and promotes the continuous regeneration of the adsorption active center.

[0095] The preparation method of the modified filler comprises: firstly subjecting the filler to silanization treatment to obtain a filler covered with a silane film, then treating the filler covered with the silane film with a modifier, treating it with a surface treatment agent, and then subjecting it to post-modification treatment to obtain a dealkalization refined preparation.

[0096] The filler has a specific surface area of ​​2500m 2 / m 3(Model 2500Y, porosity 75%) metal corrugated wire mesh structured packing. The metal is made of 304 material. The silanization treatment adopts the electrodeposition method. First, the filler 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, and dried with nitrogen. Then, cathode electrodeposition is carried out in a silanization agent (γ-aminopropyltriethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 1.2 and a thickness of 296 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 cleaning temperature is 38℃, and the cleaning time is 29 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 6.5%, sodium phosphate is 0.9%, the ultrasonic frequency of alkali cleaning is 55kHz, the alkali cleaning temperature is 86℃, and the alkali cleaning time is 28 minutes; the filler after alkali cleaning is rinsed with desalted water for 6 times and blown dry with nitrogen at 38℃. The composition of the silanization agent solution, by volume, is silanization agent: desalted water: anhydrous ethanol = 6.7:15.3:81, the pH value is 9.3, and the pre-hydrolysis time is 11.5 hours; the electrodeposition voltage is 12V, and the electrodeposition time is 56 minutes; the drying and curing temperature is 117℃, and the drying atmosphere is nitrogen.

[0097] The modifiers are pretreatment agent, toluene and zinc chloride. The preparation process of the pretreatment agent is as follows: p-chlorobenzhydryl chloride and oleum are reacted to obtain a reaction product, and the reaction product is extracted with ether. The reaction conditions of p-chlorobenzhydryl chloride and oleum are as follows: p-chlorobenzhydryl chloride and oleum, by mass fraction, p-chlorobenzhydryl chloride: oleum = 25:75, the reaction temperature is 85°C, and the treatment time is 5.5 hours. The process conditions of ether extraction are as follows: reaction product and ether, by volume, reaction product: ether = 1:18, the extraction temperature is 28°C, the extraction is continuous for 2.7 hours, the extracts are combined, and then the ether is evaporated at 65°C to obtain the pretreatment agent.

[0098] The composition of the modifier is, by weight, pretreatment agent: zinc chloride: toluene = 33:20:210. Zinc chloride uses anhydrous zinc chloride. The process of treating the filler covered with silane film with the modifier is as follows: the volume ratio of the modifier to the filler covered with silane film is 5, the immersion treatment temperature is 63°C, and the immersion treatment time is 7 hours. After treating the filler covered with silane film with the modifier, a modified filler intermediate is obtained. After the filler covered with silane film is treated with the modifier, the content of sulfonic acid group introduced into the modified filler is 0.81 mol / m 2 The secondary amine content is 0.56 mol / m 2 .

[0099] The modified filler intermediate is further surface treated with a surface treatment agent. The surface treatment agent includes N-(carbamoylmethyl)-2-aminoethanesulfonic acid, 3,5-dichloro-2-methoxyaniline, zinc chloride and toluene. By mass, N-(carbamoylmethyl)-2-aminoethanesulfonic acid: 3,5-dichloro-2-methoxyaniline: zinc chloride: toluene = 21:53:28:220. The surface treatment conditions are as follows: the volume ratio of the surface treatment agent to the modified filler intermediate is 2.3, the immersion treatment temperature is 52°C, and the immersion treatment time is 57 minutes. After treatment with the surface treatment agent, the sulfonic acid group content introduced into the modified filler by the surface treatment agent is 53mmol / m 2 The secondary amine content is 91mmol / m 2 The methoxy content is 295mmol / m 2 .

[0100] The modified filler intermediate is subjected to modification post-treatment to obtain a modified filler. The solvent used for the modification post-treatment is anhydrous ethanol. The modification post-treatment conditions are as follows: the volume ratio of the modification post-treatment agent to the filler is 5, the temperature is 90°C, the pressure (gauge pressure) is 370 kPa, each treatment time is 3.6 hours, the number of treatments is 3 times, and after the active post-treatment, it is dried in nitrogen at 118°C for 0.9 hours.

[0101] The desulfurization purified dry gas feed volume space velocity of the dealkalization refining bed is 430h -1 , the dealkalization refining agent, the adsorption temperature is 47℃, and the adsorption pressure (gauge pressure) is 1100kPa. The liquid power in the dealkalization refining bed is the liquid throw-off inertia force, which comes from the liquid high-pressure injection and the circular motion of the filler driven by the motor. The dealkalization refining bed regeneration agent solution is composed of 28% tartaric acid, 3.6% acetoxysuccinic acid, 2.9% methanesulfonic acid, and the rest is desalted water in terms of mass composition percentage. Among them, the feed ratio of desulfurized purified dry gas to regeneration agent solution is 450 by volume.

[0102] The de-alkali refining bed demister is a wire mesh demister with a separation accuracy of 3 microns and a thickness of 150 mm.

[0103] The depropylene agent in the depropylene contact tower is benzene. The contact conditions between the raw dry gas and the depropylene agent are as follows: the temperature is 11°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 dry gas to the depropylene agent is, by volume, 65.

[0104] The total nitrogen volume content in the propylene-removed purified dry gas obtained in this example is 1.4 ppm.

[0105] [Example 3]

[0106] The dry gas raw material described in this embodiment is the same as that in Example 1. The separation process of this embodiment is as follows: Figure 1 As shown, the schematic diagram of the dealkalization refiner structure is as follows Figure 2 shown.

[0107] The desulfurizing agent in the desulfurizing contact tower is N-methyldiethanolamine. The contact conditions between the raw dry gas and the desulfurizing agent are as follows: the temperature is 16°C, the pressure is, by gauge pressure, 550 kPa, and the theoretical plate number of the desulfurizing contact tower is 6. The dosage ratio of the raw dry gas to the desulfurizing agent is, by volume, 90, and the mass concentration of the desulfurizing agent is 25%.

[0108] The filler refiner is a dynamic adsorption bed which is provided with a modified filler with adsorption function, namely a dealkalizing refiner, and which promotes the turbulence of the liquid through dynamic action and promotes the continuous regeneration of the adsorption active center.

[0109] The preparation method of the modified filler comprises: firstly subjecting the filler to silanization treatment to obtain a filler covered with a silane film, then treating the filler covered with the silane film with a modifier, treating it with a surface treatment agent, and then subjecting it to post-modification treatment to obtain a dealkalization refined preparation.

[0110] The filler has a specific surface area of ​​1100m 2 / m 3 (Model 1100Y, porosity 84%) metal corrugated wire mesh structured packing. The metal is made of 304 material. The silanization treatment adopts the electrodeposition method. First, the filler 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, and dried with nitrogen. Then, cathode electrodeposition is carried out in a silanization agent (γ-aminopropyltriethoxysilane) 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 81 microns. Among them, the silanization 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 cleaning 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 ultrasonic cleaning frequency is 75kHz, the cleaning temperature is 23℃, and the cleaning time is 21 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 5.5%, sodium phosphate is 0.6%, the alkali cleaning temperature is 65℃, and the alkali cleaning time is 20 minutes; the filler after alkali cleaning is rinsed with desalted water 4 times and blown dry with nitrogen at 20℃. The composition of the silanization agent solution, by volume, is silanization agent: desalted water: anhydrous ethanol = 4.6:15:90, the pH value is 8.7, and the pre-hydrolysis time is 11 hours; the electrodeposition voltage is 8V, and the electrodeposition time is 43 minutes; the drying and curing temperature is 108℃, and the drying atmosphere is nitrogen.

[0111] The modifiers are pretreatment agent, toluene and zinc chloride. The preparation process of the pretreatment agent is as follows: p-chlorobenzhydryl chloride and oleum are reacted to obtain a reaction product, and the reaction product is extracted with ether. The reaction conditions of p-chlorobenzhydryl chloride and oleum are as follows: p-chlorobenzhydryl chloride and oleum, by mass fraction, p-chlorobenzhydryl chloride: oleum = 36:59, the reaction temperature is 67°C, and the treatment time is 3.3 hours. The process conditions of ether extraction are as follows: reaction product and ether, by volume, reaction product: ether = 1:12, the extraction temperature is 23°C, the extraction is continuous for 2.1 hours, the extracts are combined, and then the ether is evaporated at 54°C to obtain the pretreatment agent.

[0112] The composition of the modifier is, by weight, pretreatment agent: zinc chloride: toluene = 25:14:280. Zinc chloride uses anhydrous zinc chloride. The process of treating the filler covered with silane film with the modifier is as follows: the volume ratio of the modifier to the filler covered with silane film is 2, the immersion treatment temperature is 48°C, and the immersion treatment time is 5 hours. After treating the filler covered with silane film with the modifier, a modified filler intermediate is obtained. After the filler covered with silane film is treated with the modifier, the content of sulfonic acid groups introduced into the modified filler is 0.53 mol / m 2 The content of secondary amine groups is 0.20 mol / m 2 .

[0113] The modified filler intermediate is further surface treated with a surface treatment agent. The surface treatment agent includes N-(carbamoylmethyl)-2-aminoethanesulfonic acid, 3,5-dichloro-2-methoxyaniline, zinc chloride and toluene. By mass, N-(carbamoylmethyl)-2-aminoethanesulfonic acid: 3,5-dichloro-2-methoxyaniline: zinc chloride: toluene = 13:35:17:270. The surface treatment conditions are as follows: the volume ratio of the surface treatment agent to the modified filler intermediate is 1.7, the immersion treatment temperature is 37°C, and the immersion treatment time is 34 minutes. After treatment with the surface treatment agent, the sulfonic acid group content introduced into the modified filler by the surface treatment agent is 22mmol / m 2 The secondary amine content is 31mmol / m 2 The methoxy content is 63mmol / m 2 .

[0114] The modified filler intermediate is subjected to modification post-treatment to obtain a modified filler. The solvent used for the modification post-treatment is anhydrous ethanol. The modification post-treatment conditions are as follows: the volume ratio of the modification post-treatment agent to the filler is 2.4, the temperature is 68°C, the pressure (gauge pressure) is 240 kPa, each treatment time is 2.3 hours, the number of treatments is 2 times, and after the active post-treatment, it is dried in nitrogen at 105°C for 0.6 hours.

[0115] The desulfurization purified dry gas feed volume space velocity of the dealkalization refining bed is 1300h-1 , the dealkalization refining agent, the adsorption temperature is 25℃, and the adsorption pressure (gauge pressure) is 700kPa. The liquid power in the dealkalization refining bed is the liquid throw-off inertia force, which comes from the liquid high-pressure injection and the circular motion of the filler driven by the motor. The dealkalization refining bed regeneration agent solution is composed of 11% tartaric acid, 2.1% acetoxysuccinic acid, 1.2% methanesulfonic acid, and the rest is desalted water in terms of mass composition percentage. Among them, the feed ratio of desulfurized purified dry gas to regeneration agent solution is 550 by volume.

[0116] The de-alkali refining bed demister is a wire mesh demister with a separation accuracy of 5 microns and a thickness of 100 mm.

[0117] The depropylene agent in the depropylene contact tower is benzene. The contact conditions between the raw dry gas and the depropylene agent are as follows: the temperature is 24°C, the pressure is, by gauge pressure, 1000 kPa, and the theoretical plate number of the depropylene contact tower is 9. The dosage ratio of the raw dry gas to the depropylene agent is, by volume, 85.

[0118] The total nitrogen volume content in the propylene-removed purified dry gas obtained in this example is 5.4 ppm.

[0119] [Example 4]

[0120] The dealkalizing refining agent used in this embodiment is the same as that in Example 2.

[0121] The separation process for the dry gas raw material in this embodiment is the same as that in Example 2. The only difference between this embodiment and Example 2 is the dry gas raw material used. The dry gas composition, by volume ratio, includes: methane 17.8682%, ethane 8.1077%, N-methyldiethanolamine 0.0038%, propane 0.1858%, propylene 0.8411%, isobutane 0.0811%, n-butane 0.0156%, N,N-dimethylmethylamine 0.0038%, trans-butene 0.0067%, isobutylene 0.0380%, cis-butene 0.0002%, ammonia 0.0624%, cyclopropane methane Amine 0.0067%, nitrogen 13.5356%, hydrogen 29.4381%, N-methyl methylamine 0.0048%, carbon monoxide 1.4964%, aminocyclobutane 0.0077%, carbon dioxide 3.3252%, aminomethane 0.0067%, acetylene 0.0053%, 1,3-butadiene 0.0001%, hydrogen sulfide 6.6700%, C5+ alkane or olefin 1.1932%, other components 0.9498%. The volume content of basic impurities based on total nitrogen element is 650ppm.

[0122] The total nitrogen content of the obtained propylene-free purified dry gas was 2 ppm by volume.

[0123] [Example 5]

[0124] The dealkalizing refining agent used in this embodiment is the same as that in Example 2.

[0125] The separation process for the dry gas raw material in this embodiment is the same as that in Example 2. The only difference between this embodiment and Example 2 is the dry gas raw material used. The dry gas composition, by volume ratio, includes: methane 17.8853%, ethane 8.1154%, aminomethane 0.0001% ethylene 16.0057%, propane 0.1860%, propylene 0.8419%, isobutane 0.0812%, normal butane 0.0157%, trans-butene 0.0067%, ammonia 0.0008%, normal butene 0.0185%, isobutylene 0.0381%, N-methyl methylamine 0.0001%, Cis-butene 0.0002%, aminocyclobutane 0.0001%, oxygen 0.1371%, nitrogen 13.5486%, hydrogen 29.4662%, cyclopropanemethylamine 0.0001%, carbon monoxide 1.4978%, carbon dioxide 3.3284%, acetylene 0.0053%, 1,3-butadiene 0.0001%, hydrogen sulfide 6.6764%, alkanes or alkenes with carbon 5 or above 1.1943%, and other components 0.9500%. The volume content of basic impurities based on total nitrogen element is 8ppm.

[0126] The total nitrogen volume content of the obtained propylene-free purified dry gas was 0.11 ppm.

[0127] [Example 6]

[0128] The dry gas raw material described in this embodiment is the same as that in Example 1. The separation process of this embodiment is as follows: Figure 1 As shown, the schematic diagram of the dealkalization refiner structure is as follows Figure 2 shown.

[0129] The desulfurizing agent in the desulfurizing contact tower is N-methyldiethanolamine. The contact conditions between the raw dry gas and the desulfurizing agent are as follows: the temperature is 44°C, the pressure is, by gauge pressure, 1100 kPa, and the theoretical plate number of the desulfurizing contact tower is 9. The dosage ratio of the raw dry gas to the desulfurizing agent is, by volume, 58, and the mass concentration of the desulfurizing agent is 33%.

[0130] The filler refiner is a dynamic adsorption bed which is provided with a modified filler with adsorption function, namely a dealkalizing refiner, and which promotes the turbulence of the liquid through dynamic action and promotes the continuous regeneration of the adsorption active center.

[0131] The preparation method of the modified filler comprises: firstly subjecting the filler to silanization treatment to obtain a filler covered with a silane film, then treating the filler covered with the silane film with a modifier, and then treating the filler with a surface treatment agent to obtain a dealkalizing refined preparation.

[0132] The filler has a specific surface area of ​​2500m 2 / m 3(Model 2500Y, porosity 75%) metal corrugated wire mesh structured packing. The metal is made of 304 material. The silanization treatment adopts the electrodeposition method. First, the filler 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, and dried with nitrogen. Then, cathode electrodeposition is carried out in a silanization agent (γ-aminopropyltriethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 1.2 and a thickness of 296 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 cleaning temperature is 38℃, and the cleaning time is 29 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 6.5%, sodium phosphate is 0.9%, the ultrasonic frequency of alkali cleaning is 55kHz, the alkali cleaning temperature is 86℃, and the alkali cleaning time is 28 minutes; the filler after alkali cleaning is rinsed with desalted water for 6 times and blown dry with nitrogen at 38℃. The composition of the silanization agent solution, by volume, is silanization agent: desalted water: anhydrous ethanol = 6.7:15.3:81, the pH value is 9.3, and the pre-hydrolysis time is 11.5 hours; the electrodeposition voltage is 12V, and the electrodeposition time is 56 minutes; the drying and curing temperature is 117℃, and the drying atmosphere is nitrogen.

[0133] The modifiers are pretreatment agent, toluene and zinc chloride. The preparation process of the pretreatment agent is as follows: p-chlorobenzhydryl chloride and oleum are reacted to obtain a reaction product, and the reaction product is extracted with ether. The reaction conditions of p-chlorobenzhydryl chloride and oleum are as follows: p-chlorobenzhydryl chloride and oleum, by mass fraction, p-chlorobenzhydryl chloride: oleum = 25:75, the reaction temperature is 85°C, and the treatment time is 5.5 hours. The process conditions of ether extraction are as follows: reaction product and ether, by volume, reaction product: ether = 1:18, the extraction temperature is 28°C, the extraction is continuous for 2.7 hours, the extracts are combined, and then the ether is evaporated at 65°C to obtain the pretreatment agent.

[0134] The composition of the modifier is, by weight, pretreatment agent: zinc chloride: toluene = 33:20:210. Zinc chloride uses anhydrous zinc chloride. The process of treating the filler covered with silane film with the modifier is as follows: the volume ratio of the modifier to the filler covered with silane film is 5, the immersion treatment temperature is 63°C, and the immersion treatment time is 7 hours. After treating the filler covered with silane film with the modifier, a modified filler intermediate is obtained. After the filler covered with silane film is treated with the modifier, the content of sulfonic acid group introduced into the modified filler is 0.81 mol / m 2 The secondary amine content is 0.56 mol / m 2 .

[0135] The modified filler intermediate is further surface treated with a surface treatment agent. The surface treatment agent includes N-(carbamoylmethyl)-2-aminoethanesulfonic acid, 3,5-dichloro-2-methoxyaniline, zinc chloride and toluene. By mass, N-(carbamoylmethyl)-2-aminoethanesulfonic acid: 3,5-dichloro-2-methoxyaniline: zinc chloride: toluene = 21:53:28:220. The surface treatment conditions are as follows: the volume ratio of the surface treatment agent to the modified filler intermediate is 2.3, the immersion treatment temperature is 52°C, and the immersion treatment time is 57 minutes. After treatment with the surface treatment agent, the sulfonic acid group content introduced into the modified filler by the surface treatment agent is 53mmol / m 2 The secondary amine content is 91mmol / m 2 The methoxy content is 295mmol / m 2 .

[0136] The desulfurization purified dry gas feed volume space velocity of the dealkalization refining bed is 430h -1 , the dealkalization refining agent, the adsorption temperature is 47℃, and the adsorption pressure (gauge pressure) is 1100kPa. The liquid power in the dealkalization refining bed is the liquid throw-off inertia force, which comes from the liquid high-pressure injection and the circular motion of the filler driven by the motor. The dealkalization refining bed regeneration agent solution is composed of 28% tartaric acid, 3.6% acetoxysuccinic acid, 2.9% methanesulfonic acid, and the rest is desalted water in terms of mass composition percentage. Among them, the feed ratio of desulfurized purified dry gas to regeneration agent solution is 450 by volume.

[0137] The de-alkali refining bed demister is a wire mesh demister with a separation accuracy of 3 microns and a thickness of 150 mm.

[0138] The depropylene agent in the depropylene contact tower is benzene. The contact conditions between the raw dry gas and the depropylene agent are as follows: the temperature is 11°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 dry gas to the depropylene agent is, by volume, 65.

[0139] The total nitrogen volume content in the propylene-removed purified dry gas obtained in this example is 2.5 ppm.

[0140] [Example 7]

[0141] The separation process of this embodiment is as follows Figure 1 As shown, the schematic diagram of the dealkalization refiner structure is as follows Figure 2 shown.

[0142] The desulfurizing agent in the desulfurizing contact tower is N-methyldiethanolamine. The contact conditions between the raw dry gas and the desulfurizing agent are as follows: the temperature is 44°C, the pressure is, by gauge pressure, 1100 kPa, and the theoretical plate number of the desulfurizing contact tower is 9. The dosage ratio of the raw dry gas to the desulfurizing agent is, by volume, 58, and the mass concentration of the desulfurizing agent is 33%.

[0143] The filler refiner is a dynamic adsorption bed provided with a modified filler having an adsorption function, namely a dealkalizing refiner, which promotes the turbulence of the liquid through dynamic action and promotes the continuous regeneration of the adsorption active center. The preparation method of the modified filler comprises: the filler is first subjected to silanization treatment to obtain a filler covered with a silane film, and then the filler covered with a silane film is treated with a modifier to obtain the dealkalizing refiner.

[0144] The filler has a specific surface area of ​​2500m 2 / m 3 (Model 2500Y, porosity 75%) metal corrugated wire mesh structured packing. The metal is made of 304 material. The silanization treatment adopts the electrodeposition method. First, the filler 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, and dried with nitrogen. Then, cathode electrodeposition is carried out in a silanization agent (γ-aminopropyltriethoxysilane) solution, and then dried and solidified to obtain a silane film with a molar ratio of silane ether group to silicon carbon group of 1.2 and a thickness of 296 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 cleaning temperature is 38℃, and the cleaning time is 29 minutes; the composition of the alkali solution, by mass content, sodium hydroxide is 6.5%, sodium phosphate is 0.9%, the ultrasonic frequency of alkali cleaning is 55kHz, the alkali cleaning temperature is 86℃, and the alkali cleaning time is 28 minutes; the filler after alkali cleaning is rinsed with desalted water for 6 times and blown dry with nitrogen at 38℃. The composition of the silanization agent solution, by volume, is silanization agent: desalted water: anhydrous ethanol = 6.7:15.3:81, the pH value is 9.3, and the pre-hydrolysis time is 11.5 hours; the electrodeposition voltage is 12V, and the electrodeposition time is 56 minutes; the drying and curing temperature is 117℃, and the drying atmosphere is nitrogen.

[0145] The modifiers are pretreatment agent, toluene and zinc chloride. The preparation process of the pretreatment agent is as follows: p-chlorobenzhydryl chloride and oleum are reacted to obtain a reaction product, and the reaction product is extracted with ether. The reaction conditions of p-chlorobenzhydryl chloride and oleum are as follows: p-chlorobenzhydryl chloride and oleum, by mass fraction, p-chlorobenzhydryl chloride: oleum = 25:75, the reaction temperature is 85°C, and the treatment time is 5.5 hours. The process conditions of ether extraction are as follows: reaction product and ether, by volume, reaction product: ether = 1:18, the extraction temperature is 28°C, the extraction is continuous for 2.7 hours, the extracts are combined, and then the ether is evaporated at 65°C to obtain the pretreatment agent.

[0146] The composition of the modifier is, by weight, pretreatment agent: zinc chloride: toluene = 33:20:210. Zinc chloride uses anhydrous zinc chloride. The process of treating the filler covered with silane film with the modifier is as follows: the volume ratio of the modifier to the filler covered with silane film is 5, the immersion treatment temperature is 63°C, and the immersion treatment time is 7 hours. After treating the filler covered with silane film with the modifier, a modified filler intermediate is obtained. After the filler covered with silane film is treated with the modifier, the content of sulfonic acid group introduced into the modified filler is 0.81 mol / m 2 The secondary amine content is 0.56 mol / m 2 .

[0147] The desulfurization purified dry gas feed volume space velocity of the dealkalization refining bed is 430h -1 , the dealkalization refining agent, the adsorption temperature is 47℃, and the adsorption pressure (gauge pressure) is 1100kPa. The liquid power in the dealkalization refining bed is the liquid throw-off inertia force, which comes from the liquid high-pressure injection and the circular motion of the filler driven by the motor. The dealkalization refining bed regeneration agent solution is composed of 28% tartaric acid, 3.6% acetoxysuccinic acid, 2.9% methanesulfonic acid, and the rest is desalted water in terms of mass composition percentage. Among them, the feed ratio of desulfurized purified dry gas to regeneration agent solution is 450 by volume.

[0148] The de-alkali refining bed demister is a wire mesh demister with a separation accuracy of 3 microns and a thickness of 150 mm.

[0149] The depropylene agent in the depropylene contact tower is benzene. The contact conditions between the raw dry gas and the depropylene agent are as follows: the temperature is 11°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 dry gas to the depropylene agent is, by volume, 65.

[0150] The total nitrogen volume content in the propylene-removed purified dry gas obtained in this example is 5.3 ppm.

[0151] [Comparative Example 1]

[0152] The preparation of the dealkalized refined agent in this comparative example is compared with that in Example 3, in that a commercially available alkali-free refined agent with a specific surface area of ​​1100 m 2 / m 3 The metal corrugated wire mesh structured packing (model 1100Y, porosity 84%). 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.

[0153] The total nitrogen volume content of the obtained depropylene purified dry gas was 29 ppm.

[0154] [Comparative Example 2]

[0155] The dry gas raw material used in this comparative example is the same as that in Example 3, the desulfurization and depropylene removal are the same as those in Example 3, and the alkaline impurities are removed by water washing using a packed tower (model 250Y, porosity 96%). The equipment and process operating conditions of the water washing tower are as follows: temperature 35°C, pressure (gauge pressure) 1000 kPa, theoretical plate number 18, dilute sulfuric acid aqueous solution with a pH of 3, and a gas-liquid volume ratio of 40.

[0156] The total nitrogen volume content of the obtained propylene-free purified dry gas was 44 ppm.

[0157] [Comparative Example 3]

[0158] The dry gas raw material used in this comparative example is the same as that in Example 3, the desulfurization and depropylene removal are the same as those in Example 3, and the alkaline impurities are removed by using commercial NKC-9 resin (H type) (Nankai Resin Company) as the adsorbent, and a conventional fixed bed adsorption process is adopted. The adsorption conditions are as follows: the resin filling amount is 100 cubic meters, the adsorption temperature is 30°C, and the volume space velocity is 50h -1 .

[0159] In the initial stage of operation, the total nitrogen volume content in the obtained depropylene purified dry gas is 4ppm, and the adsorbent breaks through in about 7 days. Regeneration requires sulfuric acid with a mass concentration of 4% to 6%, and the volume consumption of regeneration liquid per unit volume of adsorbent is 4 to 5 times.

[0160] 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 dealkalized refined preparation, characterized in that: The dealkalizing refining agent includes filler, silane film and modified layer from inside to outside, wherein the modified layer contains sulfonic acid group and secondary amine group; in the silane film, the molar ratio of silane ether group to silicon carbon group is 0.9-1.3, and the thickness of the silane film is 50-300 microns; in the modified layer, the content of sulfonic acid group is 0.42-0.83 mol / m 2 The content of secondary amine groups is 0.17~0.59mol / m 2 .

2. The dealkalizing refining agent according to claim 1, characterized in that: The filler is at least one of a grid structured filler or a corrugated structured filler; the filler is made of metal, plastic or ceramic.

3. The dealkalizing refining agent according to claim 2, characterized in that: The filler is a metal corrugated wire mesh structured filler.

4. The dealkalized refined preparation according to claim 2, characterized in that: The specific surface area of ​​the filler is 1000 to 2600 m 2 / m 3 , the porosity is 74% to 85%.

5. The dealkalized refined preparation according to any one of claims 1 to 4, characterized in that: The outer surface of the modified layer also includes a surface treatment layer; in the surface treatment layer, the content of sulfonic acid groups is 12 to 56 mmol / m 2 The content of secondary amine groups is 19 to 101 mmol / m 2 The content of methoxyl group is 47~303mmol / m 2 .

6. The method for preparing the dealkalized refined preparation according to any one of claims 1 to 4, comprising: (11) Preparing a filler coated with a silane film; (21) The filler coated with the silane film described in step (11) is treated with a modifier to obtain a dealkalized refined preparation.

7. The preparation method according to claim 6, characterized in that: The modifier described in step (21) comprises a pretreatment agent, a catalyst and a solvent; the catalyst is selected from one of Lewis acids or Lewis bases; the solvent is selected from at least one of toluene, p-xylene, m-xylene and o-xylene; wherein the preparation method of the pretreatment agent is as follows: a pretreatment raw material is reacted with fuming sulfuric acid to obtain a pretreatment agent; the pretreatment raw material is selected from at least one of 4,4'-dichlorodiphenylmethanol, p-chlorodiphenylmethyl chloride and 4-chlorodiphenylmethane.

8. The preparation method according to claim 7, characterized in that: In step (21), the catalyst is at least one of anhydrous zinc chloride, anhydrous tin tetrachloride, and anhydrous aluminum chloride.

9. The preparation method according to claim 7, characterized in that: In step (21), the pre-treated raw material is p-chlorobenzhydryl chloride.

10. The preparation method according to claim 7, characterized in that: In step (21), the reaction conditions of the pretreated raw material and oleum are as follows: pretreated raw material and oleum, calculated by mass parts, pretreated raw material: oleum = (20-40): (50-80), the reaction temperature is 60° C.-90° C., and the reaction time is 3-6 hours.

11. The preparation method according to claim 7, characterized in that: The modifier composition described in step (21) includes, by weight, pretreatment agent: catalyst: solvent = (5-10): (4-8): (180-360).

12. The preparation method according to claim 7, characterized in that: The process of step (21) is as follows: the volume ratio of the modifier to the filler covered with the silane film obtained in step (11) is 1 to 6, the immersion treatment temperature is 45° C. to 65° C., and the immersion treatment time is 4 to 8 hours.

13. The preparation method according to claim 6, characterized in that: In step (21), after the filler coated with the silane film in step (11) is treated with a modifier, it is further surface treated with a surface treatment agent. After the surface treatment, the content of the sulfonic acid group introduced into the dealkalizing refining agent is 12 to 56 mmol / m 2 The content of secondary amine groups is 19 to 101 mmol / m 2 The content of methoxyl group is 47~303mmol / m 2 .

14. The preparation method according to claim 13, characterized in that: In step (21), the surface treatment agent comprises N-(carbamoylmethyl)-2-aminoethanesulfonic acid, 3,5-dichloro-2-methoxyaniline, a catalyst and a solvent; the catalyst is selected from one of a Lewis acid or a Lewis base; the solvent is selected from at least one of toluene, p-xylene, m-xylene and o-xylene; and / or, by weight, N-(carbamoylmethyl)-2-aminoethanesulfonic acid: 3,5-dichloro-2-methoxyaniline: catalyst: solvent = (12-23): (33-54): (16-32): (190-290); and / or, the surface treatment agent treatment conditions are as follows: liquid-to-solid volume ratio is 1.5-2.5, the immersion treatment temperature is 35° C.-55° C., and the immersion treatment time is 30-60 minutes.

15. The preparation method according to claim 14, characterized in that: In step (21), the catalyst is at least one of anhydrous zinc chloride, anhydrous tin tetrachloride, and anhydrous aluminum chloride.

16. The preparation method according to claim 6 or 13, characterized in that: After the treatment with the modifier or the surface treatment agent in step (21), a post-modification treatment is performed, wherein the solvent used for the post-modification treatment is at least one of anhydrous ethanol, anhydrous methanol, and anhydrous acetone.

17. The preparation method according to claim 16, characterized in that: In step (21), the modification post-treatment conditions are as follows: liquid-to-solid volume ratio is 2 to 6, temperature is 65°C to 100°C, gauge pressure is 200 to 400 kPa, each treatment time is 2.0 to 4.0 hours, the number of treatments is 2 to 3 times, and after the active post-treatment, drying is performed in an inert atmosphere at 100°C to 120°C for 0.5 to 1.0 hour.

18. Use of the dealkalized refined preparation according to any one of claims 1 to 5 or the dealkalized refined preparation prepared by the preparation method according to any one of claims 6 to 17 in dealkalizing impurities in dry gas, wherein: The raw dry gas is contacted with the dealkalizing refining agent to obtain a purified dry gas free of alkaline impurities.

19. The use according to claim 18, characterized in that The application adopts a dealkalizing refiner, in which a dealkalizing refining agent bed is provided, a gas collecting pipe with sealed ends is provided at the axial center position of the dealkalizing refiner, a static regeneration agent central axis distributor is provided on the inner side of the gas collecting pipe, a regeneration agent feed port is provided at the upper part of the dealkalizing refiner and is communicated with the regeneration agent central axis distributor, a regeneration agent discharge port is provided at the lower part, a raw dry gas feed port is provided on the side wall, 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 dealkalizing refining agent, and at the same time, the regeneration agent flows to the dealkalizing refining agent through the regeneration agent central axis distributor under the action of power, and adsorption and regeneration are achieved at the same time, thereby obtaining purified dry gas and regeneration agent solution after working.

20. The use according to claim 19, characterized in that The regeneration agent is selected from at least one of citric acid, tartaric acid, acetoxysuccinic acid, methanesulfonic acid, sulfuric acid and phosphoric acid.

21. The use according to claim 20, characterized in that The regeneration agent solution is composed of 10% to 30% tartaric acid, 2% to 4% acetoxysuccinic acid, 1% to 3% methanesulfonic acid, and the rest is desalted water, according to mass composition percentage.

22. The use according to claim 18, characterized in that The basic impurities contained in the raw material dry gas include at least one of ammonia, aminomethane, N-methylmethylamine, cyclopropanemethylamine, N-dimethylmethylamine, monoethanolamine, diethanolamine, aminocyclobutane, diisopropanolamine, and N-methyldiethanolamine; And / or, the volume content of total nitrogen in the raw dry gas is not less than 5 ppm, and the volume content of total nitrogen is not more than 2000 ppm.

23. The use according to claim 22, characterized in that The volume content of total nitrogen in the raw dry gas shall not be less than 50ppm, and the volume content of total nitrogen shall not be higher than 1000ppm.

24. The use according to claim 22, characterized in that The volume content of total nitrogen in the raw dry gas shall not be less than 500ppm.

25. The use according to claim 18, characterized in that In the application, the conditions of the dealkalization refining are as follows: the temperature is 20-50°C, the pressure is, according to the gauge pressure, 500-1200 kPa, and the dry gas feed volume space velocity is 300-1500 h -1 The feed ratio of dry gas to regeneration agent solution is 400 to 600 by volume.

26. The use according to claim 18, characterized in that Before the raw dry gas comes into contact with the dealkalizing refining agent, it first comes into contact with the desulfurizing agent to remove the sulfide, thereby obtaining the desulfurized purified dry gas; And / or, the purified dry gas free of alkaline impurities is contacted with a propylene removal agent to obtain the purified dry gas free of propylene.

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