CN115957617B - Dealkalization refined preparation and preparation method and application thereof - Google Patents
Dealkalization refined preparation and preparation method and application thereof Download PDFInfo
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- CN115957617B CN115957617B CN202111191673.6A CN202111191673A CN115957617B CN 115957617 B CN115957617 B CN 115957617B CN 202111191673 A CN202111191673 A CN 202111191673A CN 115957617 B CN115957617 B CN 115957617B
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- microchannel
- dry gas
- preparation
- micro
- treatment
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Abstract
本发明公开了一种脱碱精制剂及其制备方法和应用。所述脱碱精制剂包括微通道，在所述微通道的内表面由外至内包括硅烷层、改性层和第一活化层；所述改性层所含有的改性基团选自联苯基、二苯醚基或二硫醚基中的至少一种；所述第一活化层含有磺酸基和仲胺基。所述的脱碱精制剂的制备方法，包括：微通道依次经硅烷化处理，用改性剂处理，再用第一活化剂处理，得到脱碱精制剂。本发明脱碱精制剂用于分离干气中显著影响乙苯烷基化催化剂活性的碱性杂质，有效消除碱性杂质对催化剂的累积影响，能够显著延长烷基化催化剂运行周期，实现低成本、连续化生产乙苯。
The present invention discloses a dealkalizing refining agent and its preparation method and application. The dealkalizing refining agent comprises a microchannel, and the inner surface of the microchannel comprises a silane layer, a modified layer and a first activation layer from the outside to the inside; the modified group contained in the modified layer is selected from at least one of biphenyl, diphenyl ether or disulfide; the first activation layer contains a sulfonic acid group and a secondary amine group. The preparation method of the dealkalizing refining agent comprises: the microchannel is sequentially subjected to silanization treatment, treated with a modifier, and then treated with a first activating agent to obtain the dealkalizing refining agent. The dealkalizing refining agent of the present invention is used to separate alkaline impurities in dry gas that significantly affect the activity of ethylbenzene alkylation catalyst, effectively eliminate the cumulative effect of alkaline impurities on the catalyst, can significantly extend the operation cycle of the alkylation catalyst, and realize low-cost and continuous production of ethylbenzene.
Description
Technical Field
The invention relates to the technical field of ethylbenzene production from dry gas, in particular to a dealkalization refining agent and a preparation method thereof, and application thereof in deep removal of impurities (especially alkaline impurities) in dry gas.
Background
Dry gas refers to tail gas which cannot be liquefied any more in a refinery and mainly comes from a secondary processing process 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 fully utilize the part of dilute ethylene resources in the dry gas, improve the utilization rate of petroleum resources, solve the current shortage situation of ethylbenzene/styrene market at the same time, and further develop the process for preparing ethylbenzene by the dry gas. The process of preparing ethylbenzene with dry gas is generally to make ethylene, a small amount of propylene, butylene and the like in dry gas and benzene react in alkylation under the action of catalyst at the reaction temperature of 200-500 ℃ to generate ethylbenzene, propylbenzene, butylbenzene, polyalkylbenzene and the like.
The ethylbenzene alkylation catalyst generally adopts an acidic molecular sieve, and the running period of the ethylbenzene alkylation catalyst is obviously shortened due to the fact that impurities in dry gas are complex, and particularly certain alkaline impurities exist.
Patent CN109574780a discloses a method for absorbing ammonia in dry gas by using modified activated carbon, because the ammonia content in dry gas is unstable and generally fluctuates greatly at 1-500 ppm, the adsorbent is very easy to saturate when the ammonia content is higher, resulting in frequent loading and unloading of the adsorbent.
Patent CN111450662a discloses a combined deamination process of a water scrubber-cyclone-coalescer-adsorption tower, wherein the water scrubber is selected from industrial water or acidic aqueous solution, and the adsorbent is formed activated carbon, silica, alumina, formed molecular sieve, strong acid cation exchange resin and the like loaded by inorganic acid or organic acid. In the process, because the operation elasticity of the water washing rectifying tower is limited, when the ammonia content in the raw materials greatly fluctuates, the ammonia in the dry gas is difficult to effectively remove, and even if the adsorption tower is arranged at the back, the adsorbent in the adsorption tower is saturated rapidly due to the too high ammonia content in the dry gas.
The research of absorbing ammonia in phosphate fertilizer tail gas by using a rotary packed bed (chemical intermediate, 7 th 2009) discloses a process for absorbing ammonia in phosphate fertilizer tail gas by using phosphoric acid wastewater. Compared with the traditional tower equipment, the process has the advantages that the absorption efficiency is improved to a certain extent, but the deep deamination effect is general.
In conclusion, the field of removing alkaline impurities in the prior art mainly has the defects of small operation elasticity and low removal depth, so that the alkylation catalyst is continuously and slowly deactivated or rapidly deactivated. Therefore, the continuous deep and stable removal of alkaline impurities in dry gas is one of the important problems to be solved in the ethylbenzene device under the crude oil degradation background.
Disclosure of Invention
The invention aims to solve the technical problems of high content of alkaline impurities and high difficulty in continuous deep removal of alkaline impurities in dry gas in the prior art, and provides a dealkalization refined preparation, a preparation method thereof and application thereof in dealkalization of alkaline impurities in dry gas. The dealkalization refining agent is used for separating alkaline impurities in dry gas, which obviously influence the activity of an ethylbenzene alkylation catalyst, effectively eliminates the accumulated influence of the alkaline impurities on the catalyst, obviously prolongs the operation period of the alkylation catalyst, and realizes low-cost and continuous production of ethylbenzene.
The invention provides a dealkalization refining agent, which comprises a micro-channel, wherein the inner surface of the micro-channel comprises a silane layer, a modified layer and a first activation layer from outside to inside, the modified group contained in the modified layer is at least one selected from biphenyl, diphenyl ether or disulfide, and the first activation layer contains sulfonic acid groups and secondary amine groups.
In the technical scheme, in the silane layer, the molar ratio of the silicon ether group to the silicon carbon group is 0.5-1.0, and the thickness is 10-30 micrometers.
In the technical scheme, the content of the modifying groups in the modifying layer is 0.12-0.23 mol/m 2, and the thickness is 4-7 microns.
In the above technical scheme, the content of the sulfonic acid group in the first activation layer is 0.19-0.58 mol/m 2, and the content of the secondary amine group is 0.07-0.41 mol/m 2.
In the above technical scheme, preferably, the dealkalization refining agent further comprises a second activation layer on the inner surface of the first activation layer, and further preferably, in the second activation layer, the content of sulfonic acid groups is 5.8-19 mmol/m 2, the content of secondary amine groups is 9.3-34.2 mmol/m 2, and the content of methoxy groups is 19-86 mmol/m 2.
In the above technical solution, the micro-channel is preferably a baffling micro-channel, and further preferably a baffling micro-channel with a square cross section (such as rectangle or square) and a longitudinal toothed shape or wave shape, and the bending angle is 30-150 °, preferably 60-120 °. The cross section of the micro-channel is square, the width is 300-1000 micrometers, the length-width ratio is 1.5-6, the height of the modified micro-channel is 1-3 cm, and the single-section baffling span is 0.6 cm-23 cm. The micro-channel is made of metal, preferably 304, 304L, 316L or titanium.
In the above technical solution, the silylation agent used for the silane layer is at least one selected from the group consisting of phenylmethyltriethoxysilane, phenylmethyltrimethoxysilane, and the like.
In the above technical solution, the modifying agent used for the modifying layer includes a first modifying component, 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, paraxylene, metaxylene and orthoxylene. The first modifying component is selected from at least one of 2,2', 5-trichlorobiphenyl, 2, 4' -trichloro-2-hydroxydiphenyl ether and 3,3', 5' -tetrachlorodiphenyl disulfide, and preferably the first modifying component is 2, 4' -trichloro-2-hydroxydiphenyl ether.
In the above technical solution, the first activator used for the first activation layer includes aromatic hydrocarbon containing sulfonic acid group, catalyst and 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, paraxylene, metaxylene and orthoxylene. The aromatic hydrocarbon containing sulfonic acid group is preferably one or more of 3-sulfoaniline, 4-amino-1, 3-benzene disulfonic acid and 4-aniline sulfonic acid, and more preferably 4-amino-1, 3-benzene disulfonic acid. Preferably, the first activator comprises 4-amino-1, 3-benzenedisulfonic acid, zinc chloride and toluene.
In the above technical scheme, the second activator used for the second activation layer comprises sulfonic acid group-containing aliphatic hydrocarbon, 3, 5-dichloro-2-methoxyaniline, 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, paraxylene, metaxylene and orthoxylene. The sulfonic acid group-containing aliphatic hydrocarbon is preferably N- (carbamoylmethyl) -2-aminoethanesulfonic acid. Preferably, the second activator comprises N- (carbamoylmethyl) -2-aminoethanesulfonic acid, 3, 5-dichloro-2-methoxyaniline, zinc chloride and toluene.
In the technical scheme, the contents of the modified groups in the modified layer, the sulfonic acid groups and the secondary amine groups in the first activated layer and the sulfonic acid groups, the secondary amine groups and the methoxy groups in the second activated layer are all based on the inner surface area of each square meter of the micro-channel.
The second aspect of the present invention provides a method for preparing the dealkalization refinement agent, comprising:
(11) The micro-channel is subjected to silanization treatment to obtain a silanized micro-channel;
(21) Treating the silanized microchannel obtained in step (11) with a modifying agent;
(31) Treating the microchannel obtained in step (21) with a first activator to obtain a dealkalized concentrate.
In the above technical solution, the micro-channel in step (11) is preferably a baffling micro-channel, and further preferably a baffling micro-channel with a square cross section (such as rectangle or square) and a longitudinal toothed shape or wave shape, and the bending angle is 30 ° to 150 °, and preferably 60 ° to 120 °. The cross section of the micro-channel is square, the width is 300-1000 micrometers, the length-width ratio is 1.5-6, the height of the modified micro-channel is 1-3 cm, and the single-section baffling span is 0.6 cm-23 cm. The micro-channel is made of metal, preferably 304, 304L, 316L or titanium.
In the above technical scheme, the silanized micro-channel in the step (11) is a micro-channel with a silane film with a thickness of 10-30 micrometers coated on the inner surface of the micro-channel.
In the technical scheme, the method for silanizing the micro-channel in the step (11) can adopt a conventional flow modification method in the field, for example, chemical polishing solution (such as chemical polishing solution based on nitric acid and hydrofluoric acid, preferably 3% -5% of nitric acid, 2% -4% of hydrogen fluoride and 3% -6% of hydrogen peroxide based on the mass of the chemical polishing solution) is adopted, the polishing conditions are that the volume usage ratio of the chemical polishing solution to the micro-channel is 1-4, the polishing temperature is 40-60 ℃, the polishing time is 30-60 seconds) for polishing the inner surface of the micro-channel, then desalted water is adopted for cleaning (the cleaning temperature is 20-40 ℃, the cleaning time is 20-30 minutes), acetone is used for cleaning (the cleaning temperature is 20-40 ℃, the cleaning time is 20-30 minutes), alkali is used for cleaning (alkali liquor composition, sodium hydroxide is 5% -7% based on the mass content, sodium phosphate is 0.5% -1%, the alkali cleaning temperature is 60-90 ℃, the alkali cleaning time is 20-30 minutes), desalted water is used for cleaning for 4-6 times, and the cleaning is used for drying nitrogen gas at 20-40 ℃. And then, circularly silanizing by adopting a silane reagent (at least one of phenylmethyltriethoxysilane, phenylmethyltrimethoxysilane and the like) solution, and drying and curing to obtain the silane layer with the thickness of 10-30 microns. The silanization treatment condition is that the silanization reagent solution comprises, by volume, desalted water, absolute ethyl alcohol= (2.2-4.3), absolute ethyl alcohol= (11-16), pH (82-98) and pH (8-9, and the preparation method of the silanization reagent solution comprises the steps of mixing the silanization reagent, the desalted water and the absolute ethyl alcohol according to the proportion for prehydrolysis, wherein the prehydrolysis time is 12-18 hours. The cyclic silylation is carried out under the conditions that the silylation temperature is 40-60 ℃ and the silylation time is 10-20 minutes. The temperature of drying and curing is 100-120 ℃, and the drying atmosphere is nitrogen.
In the above technical solution, the modifying agent in step (21) includes a first modifying component, 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, paraxylene, metaxylene and orthoxylene. The first modifying component is selected from at least one of 2,2', 5-trichlorobiphenyl, 2, 4' -trichloro-2-hydroxydiphenyl ether and 3,3', 5' -tetrachlorodiphenyl disulfide, and preferably the first modifying component is 2, 4' -trichloro-2-hydroxydiphenyl ether. The catalyst comprises, by mass, a first modified component, a solvent= (4.5-9.1): (3.6-7.3): (190-390).
In the technical scheme, the process of treating the silanized micro-channel in the step (11) by using the modifier in the step (21) comprises the steps of enabling the modifier to enter the micro-channel from the micro-channel inlet and flow out of the micro-channel outlet, and the process is circularly carried out, wherein the fluid linear velocity of the modifier on the inner surface of the micro-channel is controlled to be 0.1-0.3 m/s, the modification temperature is controlled to be 48-69 ℃, and the modification time is controlled to be 3.5-7.5 hours. And (3) treating the silanized micro-channel in the step (11) with a modifier to obtain a modified silanized micro-channel intermediate.
In the above technical solution, in step (21), it is preferable that the pre-activated modified silylated microchannel intermediate is obtained by performing a modification post-treatment after treating the silylated microchannel obtained in step (11) with a modifier. The preactivator used for the modified post-treatment can be one or more of absolute methanol, absolute ethanol and absolute acetone, and the preferred preactivator is absolute ethanol. The modification post-treatment process is as follows, the preactivator enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the preactivator on the inner surface of the micro-channel is controlled to be 0.23-0.45 m/s, the treatment temperature after modification is 60-80 ℃, the modification time is 1-3 hours, and the preactivator is dried for 0.5-1.0 hour at 110-130 ℃ in inert atmosphere (such as nitrogen).
In the above technical scheme, in step (31), the microchannel obtained in step (21) (i.e. the modified silanized microchannel intermediate or the preactivated modified silanized microchannel intermediate) is treated with the first activator to obtain the dealkalized preparation. Wherein the content of sulfonic acid groups in the dealkalization refined agent which is treated by the first activator is 0.19-0.58 mol/m 2, and the content of secondary amino groups is 0.07-0.41 mol/m 2.
In the above technical solution, in step (31), the first activator used includes aromatic hydrocarbon containing sulfonic acid group, catalyst and 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, paraxylene, metaxylene and orthoxylene. The aromatic hydrocarbon containing sulfonic acid group is preferably one or more of 3-sulfoaniline, 4-amino-1, 3-benzene disulfonic acid and 4-aniline sulfonic acid, and more preferably 4-amino-1, 3-benzene disulfonic acid. Preferably, the first activator comprises 4-amino-1, 3-benzenedisulfonic acid, zinc chloride and toluene. According to the mass portion, the aromatic hydrocarbon containing the sulfonic group is catalyst, solvent= (4.8-9.7): (4-7.7): (200-370).
In the technical scheme, in the step (31), the process of treating the silanized filler intermediate or the preactivated modified silanized filler intermediate obtained in the step (21) by using the first activator comprises the steps of enabling the first activator to enter the micro-channel from the micro-channel inlet and flow out of the micro-channel outlet, and circularly carrying out the process, wherein the fluid linear velocity of the first activator on the inner surface of the micro-channel is controlled to be 0.11-0.32 m/s, the modification temperature is controlled to be 48-69 ℃, and the modification time is controlled to be 3.6-7.5 hours.
In the above technical scheme, in step (31), preferably, the micro-channel treated by the first activator is treated by the second activator to obtain the dealkalized refined agent. Specifically, after the treatment by the first activator, solid-liquid separation is carried out, and the obtained solid is contacted with the second activator to carry out the second activation treatment. Wherein the content of sulfonic acid groups in the dealkalized refined preparation after being treated by the second activator is 5.8-19 mmol/m 2, the content of secondary amino groups is 9.3-34.2 mmol/m 2, and the content of methoxy groups is 19-86 mmol/m 2.
In the above technical scheme, in step (31), preferably, the second activator used includes sulfonic acid group-containing aliphatic hydrocarbon, 3, 5-dichloro-2-methoxyaniline, catalyst and 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, paraxylene, metaxylene and orthoxylene. The sulfonic acid group-containing aliphatic hydrocarbon is preferably N- (carbamoylmethyl) -2-aminoethanesulfonic acid. Preferably, the second activator comprises N- (carbamoylmethyl) -2-aminoethanesulfonic acid, 3, 5-dichloro-2-methoxyaniline, zinc chloride and toluene. According to the mass portion, the catalyst comprises 3, 5-dichloro-2-methoxyl aniline, solvent= (3.7-7.3), 6.2-13, 5-10 and 140-360.
In the above technical solution, in the step (31), the condition of the treatment with the second activator includes purging the modifier in the microchannel with an inert gas (such as nitrogen) until no free liquid flows out. Controlling the linear velocity of the fluid on the inner surface of the micro-channel to be 0.32-0.54 m/s, the treatment temperature to be 40-55 ℃ and the modification time to be 1-2 hours.
In the above technical solution, in step (31), preferably, the dealkalization refinement is obtained by performing the activation after the first activation treatment on the micro-channel and/or the second activation treatment on the micro-channel. The agent used for the activation post-treatment is at least one of absolute ethyl alcohol and benzene, and preferably absolute ethyl alcohol. The condition of the activation post-treatment is that the medicament enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the solvent used for the activation post-treatment on the inner surface of the micro-channel is controlled to be 0.23-0.45 m/s, the activation post-treatment temperature is controlled to be 60-80 ℃, and the treatment time is controlled to be 1-3 hours. After the activation, inert gas (such as nitrogen) is used for purging for 0.5-1.0 hour at 110-130 ℃.
The third aspect of the invention provides an application of the dealkalization refined preparation provided in the first aspect or the dealkalization refined preparation prepared by the method in the second aspect in dealkalization impurities of dry gas.
In the technical scheme, the method comprises the steps of contacting raw material dry gas with a dealkalization refining agent to obtain purified dry gas with dealkalization impurities.
In the above technical solution, preferably, in the application, a micro-channel refiner is adopted, wherein a micro-channel module formed by dealkalized refined agents connected in parallel and/or in series is arranged inside the micro-channel refiner, one end of the micro-channel refiner is provided with a raw material dry gas inlet and an inlet dry gas distributor, the raw material dry gas inlet is connected with the inlet dry gas distributor, the inlet dry gas distributor is connected with the micro-channel module, the other end of the micro-channel refiner is provided with a purified dry gas collecting pipe and a purified dry gas outlet, the purified dry gas collecting pipe is connected with the purified dry gas outlet, the micro-channel module is connected with the purified dry gas collecting pipe, the upper end of the micro-channel refiner is provided with a regenerant solution inlet and an inlet regenerant solution distributor, the regenerant solution inlet is connected with the micro-channel module, a mist separation layer is arranged in the micro-channel pipeline, and the lower end of the micro-channel refiner is provided with a regenerant solution collector, and the regenerant solution outlet is communicated with the regenerant liquid collector.
In the above technical scheme, in the application, preferably, the microchannel refiner is filled with 500-1000 modified microchannel modules, each modified microchannel module is provided with 1000-2000 dealkalization refinements, and the interval between two adjacent parallel dealkalization refinements is 300-500 micrometers. In each modified microchannel, the cross section is square, the width is 300-1000 micrometers, the length-width ratio is 1.5-6, and the height of the dealkalization refined agent is 1-3 cm. The micro-channel is preferably a baffling micro-channel, more preferably a tooth-shaped or wave-shaped baffling micro-channel, the bending angle is 30-150 degrees, preferably 60-120 degrees, and the single-section baffling span is 0.6-23 cm. And a mist separation layer is arranged in the micro-channel, and the separation precision is 3-10 microns.
In the above technical scheme, in the application, a micro-channel refiner is adopted, wherein a micro-channel module formed by dealkalization refining agents connected in parallel and/or in series is arranged in the micro-channel refiner, when the micro-channel refiner is used, raw material dry gas enters the micro-channel module through an inlet dry gas distributor, meanwhile, regenerant solution enters the micro-channel module through an inlet regenerant solution distributor, under the action of power, the regenerant solution and the dry gas are dispersed in the micro-channel and pass through the micro-channel, adsorption and regeneration are realized, and a mist separation layer is arranged in the micro-channel to capture the regenerant solution after coalescence work, so that purified dry gas and the regenerant solution after work are obtained. The method comprises the following steps that raw dry gas sequentially passes through a raw dry gas feed port and a dry gas distributor to enter a micro-channel of a dealkalized refining agent and flow forwards in the micro-channel in a high-speed baffling way, alkaline impurities in the dry gas are selectively adsorbed to a first or a second activator treatment layer in the micro-channel of the dealkalized refining agent, meanwhile, the regenerant solution enters the micro-channel refiner from the regenerant solution feed port through the inlet regenerant solution distributor and is collided and dispersed with raw dry gas entering through the inlet dry gas distributor, on one hand, part of the regenerant solution flows into the micro-channel under the action of dry gas flow to regenerate active sites adsorbed and saturated in the micro-channel, on the other hand, part of the regenerant solution directly reacts with alkaline impurities in the dry gas, then the regenerant solution is captured and coalesced through a mist separation layer arranged in the micro-channel, then is collected to a regenerant solution collector through a regenerant solution outlet, then enters the regenerant solution collector, and the obtained dry gas is collected by a micro-channel dry gas collection pipe and then discharged through a purified dry gas outlet.
In the above technical scheme, in the application, the regenerant is at least one selected from citric acid, tartaric acid, acetic acid-based succinic acid, methanesulfonic acid, sulfuric acid and phosphoric acid, preferably, the regenerant solution comprises, by mass, 10% -30% of tartaric acid, 2% -4% of acetic acid-based succinic acid, 1% -3% of methanesulfonic acid and the balance desalted water.
In the above technical scheme, in the application, the micro-channel is used as an independent pipeline unit to be distributed in the micro-channel module to form a basic contact unit for removing alkaline impurities, liquid baffling, crushing and high-speed turbulence are promoted under the action of power, the micro-channel is a multi-phase contact unit integrating adsorption and regeneration, on-line in-situ real-time continuous adsorption and regeneration are adopted, namely in-situ regeneration is carried out while adsorption is carried out in the micro-channel, and the regeneration of the adsorption center is realized by contacting mass transfer with a saturated adsorption center by a high-speed turbulence regenerant. The power is gas driving force and liquid high-pressure injection, preferably gas driving force. The gas driving force is derived from a process system gas delivery apparatus, and/or a gas compressor.
In the above technical scheme, in the application, the volume space velocity of the raw material dry gas is 600-3000 h -1, the adsorption temperature is 20-50 ℃, the adsorption pressure (gauge pressure) is 500-1200 kPa, and the feed quantity ratio of the raw material dry gas to the regenerant solution is 400-600 by volume.
In the above technical solution, in the application, the obtained purified dry gas with the alkali impurities removed is preferably subjected to cyclone separation to remove trace mist entrained in the dry gas. The cyclone separation can be a conventional cyclone separator in the field, and the separation precision is 200-500 micrometers.
In the technical scheme, the raw material dry gas is derived from catalytic cracking, thermal cracking, delayed coking and hydrocracking of a refinery. The dry gas of the raw material comprises, but is not limited to, ethylene, methane, ethane, propane, propylene, isobutane, n-butane, fumaric acid, n-butene, isobutene, cis-butene, oxygen, nitrogen, hydrogen, carbon monoxide, carbon dioxide, acetylene, 1, 3-butadiene, alkane or alkene with more than five carbon atoms and alkaline impurities, wherein the alkaline impurities comprise at least one of chain or cyclic nitrogen-containing impurities, and are derived from the nitrogen-containing impurities and degradation components thereof, an amino desulfurizing agent and degradation components thereof in the crude oil. In the raw material dry gas, the volume content of ethylene is 5% -40%, preferably 10% -20%. The raw material dry gas has a volume content of not less than 5ppm, preferably not less than 50ppm, more preferably not less than 500ppm, based on total nitrogen elements, not more than 2000ppm, preferably not more than 1000ppm, based on total nitrogen elements.
In the above technical scheme, the alkaline impurities include, but are not limited to, at least one of ammonia, aminomethane, N-methyl methylamine, cyclopropanemethylamine, N-dimethyl methylamine, monoethanolamine, diethanolamine, aminocyclobutane, diisopropanolamine, N-methyldiethanolamine and the like.
In the above technical scheme, the raw material dry gas also includes sulfide (such as hydrogen sulfide, etc.). According to the requirements on the content of sulfide in the product dry gas, the raw material dry gas can be contacted with a desulfurizing agent to remove sulfide before the raw material dry gas is contacted with a dealkalized refining agent, so that the desulfurization purified dry gas is obtained. The desulfurizing agent is a conventional desulfurizing agent in the field, preferably an alcohol amine, such as at least one of diethanolamine and N-methyldiethanolamine. The condition of the contact of the raw material dry gas and the desulfurizing agent is that the temperature is 20-50 ℃, the pressure is 600-1300 kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 6-11. The dosage ratio of the raw material dry gas to the desulfurizing agent is 60-110% by volume, and the mass concentration of the desulfurizing agent solution is 25-40%.
In the above technical scheme, preferably, the obtained desulfurization purified dry gas is washed with water and then subjected to alkali impurity removal. The washing medium of the water washing is desalted water. The conditions of the contact of the obtained desulfurization purified dry gas and desalted water are that the temperature is 20-50 ℃, the pressure is 600-1300 kPa according to the gauge pressure, and the gas-liquid ratio is 10-30 according to the volume.
According to the technical scheme, according to the requirement on the propylene content in the product dry gas, the purified dry gas with the alkaline impurities removed can be contacted with a propylene removing agent to obtain the purified dry gas with propylene removed. Wherein the propylene removing agent is a conventional propylene removing agent in the field, and is preferably at least one of benzene and diethylbenzene. The condition of the contact of the dry gas and the propylene removing agent is that the temperature is 10-20 ℃, the pressure is 900-1500 kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 9-16. The dosage ratio of the dry gas to the propylene removing agent is 90-120 by volume.
In the above-described technical scheme, the total nitrogen volume content in the obtained purified dry gas is preferably not higher than 5ppm, more preferably not higher than 3ppm, and still more preferably not higher than 1ppm.
In the above technical scheme, preferably, the obtained purified dry gas can meet the requirement of long-period operation of the ethylbenzene alkylation catalyst.
In a third aspect, the present invention provides a separation system for removing impurities from dry gas, comprising:
1) The desulfurization contact tower is used for removing hydrogen sulfide in the dry gas raw material;
2) The dealkalization refining system is used for removing alkaline impurities in the desulfurized and purified dry gas;
3) The demister is used for removing trace mist carried in the dealkalized and refined dry gas;
4) The propylene removal contact tower is used for removing propylene in the dry gas after dealkalization and purification.
In the technical scheme, the dealkalized refined dry gas scrubber is arranged and is used for separating impurities carried in the desulfurized and purified dry gas.
In the technical scheme, the dealkalization refining system comprises a micro-channel refiner, wherein a dealkalization refining agent is arranged for removing alkaline impurities in dry gas.
In the above technical scheme, preferably, a mist removing layer is arranged at the downstream of the micro-channel in the dealkalization refining system and is used for removing trace mist carried in dealkalization refined dry gas.
In the above technical solution, preferably, a regenerant storage tank is provided for buffering the regenerant, and the regenerant is led into and out of the microchannel refiner through the liquid conveying device.
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 a process value (for example, not less than 95%).
In the technical scheme, the high-pressure pump is arranged for pressurized conveying of the regenerant.
Compared with the prior art, the invention has the following advantages:
1. The inventor of the present invention has found that alkaline impurities which have a significant influence on ethylbenzene alkylation catalysts exist in dry gas raw materials, and the impurities can be accumulated in the catalysts continuously, so that the activity of the ethylbenzene catalysts is reduced, and the operation period is shortened. Due to the fluctuation of the crude oil raw material and the fluctuation of the desulfurization process, the alkaline impurities in the dry gas raw material continuously and greatly fluctuate. If fixed bed adsorption is performed only by conventional adsorbents such as ion exchange resins, activated carbon, etc., the adsorbents are easily saturated, conventional regeneration operations are frequent, and the amount of wastewater discharge is large. The inventor finds that through the modified micro-channel, the alkaline impurities in the raw material dry gas are deeply adsorbed by utilizing the high active groups on the micro-channel, and meanwhile, the preferable low-corrosivity regenerant with a desorption function is adopted to continuously replace and adsorb the micro-interface by utilizing the power such as the throwing inertia force of liquid, so that the problem that the dealkalization refined agent is difficult to regenerate in situ is solved, and the good effect of simultaneously carrying out continuous adsorption and regeneration is realized. Meanwhile, because the active center of the dealkalization refining agent is regenerated by adopting the high-frequency pulse of the regenerant, even if the content of alkaline impurities in the dry gas raw material greatly fluctuates, a sufficient number of fresh active centers are used for continuous adsorption, and the problem of low elasticity of the conventional rectification deamination operation is solved.
2. In the modification process of the micro-channel, the silane layer is formed on the inner surface of the micro-channel, and then the micro-channel is modified by the modifier, so that the strong supporting and dispersing functions of the micro-channel can be fully exerted, the micro-channel is protected from corrosion, the service life is prolonged, and then the modification of the activator is utilized, wherein the first activator can modify the surface of the silane layer to form a modified layer with an adsorption active center with proper adsorption strength, and the modified layer has good adsorption and regeneration effects in continuous adsorption and regeneration operation. Preferably, the second active agent is adopted to modify the micro-channel, so that the air film resistance when the dry gas is contacted with the modified layer formed by the first active agent treatment can be reduced, the mass transfer rate is improved, the modified layer formed by the second active agent treatment has a certain absorption effect on each component in the dry gas, a dry gas concentration area with a certain thickness is formed, the concentration area is in dynamic balance with the dry gas main body area, and alkaline impurity components are continuously exchanged to the modified layer formed by the first active agent treatment, so that the deep removal of alkaline impurities in the dry gas is realized. Meanwhile, the regenerant disclosed by the invention has good permeability, and particularly, alkaline impurities adsorbed in a modified layer formed by treating the first active agent can be effectively desorbed so as to recover the active center of the dealkalized refined agent, so that good balance between continuous adsorption and regeneration is realized.
3. The method solves the problems of high content of trace alkaline impurities affecting the ethylbenzene alkylation catalyst and short operation period of the alkylation catalyst in the existing dry gas raw material, greatly improves the operation period of the alkylation catalyst by deeply and continuously adsorbing the alkaline impurities in the dry gas raw material, and reduces the ethylbenzene production cost.
Drawings
FIG. 1 is a schematic diagram of a separation system for removing impurities from dry gas according to the present invention;
wherein reference numerals are as follows:
0101 is a desulfurization contact tower, 0102 is a propylene removal contact tower, 2101 is a dry gas scrubber, 2102 is a microchannel refiner, 2103 is a liquid collector, 2104 is a regenerant solution storage tank, 2105 is a regenerant solution circulating pump, 2106 is a cyclone separator, 0201 is a desulfurizing agent inlet, 0202 is a raw material dry gas inlet, 0203 is a desulfurizing agent rich solution outlet, 0204 is a propylene removal agent inlet, 0205 is a propylene removal purifying dry gas outlet, 0206 is a propylene removal agent rich solution outlet, 2201 is a washing water inlet, 2202 is a washing water rich solution outlet, 2203 is a microchannel reactor inlet, 2204 is a regenerant solution inlet, 2205 is a regenerant solution outlet, 2206 is a fresh regenerant solution or regenerant lean solution inlet, 2207 is a regenerant solution rich solution outlet, and 2208 is a cyclone separator condensate outlet;
FIG. 2 is a schematic illustration of a partial microchannel gas-liquid flow in accordance with the present invention;
wherein reference numerals are as follows:
2109 is a regenerant solution inlet, 2110 is a raw material dry gas inlet, 2111 is a modified microchannel, 2112 is a mist separation layer in the modified microchannel, 2113 is a height, and 2114 is a single-section baffling span.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the invention, the inner surface of the microchannel comprises a silane layer, a modified layer and a first activation layer from outside to inside, wherein the silane layer is arranged on the inner surface of the microchannel, the modified layer is arranged on the inner surface of the silane layer, and the first activation layer is arranged on the inner surface of the modified layer.
In the invention, the inner surface of the microchannel comprises a silane layer, a modified layer, a first activation layer and a second activation layer from outside to inside, wherein the silane layer is arranged on the inner surface of the microchannel, the modified layer is arranged on the inner surface of the silane layer, the first activation layer is arranged on the inner surface of the modified layer, and the second activation layer is arranged on the inner surface of the first activation layer.
In the present invention, the analysis of the lower hydrocarbon component was carried out by using a gas chromatography Agilent 7890A GC (Agilent, usa) equipped with an HP-PLOT Al 2O3 KCl (50 m×0.53mm×15 μm) capillary chromatography column, the column temperature was maintained at 100 ℃ for 10 minutes, and then raised to 120 ℃ for 3 minutes at 30 ℃ minutes. Carrier gas He flow rate 3 mL/min, sample injection amount 0.1mL (quantitative loop), split ratio 5:1, sample inlet temperature 250 ℃, detector (FID) temperature 250 ℃. According to the invention, the nitrogen element content in the dry gas material is tested by adopting a Mitsubishi sulfur nitrogen analyzer NSX-2100V analyzer, wherein the analysis method is that the argon flow is 200 mL/min, the oxygen flow is 400 mL/min, and the combustion temperature is 1000-1050 ℃.
The invention relates to a separation system for removing impurities in dry gas (shown in figure 1), which comprises 0101 as a desulfurization contact tower, 0102 as a propylene removal contact tower, 2101 as a dry gas scrubber, 2102 as a microchannel refiner, 2103 as a liquid collector, 2104 as a regenerant solution storage tank, 2105 as a regenerant solution circulating pump and 2106 as a cyclone separator. Dry gas raw materials (such as raw materials from refinery catalytic cracking, thermal cracking, delayed coking and hydrocracking) enter a desulfurization contact tower 0101 from a raw material dry gas inlet 0202 to be in countercurrent contact with an amine desulfurizing agent from a desulfurizing agent inlet 0201, sulfur compounds such as hydrogen sulfide in the dry gas are removed, a bottom extract of the desulfurization contact tower 0101 is led out to a desulfurizing agent regeneration unit from a desulfurizing agent rich liquid outlet 0203, a top gas phase of the desulfurization contact tower 0101 is then entered into a dry gas scrubber 2101 to be contacted with desalted water from a washing water inlet 2201, colloid dust carried in the desulfurized dry gas is washed and removed, washing rich liquid of the dry gas scrubber 2101 is discharged to a sewage treatment unit from a washing water rich liquid outlet 2202, top extract of the dry gas scrubber 2101 is then distributed through a microchannel refiner inlet 2203 and then enters a microchannel refiner, alkaline impurities in the dry gas are adsorbed by active groups on a modified microchannel, a regenerating agent solution in a regenerating agent solution storage tank 2104 is simultaneously conveyed to a regenerating agent solution 2102 through a regenerating agent solution circulating pump 2105 from a regenerating agent solution inlet 2204 to a microchannel refiner face, and a regenerating agent solution is discharged from a high-frequency channel to a regenerating agent solution is discharged from a high-frequency channel 2205 under the action of a regenerating agent solution. When the utilization rate of the regenerant reaches a process value (e.g., 95%) the liquid level in the regenerant storage tank 2104 is discharged to 1% -5% through the regenerant rich liquid outlet 2207, and then fresh regenerant or the regenerant lean liquid regenerated by the regenerant regeneration unit is added through the fresh regenerant or the regenerant lean liquid inlet 2206. The dry gas at the outlet of the microchannel refiner 2102 is removed free mist carried in the dry gas at the outlet of the microchannel refiner through a cyclone 2106, a condensate outlet 2208 of the cyclone 2106 is discharged to a sewage treatment unit or a regenerant solution storage tank 2104, the top produced gas of the cyclone 2106 is subjected to countercurrent contact with the propylene removing agent from a propylene removing agent inlet 0204 through a supercharging device or directly enters a propylene removing contact tower 0102, propylene in the dry gas is removed, a bottom produced material of the propylene removing contact tower 0102 is extracted from a propylene removing agent rich liquid outlet 0206 to a propylene removing agent regeneration unit, and the propylene removing purified dry gas is discharged out of a dealkylation reaction system through a propylene removing purified dry gas outlet 0205 at the top of the propylene removing contact tower 0102.
The gas-liquid flow in the modified micro-channel is shown in fig. 2, and the micro-channel is a tooth-shaped baffling micro-channel longitudinally, wherein the height 2113 of the modified micro-channel and the single-section baffling span 2114 are provided. The regenerant solution entering from the regenerant solution inlet 2109 and the raw material dry gas entering from the raw material dry gas inlet 2110 are impacted and mixed and then flow forward in the modified micro-channel 2111, alkaline impurities in the dry gas are adsorbed by active groups on the inner surface of the modified micro-channel, the adsorbed and purified dry gas enters a later-stage modified micro-channel to be continuously adsorbed after being coalesced and separated into liquid by a mist separation layer 2112 in the modified micro-channel, and the regenerant solution is subjected to high-frequency random turbulence on the inner surface of the modified micro-channel under the action of the driving force of the dry gas to regenerate the adsorbed active sites, then enters a liquid collector 2103 after being intercepted by the mist separation layer 2112 in the micro-channel, and returns to the regenerant solution storage tank 2104.
[ Example 1]
The dry gas raw material in the embodiment is derived from a catalytic cracking device of a refinery, and the dry gas composition comprises the following components in percentage by volume:
Methane 17.8783%, ethane 8.1123%, ethylene 15.9995%, propane 0.1859%, propylene 0.8416%, isobutane 0.0811%, N-butane 0.0157%, fumaric acid 0.0067%, N-butene 0.0185%, isobutylene 0.0381%, maleic acid 0.0002%, oxygen 0.1370%, nitrogen 13.5433%, hydrogen 29.4547%, carbon monoxide 1.4972%, carbon dioxide 3.3271%, acetylene 0.0053%,1, 3-butadiene 0.0001%, hydrogen sulfide 6.6738%, ammonia 0.0260%, aminomethane 0.0028%, N-methyl methylamine 0.0020%, N, N-dimethyl methylamine 0.0016%, N-methyl diethanolamine 0.0016%, cyclopropanemethylamine 0.0028%, aminocyclobutane 0.0032%, alkanes or olefins 1.1938%, and other components 0.9500%. Wherein the alkaline impurity is present in an amount of 280ppm by volume based on total nitrogen element.
The separation flow of this example is shown in FIG. 1, and the partial microchannel gas-liquid flow diagram of the dealkalization refiner used is shown in FIG. 2.
The preparation method of the dealkalization refined agent comprises the steps of firstly carrying out silanization treatment on a microchannel to obtain a silanization microchannel, then treating the silanization microchannel with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization refined agent.
The microchannel refiner is filled with 760 microchannel modules, each microchannel module is provided with 1600 modification microchannels, and the interval between two adjacent parallel modification microchannels is 400 micrometers. The modified micro-channel is a tooth-shaped baffling micro-channel, the bending angle is 90 degrees, and each tooth-shaped baffling span is 4 cm. In each modified microchannel, the width of the channel cross section was 650 microns, the length of the channel was 3300 microns, and the height of the modified microchannel was 2 cm. The modified micro-channel is made of metal 316L. The silanization treatment adopts a flow modification method, firstly adopts chemical polishing solution to polish the inner surface of a micro-channel, then adopts desalted water for cleaning, acetone for cleaning, alkali for cleaning, desalted water for flushing and nitrogen for blow-drying, then adopts silane reagent (aniline methyltriethoxysilane) solution for cyclic silanization, and finally obtains a silane film with the molar ratio of silicon ether group to silicon carbon group of 0.7 and thickness of 21 microns through drying and solidification. The silanization treatment conditions comprise, by mass, 4% of nitric acid, 3% of hydrogen fluoride and 4.5% of hydrogen peroxide, wherein the volume ratio of the chemical polishing solution to the micro-channels is 2.5, the polishing temperature is 50 ℃, the polishing time is 45 seconds, the desalted water cleaning condition comprises 30 ℃ of cleaning temperature, 25 minutes of cleaning time, 30 ℃ of cleaning time of acetone cleaning condition comprises 25 minutes of cleaning time, alkali liquor composition comprises, by mass, 6% of sodium hydroxide, 0.7% of sodium phosphate, 75 ℃ of alkali washing temperature and 25 minutes of alkali washing time, the micro-channels after alkali washing are flushed 5 times by desalted water flow and are dried by nitrogen at 30 ℃, the silanization reagent solution comprises, by volume, a silanization reagent comprises desalted water, absolute ethyl alcohol=3.3:13:91, the pH value is 8.5, the pre-hydrolysis time is 15 hours, and the cyclic silanization condition comprises 50 ℃ of silanization temperature and 15 minutes. The drying and curing temperature is 110 ℃, and the drying atmosphere is nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portion of the modifier is 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=6.8:5.5:290. The zinc chloride is anhydrous zinc chloride. The modifier is processed under the following conditions that the modifier enters the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid on the inner surface of the micro-channel is controlled to be 0.2 m/s, the modifying temperature is 59 ℃, and the modifying time is 5.5 hours. And (3) treating the silanized micro-channel with a modifier to obtain a modified silanized micro-channel intermediate. The modified group diphenyl ether group content in the modified layer of the dealkalized refining agent is 0.18mol/m 2 after modification treatment, and the thickness is 5.4 micrometers.
And (3) carrying out modification post-treatment after modification to obtain the preactivated modified silanization microchannel intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The modification post-treatment conditions are as follows, the preactivator enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the preactivator on the inner surface of the micro-pore canal is controlled to be 0.34 m/s, the treatment temperature after modification is 70 ℃, the modification time is 2.0 hours, and the preactivator is dried in nitrogen for 0.7 hours at 120 ℃.
The pre-activated modified silanized filler intermediate is subjected to a first activator and a second activator in sequence. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the 4-amino-1, 3-benzene disulfonic acid is zinc chloride and the weight part of the toluene=7.3:5.8:280. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight portion of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline, the zinc chloride and the toluene are respectively 5.5:9.6:7:240. The zinc chloride is anhydrous zinc chloride. The first activator is treated by entering the micro-channel from the micro-channel inlet and flowing out from the micro-channel outlet, and the process is circularly carried out, wherein the fluid linear speed of the first activator on the inner surface of the micro-channel is controlled to be 0.21 m/s, the modification temperature is 58 ℃, and the modification time is 5.5 hours. The second activator treatment was performed under conditions such that nitrogen was used to purge the microchannel until no free liquid was flowing out. The second activator was controlled to have a fluid linear velocity of 0.43 m/s at the inner surface of the microchannel at a treatment temperature of 47 ℃ and a modification time of 1.5 hours. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The activation post-treatment conditions are as follows, the agent enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the agent used for the activation post-treatment on the inner surface of the micro-pore canal is controlled to be 0.34 m/s, the activation post-treatment temperature is controlled to be 70 ℃, and the treatment time is controlled to be 2.0 hours. After the activation, the reaction mixture was purged with nitrogen at 120℃for 0.7 hour.
The prepared dealkalization refining agent is treated by a first activator, the content of sulfonic acid groups in the dealkalization refining agent is 0.38mol/m 2, the content of secondary amino groups is 0.24mol/m 2, the content of sulfonic acid groups in the dealkalization refining agent is 12.3mmol/m 2, the content of secondary amino groups is 21mmol/m 2, and the content of methoxy groups is 53mmol/m 2.
In the microchannel refiner, the feed volume space velocity of the pretreated dry gas of the microchannel refiner is 1900h -1, the adsorption temperature is 35 ℃, and the adsorption pressure (gauge pressure) is 850kPa. The regenerant solution comprises tartaric acid, acetic acid-based succinic acid, methanesulfonic acid and desalted water, wherein the regenerant solution comprises, by mass, 20% of tartaric acid, 3% of acetic acid-based succinic acid, 2% of methanesulfonic acid and the balance of desalted water. Wherein the feed ratio of the dry gas of the raw material to the regenerant solution is 500 by volume.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the raw material dry gas and the desulfurizing agent is that the temperature is 35 ℃, the pressure is 950kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 8. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 85 percent by volume, and the mass concentration of the desulfurizing agent is 32 percent. In the dry gas scrubber, the scrubbing medium is desalted water. The conditions for contacting the desulphurized and purified dry gas with desalted water are as follows, the temperature is 35 ℃, the pressure is 950kPa by gauge pressure, and the gas-liquid ratio is 20 by volume.
The micro-channel is internally provided with a mist separation layer, and the separation precision is 6 microns. The cyclone separator is a cyclone separator, and the separation precision is 350 microns.
In the propylene removing contact tower, the propylene removing agent is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 15 ℃, the pressure is 1200kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 12. The ratio of the dry gas of the raw material to the propylene removing agent is 105 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 2.6ppm.
[ Example 2]
The dry gas feed described in this example is the same as in example 1, the separation scheme in this example is shown in FIG. 1, and the partial microchannel gas-liquid flow schematic of the dealkalized refiner used is shown in FIG. 2.
The preparation method of the dealkalization refined agent comprises the steps of firstly carrying out silanization treatment on a microchannel to obtain a silanization microchannel, then treating the silanization microchannel with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization refined agent.
The microchannel refiner is filled with 900 microchannel modules, each microchannel module is provided with 1800 modification microchannels, and the interval between two adjacent parallel modification microchannels is 350 micrometers. The modified micro-channel is a tooth-shaped baffling micro-channel, the bending angle is 60 degrees, and each tooth-shaped baffling span is 1.8 cm. In each modified microchannel, the width of the channel cross section was 360 micrometers, the length of the channel was 650 micrometers, and the height of the modified microchannel was 1.5 cm. The modified micro-channel is made of metal 316L. The silanization treatment adopts a flow modification method, firstly adopts chemical polishing solution to polish the inner surface of a micro-channel, then adopts desalted water for cleaning, acetone for cleaning, alkali for cleaning, desalted water for flushing and nitrogen for blow-drying, then adopts silane reagent (aniline methyltriethoxysilane) solution for cyclic silanization, and finally obtains a silane film with the molar ratio of silicon ether group to silicon carbon group of 0.9 and the thickness of 26 microns through drying and solidification. The silanization treatment conditions comprise, by mass, 4.5% of chemical polishing solution, 3.5% of hydrogen fluoride and 5% of hydrogen peroxide, wherein the volume ratio of the chemical polishing solution to the micro-channels is 3.5, the polishing temperature is 55 ℃, the polishing time is 50 seconds, the cleaning temperature of desalted water is 35 ℃, the cleaning time is 28 minutes, the acetone flowing cleaning temperature is 35 ℃, the cleaning time is 28 minutes, the alkali liquor is composed of, by mass, 6.5% of sodium hydroxide, 0.9% of sodium phosphate, the alkali cleaning temperature is 85 ℃, the alkali cleaning time is 28 minutes, the micro-channels after alkali cleaning are flushed with desalted water flowing for 6 times, and are dried by nitrogen at 35 ℃, the silanization reagent solution is composed of, by volume, desalted water, absolute ethyl alcohol=3.7:14:82, the pH value is 8.7, the prehydrolysis time is 17.3 hours, the cyclic silanization conditions are as follows, the temperature is 56 ℃, the silanization time is 18 minutes, the drying curing temperature is 118 ℃ and the drying atmosphere is nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=8.5:7.1:205. The zinc chloride is anhydrous zinc chloride. The modifier is processed under the following conditions that the modifier enters the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid on the inner surface of the micro-channel is controlled to be 0.12 m/s, the modification temperature is 67 ℃, and the modification time is 7.3 hours. And (3) treating the silanized micro-channel with a modifier to obtain a modified silanized micro-channel intermediate. The modified group diphenyl ether group content in the modified layer of the dealkalized refining agent is 0.22mol/m 2 after modification treatment, and the thickness is 6 micrometers.
And (3) carrying out modification post-treatment after modification to obtain the preactivated modified silanization microchannel intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The modification post-treatment conditions are as follows, the preactivator enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the preactivator on the inner surface of the micro-pore canal is controlled to be 0.25 m/s, the treatment temperature after modification is 78 ℃, the modification time is 2.6 hours, and the preactivator is dried in nitrogen for 0.9 hours at 127 ℃.
The pre-activated modified silanized filler intermediate is subjected to a first activator and a second activator in sequence. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the 4-amino-1, 3-benzene disulfonic acid is zinc chloride and the weight part of the toluene=9.5:7.3:210. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight portion of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline, the zinc chloride and the toluene=7.1:12:9:180. The zinc chloride is anhydrous zinc chloride. The first activator is treated by entering the micro-channel from the micro-channel inlet and flowing out from the micro-channel outlet, and the process is circularly carried out, wherein the fluid linear speed of the first activator on the inner surface of the micro-channel is controlled to be 0.13 m/s, the modification temperature is 66 ℃, and the modification time is 7.2 hours. The second activator treatment was performed under conditions such that nitrogen was used to purge the microchannel until no free liquid was flowing out. The second activator was controlled to have a fluid linear velocity of 0.34 m/s at the inner surface of the microchannel at a treatment temperature of 53C and a modification time of 1.7 hours. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The activation post-treatment conditions are as follows, the agent enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the agent used for the activation post-treatment on the inner surface of the micro-pore canal is controlled to be 0.25 m/s, the activation post-treatment temperature is 78 ℃, and the treatment time is 2.6 hours. After the activation treatment, nitrogen was purged at 126 ℃ for 0.8 hours.
The prepared dealkalization refining agent is treated by a first activator, the content of sulfonic acid groups in the dealkalization refining agent is 0.52mol/m 2, the content of secondary amino groups is 0.35mol/m 2, the content of sulfonic acid groups in the dealkalization refining agent is 16.1mmol/m 2, the content of secondary amino groups is 28.7mmol/m 2, and the content of methoxy groups is 84mmol/m 2.
In the microchannel refiner, the feed volume space velocity of the pretreated dry gas of the microchannel refiner is 1300h -1, the adsorption temperature is 45 ℃, and the adsorption pressure (gauge pressure) is 1100kPa. The regenerant solution comprises tartaric acid, acetic acid-based succinic acid, methanesulfonic acid and desalted water, wherein the regenerant solution comprises, by mass, 25% of tartaric acid, 3.5% of acetic acid-based succinic acid, 2.5% of methanesulfonic acid and the balance of desalted water. Wherein the feed ratio of the dry gas of the raw material to the regenerant solution is 450 by volume.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the raw material dry gas and the desulfurizing agent is that the temperature is 47 ℃, the pressure is 1200kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 10. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 65 percent by volume, and the mass concentration of the desulfurizing agent is 38 percent. In the dry gas scrubber, the scrubbing medium is desalted water. The conditions for contacting the desulphurized and purified dry gas with desalted water are as follows, the temperature is 25 ℃, the pressure is 1200kPa by gauge pressure, and the gas-liquid ratio is 12 by volume.
The micro-channel is internally provided with a mist separation layer, and the separation precision is 4 microns. The cyclone separator is a cyclone separator, and the separation precision is 300 micrometers.
In the propylene removing contact tower, the propylene removing agent is benzene. The conditions for contacting the dry raw material gas with the propylene removing agent are that the temperature is 12 ℃, the pressure is 1400kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 15. The dosage ratio of the dry gas of the raw material to the propylene removing agent is 95 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 0.65ppm.
[ Example 3]
The dry gas raw material in this example is the same as that in example 1, the separation flow is shown in fig. 1, and the local micro-channel gas-liquid microscopic flow is shown in fig. 2.
The preparation method of the dealkalization refined agent comprises the steps of firstly carrying out silanization treatment on a microchannel to obtain a silanization microchannel, then treating the silanization microchannel with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization refined agent.
The microchannel refiner is filled with 600 microchannel modules, each microchannel module is provided with 1300 modification microchannels, and the interval between two adjacent parallel modification microchannels is 450 micrometers. The modified micro-channel is a tooth-shaped baffling micro-channel, the bending angle is 120 degrees, and each tooth-shaped baffling span is 8.9 cm. In each modified microchannel, the width of the channel cross section was 800 micrometers, the length of the channel was 4500 micrometers, and the height of the modified microchannel was 2.5 cm. The modified micro-channel is made of metal 316L. The silanization treatment adopts a flow modification method, firstly adopts chemical polishing solution to polish the inner surface of a micro-channel, then adopts desalted water for cleaning, acetone for cleaning, alkali for cleaning, desalted water for flushing and nitrogen for blow-drying, then adopts silane reagent (aniline methyltriethoxysilane) solution for cyclic silanization, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.6 and the thickness of 16 microns through drying and solidification. The silanization treatment conditions comprise, by mass, 3.5% of a chemical polishing solution, 2.5% of hydrogen fluoride and 4% of hydrogen peroxide, wherein the volume ratio of the chemical polishing solution to the micro-channels is 2, the polishing temperature is 45 ℃, the polishing time is 40 seconds, the desalted water cleaning temperature is 25 ℃, the cleaning time is 22 minutes, the acetone flowing cleaning temperature is 25 ℃, the cleaning time is 22 minutes, the alkali solution is composed, by mass, 5.5% of sodium hydroxide, 0.6% of sodium phosphate, the alkali cleaning temperature is 65 ℃, the alkali cleaning time is 23 minutes, the micro-channels after alkali cleaning are washed 5 times by desalted water flowing and blow-dried by nitrogen at 25 ℃, the silanization reagent solution is composed, by volume, the silanization reagent comprises desalted water, absolute ethyl alcohol=2.3:12:97, the pH value is 8.2, the prehydrolysis time is 12.6 hours, the cyclic silanization conditions comprise that the silanization temperature is 44 ℃ and the silanization time is 13 minutes. The drying and curing temperature is 106 ℃, and the drying atmosphere is nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=4.7:3.8:360. The zinc chloride is anhydrous zinc chloride. The modifier is processed under the following conditions that the modifier enters the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid on the inner surface of the micro-channel is controlled to be 0.28 m/s, the modifying temperature is 50 ℃, and the modifying time is 3.7 hours. And (3) treating the silanized micro-channel with a modifier to obtain a modified silanized micro-channel intermediate. The modified group diphenyl ether group content in the modified layer of the dealkalized refining agent is 0.18mol/m 2 after modification treatment, and the thickness is 4.6 micrometers.
And (3) carrying out modification post-treatment after modification to obtain the preactivated modified silanization microchannel intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The modification post-treatment conditions are as follows, the preactivator enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the preactivator on the inner surface of the micro-pore canal is controlled to be 0.43 m/s, the treatment temperature after modification is 65 ℃, the modification time is 1.4 hours, and the preactivator is dried in nitrogen for 0.6 hours at 115 ℃.
The modified silanized filler intermediate is sequentially treated with a first activator and a second activator. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the 4-amino-1, 3-benzene disulfonic acid is zinc chloride and the weight part of the toluene is 5.1:4.2:350. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight portion of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline, the zinc chloride is toluene=3.9:6.5:6.3:320. The zinc chloride is anhydrous zinc chloride. The first activator is treated by entering the micro-channel from the micro-channel inlet and flowing out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid of the first activator on the inner surface of the micro-channel is controlled to be 0.3 m/s, the modification temperature is 50 ℃, and the modification time is 4 hours. The treatment condition of the second activator treatment is that nitrogen is adopted to purge the micro-channel until no free liquid flows out, the fluid linear speed of the second activator on the inner surface of the micro-channel is controlled to be 0.51 m/s, the treatment temperature is 43 ℃, and the modification time is 1.2 hours. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The activation post-treatment conditions are as follows, the agent enters the interior of the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out. Wherein, the fluid linear velocity of the agent used for the activation post-treatment on the inner surface of the micro-pore canal is controlled to be 0.39 m/s, the activation post-treatment temperature is 66 ℃, and the treatment time is 1.3 hours. After the activation, the reaction mixture was purged with nitrogen at 113℃for 0.6 hour.
The prepared dealkalization refining agent is treated by a first activator, the content of sulfonic acid groups in the dealkalization refining agent is 0.27mol/m 2, the content of secondary amino groups is 0.12mol/m 2, the content of sulfonic acid groups in the dealkalization refining agent is 7.6mmol/m 2, the content of secondary amino groups is 11mmol/m 2, and the content of methoxy groups is 23mmol/m 2.
In the microchannel refiner, the pretreated dry gas feed volume space velocity was 2600h -1, the adsorption temperature was 25 ℃, and the adsorption pressure (gauge pressure) was 600kPa. The regenerant solution comprises 15% of tartaric acid, 2.5% of acetic acid, 1.5% of methanesulfonic acid and desalted water, and the balance of desalted water. Wherein the ratio of dry gas to regenerant solution is 550 by volume.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 23 ℃, the pressure is 700kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 7. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 104 percent by volume, and the mass concentration of the desulfurizing agent is 27 percent. In the dry gas scrubber, the scrubbing medium is desalted water. The conditions for contacting the desulphurized and purified dry gas with desalted water are as follows, the temperature is 45 ℃, the pressure is 700kPa by gauge pressure, and the gas-liquid ratio is 26 by volume.
The micro-channel is internally provided with a mist separation layer, and the separation precision is 8 microns. The cyclone separator is a cyclone separator, and the separation precision is 400 micrometers.
In the propylene removing contact tower, the propylene removing agent is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 18 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 10. The ratio of the dry gas of the raw material to the propylene removing agent is 115 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 3.2ppm.
[ Example 4]
The dealkalization essential agent used in this example was the same as that used in example 2.
The separation process for dry gas feed of this example is the same as that of example 2. This example is only different from example 2 in the dry gas feed used. The dry gas comprises, by volume, methane 17.8711%, ethane 8.1090%, ethylene 15.9930%, propane 0.1859%, propylene 0.8412%, isobutane 0.0811%, N-butane 0.0157%, fumaric acid 0.0067%, N-butene 0.0185%, isobutene 0.0381%, maleic acid 0.0002%, oxygen 0.1369%, nitrogen 13.5378%, hydrogen 29.4428%, carbon monoxide 1.4966%, carbon dioxide 3.3258%, acetylene 0.0053%,1, 3-butadiene 0.0001%, hydrogen sulfide 6.6711%, ammonia 0.0520%, aminomethane 0.0056%, N-methyl methylamine 0.0040%, N, N-dimethyl methylamine 0.0032%, N-methyl diethanolamine 0.0032%, cyclopropane methylamine 0.0056%, aminocyclobutane 0.0064%, alkanes or olefins 1.1934%, and other components 0.9500%. Wherein the alkaline impurity is present in a volume content of 580ppm based on total nitrogen element.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 1.3ppm.
[ Example 5]
The dealkalization essential agent used in this example was the same as that used in example 2.
The separation process for dry gas feed of this example is the same as that of example 2. This example is only different from example 2 in the dry gas feed used. The dry gas comprises, by volume, methane 17.8853%, ethane 8.1155%, ethylene 16.0058%, propane 0.1860%, propylene 0.8419%, isobutane 0.0812%, N-butane 0.0157%, fumaric acid 0.0067%, N-butene 0.0185%, isobutene 0.0381%, maleic acid 0.0002%, oxygen 0.1371%, nitrogen 13.5486%, hydrogen 29.4663%, carbon monoxide 1.4978%, carbon dioxide 3.3284%, acetylene 0.0053%,1, 3-butadiene 0.0001%, hydrogen sulfide 6.6764%, ammonia 0.0007%, aminomethane 0.0001%, N-methyl methylamine 0.0001%, cyclopropane methylamine 0.0001%, aminocyclobutane 0.0001%, alkanes or olefins 1.1943% above carbon five and other components 0.9500%. Wherein the alkaline impurity is 7.5ppm by volume based on total nitrogen element.
The total nitrogen volume content in the obtained propylene-removed purified dry gas is 0.03ppm.
[ Example 6]
The dry gas feed described in this example is the same as in example 1. The separation flow of this example is the same as that of example 1.
The preparation method of the dealkalization preparation comprises the steps of firstly carrying out silanization treatment on a microchannel to obtain a silanization microchannel, then treating the silanization microchannel with a modifier, and sequentially carrying out treatment with a first activator and a second activator to obtain the dealkalization preparation.
The microchannel refiner is filled with 600 microchannel modules, each microchannel module is provided with 1300 modification microchannels, and the interval between two adjacent parallel modification microchannels is 450 micrometers. The modified micro-channel is a tooth-shaped baffling micro-channel, the bending angle is 120 degrees, and each tooth-shaped baffling span is 8.9 cm. In each modified microchannel, the width of the channel cross section was 800 micrometers, the length of the channel was 4500 micrometers, and the height of the modified microchannel was 2.5 cm. The modified micro-channel is made of metal 316L. The silanization treatment adopts a flow modification method, firstly adopts chemical polishing solution to polish the inner surface of a micro-channel, then adopts desalted water for cleaning, acetone for cleaning, alkali for cleaning, desalted water for flushing and nitrogen for blow-drying, then adopts silane reagent (aniline methyltriethoxysilane) solution for cyclic silanization, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.6 and the thickness of 16 microns through drying and solidification. The silanization treatment conditions comprise, by mass, 3.5% of a chemical polishing solution, 2.5% of hydrogen fluoride and 4% of hydrogen peroxide, wherein the volume ratio of the chemical polishing solution to the micro-channels is 2, the polishing temperature is 45 ℃, the polishing time is 40 seconds, the desalted water cleaning temperature is 25 ℃, the cleaning time is 22 minutes, the acetone flowing cleaning temperature is 25 ℃, the cleaning time is 22 minutes, the alkali solution is composed, by mass, 5.5% of sodium hydroxide, 0.6% of sodium phosphate, the alkali cleaning temperature is 65 ℃, the alkali cleaning time is 23 minutes, the micro-channels after alkali cleaning are washed 5 times by desalted water flowing and blow-dried by nitrogen at 25 ℃, the silanization reagent solution is composed, by volume, the silanization reagent comprises desalted water, absolute ethyl alcohol=2.3:12:97, the pH value is 8.2, the prehydrolysis time is 12.6 hours, the cyclic silanization conditions comprise that the silanization temperature is 44 ℃ and the silanization time is 13 minutes. The drying and curing temperature is 106 ℃, and the drying atmosphere is nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=4.7:3.8:360. The zinc chloride is anhydrous zinc chloride. The modifier is processed under the following conditions that the modifier enters the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid on the inner surface of the micro-channel is controlled to be 0.28 m/s, the modifying temperature is 50 ℃, and the modifying time is 3.7 hours. And (3) treating the silanized micro-channel with a modifier to obtain a modified silanized micro-channel intermediate. The modified group diphenyl ether group content in the modified layer of the dealkalized refining agent is 0.18mol/m 2 after modification treatment, and the thickness is 4.6 micrometers.
The modified silanized filler intermediate is sequentially treated with a first activator and a second activator. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the 4-amino-1, 3-benzene disulfonic acid is zinc chloride and the weight part of the toluene is 5.1:4.2:350. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight portion of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline, the zinc chloride is toluene=3.9:6.5:6.3:320. The zinc chloride is anhydrous zinc chloride. The first activator is treated by entering the micro-channel from the micro-channel inlet and flowing out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid of the first activator on the inner surface of the micro-channel is controlled to be 0.3 m/s, the modification temperature is 50 ℃, and the modification time is 4 hours. The treatment condition of the second activator treatment is that nitrogen is adopted to purge the micro-channel until no free liquid flows out, the fluid linear speed of the second activator on the inner surface of the micro-channel is controlled to be 0.51 m/s, the treatment temperature is 43 ℃, and the modification time is 1.2 hours. The dealkalization refined preparation is obtained through the activation modification.
The prepared dealkalization refining agent is treated by a first activator, the content of sulfonic acid groups in the dealkalization refining agent is 0.25mol/m 2, the content of secondary amino groups is 0.11mol/m 2, the content of sulfonic acid groups in the dealkalization refining agent is treated by a second activator and is 7.2mmol/m 2, the content of secondary amino groups is 10.4mmol/m 2, and the content of methoxy groups is 22mmol/m 2.
In the microchannel refiner, the pretreated dry gas feed volume space velocity was 2600h -1, the adsorption temperature was 25 ℃, and the adsorption pressure (gauge pressure) was 600kPa. The regenerant solution comprises 15% of tartaric acid, 2.5% of acetic acid, 1.5% of methanesulfonic acid and desalted water, and the balance of desalted water. Wherein the ratio of dry gas to regenerant solution is 550 by volume.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 23 ℃, the pressure is 700kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 7. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 104 percent by volume, and the mass concentration of the desulfurizing agent is 27 percent. In the dry gas scrubber, the scrubbing medium is desalted water. The conditions for contacting the desulphurized and purified dry gas with desalted water are as follows, the temperature is 45 ℃, the pressure is 700kPa by gauge pressure, and the gas-liquid ratio is 26 by volume.
The micro-channel is internally provided with a mist separation layer, and the separation precision is 8 microns. The cyclone separator is a cyclone separator, and the separation precision is 400 micrometers.
In the propylene removing contact tower, the propylene removing agent is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 18 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 10. The ratio of the dry gas of the raw material to the propylene removing agent is 115 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 5.3ppm.
[ Example 7]
The dry gas feed described in this example is the same as in example 1. The separation flow of this example is the same as that of example 1.
The preparation method of the dealkalization preparation comprises the steps of firstly carrying out silanization treatment on a microchannel to obtain a silanization microchannel, then treating the silanization microchannel with a modifier, and obtaining the dealkalization preparation with a first activator.
The microchannel refiner is filled with 600 microchannel modules, each microchannel module is provided with 1300 modification microchannels, and the interval between two adjacent parallel modification microchannels is 450 micrometers. The modified micro-channel is a tooth-shaped baffling micro-channel, the bending angle is 120 degrees, and each tooth-shaped baffling span is 8.9 cm. In each modified microchannel, the width of the channel cross section was 800 micrometers, the length of the channel was 4500 micrometers, and the height of the modified microchannel was 2.5 cm. The modified micro-channel is made of metal 316L. The silanization treatment adopts a flow modification method, firstly adopts chemical polishing solution to polish the inner surface of a micro-channel, then adopts desalted water for cleaning, acetone for cleaning, alkali for cleaning, desalted water for flushing and nitrogen for blow-drying, then adopts silane reagent (aniline methyltriethoxysilane) solution for cyclic silanization, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.6 and the thickness of 16 microns through drying and solidification. The silanization treatment conditions comprise, by mass, 3.5% of a chemical polishing solution, 2.5% of hydrogen fluoride and 4% of hydrogen peroxide, wherein the volume ratio of the chemical polishing solution to the micro-channels is 2, the polishing temperature is 45 ℃, the polishing time is 40 seconds, the desalted water cleaning temperature is 25 ℃, the cleaning time is 22 minutes, the acetone flowing cleaning temperature is 25 ℃, the cleaning time is 22 minutes, the alkali solution is composed, by mass, 5.5% of sodium hydroxide, 0.6% of sodium phosphate, the alkali cleaning temperature is 65 ℃, the alkali cleaning time is 23 minutes, the micro-channels after alkali cleaning are washed 5 times by desalted water flowing and blow-dried by nitrogen at 25 ℃, the silanization reagent solution is composed, by volume, the silanization reagent comprises desalted water, absolute ethyl alcohol=2.3:12:97, the pH value is 8.2, the prehydrolysis time is 12.6 hours, the cyclic silanization conditions comprise that the silanization temperature is 44 ℃ and the silanization time is 13 minutes. The drying and curing temperature is 106 ℃, and the drying atmosphere is nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=4.7:3.8:360. The zinc chloride is anhydrous zinc chloride. The modifier is processed under the following conditions that the modifier enters the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid on the inner surface of the micro-channel is controlled to be 0.28 m/s, the modifying temperature is 50 ℃, and the modifying time is 3.7 hours. And (3) treating the silanized micro-channel with a modifier to obtain a modified silanized micro-channel intermediate. The modified group diphenyl ether group content in the modified layer of the dealkalized refining agent is 0.18mol/m 2 after modification treatment, and the thickness is 4.6 micrometers.
The modified silylated filler intermediate is subjected to a first activator treatment. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the 4-amino-1, 3-benzene disulfonic acid is zinc chloride and the weight part of the toluene is 5.1:4.2:350. The zinc chloride is anhydrous zinc chloride. The first activator is treated by entering the micro-channel from the micro-channel inlet and flowing out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid of the first activator on the inner surface of the micro-channel is controlled to be 0.3 m/s, the modification temperature is 50 ℃, and the modification time is 4 hours. The dealkalization refined preparation is obtained through the activation modification.
The content of sulfonic acid groups in the dealkalized refined preparation which is treated by the first activator is 0.25mol/m 2, and the content of secondary amino groups is 0.11mol/m 2.
In the microchannel refiner, the pretreated dry gas feed volume space velocity was 2600h -1, the adsorption temperature was 25 ℃, and the adsorption pressure (gauge pressure) was 600kPa. The regenerant solution comprises 15% of tartaric acid, 2.5% of acetic acid, 1.5% of methanesulfonic acid and desalted water, and the balance of desalted water. Wherein the ratio of dry gas to regenerant solution is 550 by volume.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 23 ℃, the pressure is 700kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 7. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 104 percent by volume, and the mass concentration of the desulfurizing agent is 27 percent. In the dry gas scrubber, the scrubbing medium is desalted water. The conditions for contacting the desulphurized and purified dry gas with desalted water are as follows, the temperature is 45 ℃, the pressure is 700kPa by gauge pressure, and the gas-liquid ratio is 26 by volume.
The micro-channel is internally provided with a mist separation layer, and the separation precision is 8 microns. The cyclone separator is a cyclone separator, and the separation precision is 400 micrometers.
In the propylene removing contact tower, the propylene removing agent is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 18 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 10. The ratio of the dry gas of the raw material to the propylene removing agent is 115 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 12.5ppm.
[ Example 8]
The preparation method of the dealkalization refined agent comprises the steps of firstly carrying out silanization treatment on a microchannel to obtain a silanization microchannel, then treating the silanization microchannel with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization refined agent. The dealkalizing refined agent adopted in this example is different from that in example 3 only in that the modifier and the modification method are different, and the first modification component is selected from 2,2', 5-trichlorobiphenyl, specifically, 2', 5-trichlorobiphenyl, zinc chloride and toluene, wherein the weight portion of the 2,2', 5-trichlorobiphenyl is zinc chloride and toluene=4.6:5.5:320. The zinc chloride is anhydrous zinc chloride. The modifier is processed under the following conditions that the modifier enters the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out, wherein the linear velocity of the fluid on the inner surface of the micro-channel is controlled to be 0.29 m/s, the modifying temperature is 49 ℃, and the modifying time is 3.6 hours. And (3) treating the silanized micro-channel with a modifier to obtain a modified silanized micro-channel intermediate.
The prepared dealkalization refining agent has the content of modified groups (biphenyl groups) introduced into the dealkalization refining agent through a modifier of 0.17mol/m 2, the thickness of a modified layer of 4.5 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activator of 0.26mol/m 2, the content of secondary amino groups of 0.12mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activator of 7.5mmol/m 2, the content of secondary amino groups of 10.8mmol/m 2 and the content of methoxy groups of 22mmol/m 2.
The dry gas feed described in this example is the same as in example 3. The separation procedure of this example is the same as that of example 3.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 3.6ppm.
[ Example 9]
The preparation method of the dealkalization refined agent comprises the steps of firstly carrying out silanization treatment on a microchannel to obtain a silanization microchannel, then treating the silanization microchannel with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization refined agent. The dealkalizing refined agent adopted in this example is different from that in example 3 only in that the modifier and the modification method are different, and the first modification component is selected from 3,3', 5' -tetrachlorodiphenyl disulfide, specifically, 3', 5' -tetrachlorodiphenyl disulfide, zinc chloride and toluene, and the weight portion of 3,3', 5' -tetrachlorodiphenyl disulfide is zinc chloride and toluene=5.9:4.1:380. The zinc chloride is anhydrous zinc chloride. Modifier treatment conditions the modifier enters the micro-channel from the micro-channel inlet and flows out from the micro-channel outlet, and the process is circularly carried out, wherein the fluid linear speed of the modifier on the inner surface of the micro-channel is controlled to be 0.26 m/s, the modification temperature is 52 ℃, and the modification time is 3.9 hours. And (3) treating the silanized micro-channel with a modifier to obtain a modified silanized micro-channel intermediate.
The prepared dealkalization refining agent has the content of modification groups (disulfide groups) introduced into the dealkalization refining agent through a modifying agent of 0.16mol/m 2, the thickness of a modified layer of 4.2 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.25mol/m 2, the content of secondary amino groups of 0.11mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activating agent of 7.3mmol/m 2, the content of secondary amino groups of 10.5mmol/m 2 and the content of methoxy groups of 22mmol/m 2.
The dry gas feed described in this example is the same as in example 3. The separation procedure of this example is the same as that of example 3.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 4.2ppm.
Comparative example 1
This comparative example is compared to example 3 only in that no modified microchannels are used. The dry gas feed used in this comparative example was the same as in example 3, and the separation process for the dry gas feed was the same as in example 3.
The total nitrogen volume content in the obtained propylene-removed purified dry gas is 15ppm.
Comparative example 2
The dry gas feedstock used in this comparative example was the same as in example 3, and the desulfurization and dealkylation was the same as in example 3, and the dealkalization was carried out by eluting with water using a packed column (model 250Y). The operation conditions of the water scrubber and the process are that the temperature is 35 ℃, the pressure (gauge pressure) is 1000kPa, the theoretical plate number is 18, the dilute sulfuric acid aqueous solution with pH value of 3 is adopted, and the gas-liquid volume ratio is 40.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 36ppm.
[ Comparative example 3]
The dry gas raw material used in this comparative example was the same as in example 3, and the desulfurization and dealkylation were carried out in the same manner as in example 3, and the dealkalized impurity was obtained by using commercial 002SC H resin (Su Qing resin Co.) as an adsorbent under the conditions of 120 cubic meters of resin packing, 30℃of adsorption temperature and 50H -1 of volume space velocity by using a conventional fixed bed adsorption process.
At the initial stage of application, the total nitrogen volume content in the obtained propylene-removing purified dry gas is 5ppm, the adsorbent penetrates in about 13 days, 4% -6% sulfuric acid is used for regeneration, and the volume consumption of the regeneration liquid of the adsorbent per unit volume is 4-5 times.
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (37)
Priority Applications (1)
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| CN103987754A (en) * | 2011-12-16 | 2014-08-13 | 三键精密化学有限公司 | Curable resin composition |
| CN107849348A (en) * | 2015-03-31 | 2018-03-27 | 气凝胶科技有限责任公司 | Aerogel material and its production method |
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| TW200628465A (en) * | 2004-10-28 | 2006-08-16 | Theravance Inc | Process for preparing substituted 4-amino-1-(pyridylmethyl) piperidine and related compounds |
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| JP5957945B2 (en) * | 2011-03-03 | 2016-07-27 | 住友化学株式会社 | Addition polymerization method, prepolymerized catalyst component for addition polymerization, and method for producing addition polymer |
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| CN103987754A (en) * | 2011-12-16 | 2014-08-13 | 三键精密化学有限公司 | Curable resin composition |
| CN107849348A (en) * | 2015-03-31 | 2018-03-27 | 气凝胶科技有限责任公司 | Aerogel material and its production method |
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