CN102021016A - Method for deacidification of alkylation reaction product - Google Patents
Method for deacidification of alkylation reaction product Download PDFInfo
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for deacidification of an alkylation reaction product. In the method, after being subject to gravity settling, mixed emulsified liquid of the alkylation reaction product (hydrocarbon oil) and sulfuric acid passes through a component with hydrophobic modified ceramic membrane at a membrane surface speed of 0.01-5m/s for separation, and the deacidification of oil is achieved in a cross current filtration mode under the operation pressure of 0.01-0.3MPa and at the operation temperature of 0-40 DEG C. Under the push of pressure, the oil passes through the ceramic membrane, acid in the oil is trapped, and the acid content in the obtained oil is lower than 100ppm, thereby greatly reducing alkaline usage and waste water generation amount in an acid-base refine system of an alkylation technology and reducing the use of electrostatic precipitation; and the ceramic membrane surface is subject to hydrophobic modification, thus the contact angle of water droplet on the membrane surface is 70 degrees-16 degrees. The method is suitable for removal of polar liquid in various oils, has the advantages of simple process, low energy consumption, high separation precision, no environment pollution and high economic and practical value, and is easy to achieve industrial application.
Description
Technical field
The present invention relates to a kind of alkylation reaction product acid stripping method, belong to the membrane sepn field.
Background technology
Motor vehicle exhaust has become the main source of China's many big cities topsoil, is seriously perplexing people's life, and therefore, the gasoline of producing cleaning is extremely urgent, and alkylate oil is the ideal composition of clean gasoline.The sulfuric acid process alkylation process of the most employing of China at present, alkylation reaction product need adopt vitriol oil washing to remove sulfuric ester, and the reactant after the pickling enters settling vessel.But settling vessel can not be removed sulfuric acid fully, and particularly, in order to improve catalyzed reaction efficient, the sulfuric acid in reactor is stirred and is treated as fine droplets, has increased settlement separate difficulty.These sulfuric acid enter subsequent technique, cause the production unit heavy corrosion.The normal method that adopts is that through electrostatic precipitation, the mode of electrostatic precipitation is separated removal sulfuric acid after soda lye wash again with the emulsion after the pickling in the actual production at present.Adopt this method, can remove the sulfuric acid in the alkylation reaction product effectively, but need to use a large amount of alkali and produce a large amount of waste water, simultaneous problem is that system's seriously corroded and electric precipitator send electricity undesired, and the major cause of system's seriously corroded to be exactly electric precipitator come into operation undesired causing.Therefore be badly in need of developing new separation technology efficiently.
A small amount of vitriolic removal is a kind of removal of non-polar solvent system Semi-polarity drop in the alkylated reaction thing, the existing both at home and abroad correlative study that can use for reference, and wherein oil dehydrating is typical process.The more oil dehydrating method of present industrial use mainly contains:
(1). gravitational separation process
Be gravitational settling, its principle is to utilize the immiscible property of density difference and the oil and the water of oil and water, and realization water droplet and fluid separates under static or low speed flow state.Gravitational settling can be removed large-size water droplet in the fluid to reach the purpose that tentatively dewaters.One use gravitational separation process of fluid that aqueous concentration is bigger is handled.From service condition, the major equipment of gravitational settling has except that water pot, removes pond etc., needs very big container and very low flow velocity, and the treatment time is longer.
(2). centrifugal separation
Centrifugal separation is to make the container high speed rotating that oil-water mixture is housed, and forms centrifuge field and realizes oily water separation, and common equipment is a cyclone separator.Cyclone separator originates from Britain, and early stage bicone cyclone separator develops into now and has the identical separation performance with bicone but treatment capacity will exceed one times the tapered cyclone separator of list.Also at numerous and confused research centrifuge separator, for the higher mixed system of water content, there is good effect in domestic a lot of R﹠D institution, but when disperseing for water content less system, especially water droplet, treatment effect is undesirable.
(3). vacuum hydro-extraction
Vacuum hydro-extraction is meant because oil is different with the boiling point of water, can makes the two separation by the method for vacuum distilling.This method can be removed free water, emulsified water and dissolving water, promptly can remove the whole water in the fluid, but need fluid be heated to the boiling point of water under this pressure under vacuum, so energy consumption is very high.One capacity of the equipment of vacuum hydro-extraction is less, and processing efficiency is lower.
(4). chemical demulsification method
Chemical dehydration is exactly to add some macromolecular organic compound in oil product, this material can be adsorbed on the oily water termination, reduce the physical strength of interfacial film, change the emulsion type, destroy the stability of emulsion, make small droplets be merged into bigger drop, this kind material is commonly called emulsion splitter.Chemical demulsification method removes moisture in the oil product, owing to add chemical agent, can introduce new impurity in oil product.Because chemical demulsifier has very high surfactivity, may cause follow-up sewage disposal difficulty.Therefore remain the new emulsion splitter of the friendly type of development environment.
(5). ultrasonic separation method
The ultrasonication oil-water mixture can produce cohesion, hole or cavitation effect in mixed solution.When ultrasonic wave is passed through mixed solution, can cause the vibration of small water droplet.Because the particle that varies in size has different relative vibration velocities, water droplet will collide mutually, bonding, and the volume of water droplet increases gradually.Water droplet after the increase can sink by gravity, reaches isolating purpose.For a large amount of oil-water mixtures, directly use the ultrasonic wave separating effect not good, one need be used in combination with other separation methods.
(6). EDN
The ultimate principle of oil product electro-dewatering is: to the oil product extra electric field in the encloses container, make the globule polarization in the oil emulsion, become electric dipole, electric dipole attracts each other, make droplet aggregate into the bigger globule, sedimentation under action of gravity and separating with oil product.But, high-voltage field removes moisture in the oil product, when handling the higher oil emulsion of water content, understand the strength of electric field that produces electrical breakdown and can't set up interpolar necessity, so the electricity method of taking off is not suitable for independent use, preferably as the post-order process of other treatment process, and electricity to take off the method energy consumption big, the residence time is long.
By above various methodologies as can be seen, conventional oil dehydrating method has its distinctive advantage, and, less investment simple as equipment, dehydrating effect are good or the like, but also exist the shortcoming of relatively giving prominence to.
Along with the pay attention to day by day of people to environment protection, oil dehydrating needs lower pollution, few energy consumption, easy-operating method.The hold facility volume is little, simple to operate, low power consumption and other advantages is applied to every field more and more widely and membrane separation technique relies on.
Membrane separation process carries out oil dehydrating, is lipophilicity or the wetting ability of utilizing porous membrane, by screening, film phase-splitting, reverse osmosis or super penetration theory oil in liquid/liquid dispersion system and water is separated.If the precision height that dewaters that requires can also utilize more high-precision film will dissolve water and remove.
Chinese patent CN101530680A has announced the method for utilizing hydrophobic organic membrane to carry out oil dehydrating.The filtering traffic of this method is 10ml/min～500ml/min, and the moisture rejection can reach more than 99%, and hydrophobic membrane can reach 2～5 months work-ing life.This method energy consumption is low, the dehydration rate height, but the life-span of hydrophobic organic membrane is shorter, needs periodic replacement.
(Ezzati A such as Ezzati, Gorouhi E, Mohammadi T.Separation of water in oilemulsions using microfiltration[J] Desalination, 2005,185:371-38.) be water/gasoline system of the hydrophobic PTFE membrane sepn water content 5-20% of 0.45 μ m with the aperture, under optimal conditions, the permeation flux that obtains is 40L/m
2.h, the rejection to water reaches 95%.(Hu B such as Hu, Scott K.Microfiltration of water in oil emulsions and evaluation of fouling mechanism[J] Chem Eng J, 2008,136:210-220.) to adopt the aperture be that the hydrophobic PTFE membrane sepn water content of 0.2 μ m is water/kerosene system of 30%, at transmembrane pressure is 0.6bar, crossflow velocity is under the 1.5m/s, and obtaining the steady seepage flux is 20L/m
2H.The hydrophobic PTFE film that these two kinds of methods are used have the problem that needs the periodic replacement film too, and the steady seepage flux of gained is also lower.
Advantages such as and ceramic membrane is good because of having chemical stability, and physical strength is big, and anti-microbe ability is strong have been applied in the oily water separation field more and more.
People such as Ceng Jianxian (Ceng Jianxian, Zheng Lifeng. experimental study [J] the process engineering journal of ceramic membrane purifying solvent oil, 2010,10:488～492) to adopt mean pore size be that the ceramic membrane of 0.2 μ m is that the solvent oil of 0.5wt% carries out micro-filtration and separates to water content, investigated the influence to membrane flux and aluminium powder rejection of operating time, transmembrane pressure, cross-flow velocity, temperature.Under suitable operational condition, the film stabilized flux that obtains is 144.5L/ (m
2H).The resulting membrane flux of this method is also little, and exists more serious film to pollute with this method purifying solvent oil, needs recoil and solvent cleaning to recover membrane flux.
Summary of the invention
The objective of the invention is to solve problems such as system's corrosion in the existing alkylation reaction product depickling technology and settling vessel instability, a kind of efficient, environmental protection, energy-conservation alkylation reaction product acid stripping method are provided.
Technical scheme of the present invention is: membrane separation process principle of the present invention is: the ceramic membrane surface oleophilic drainage of hydrophobically modified, under the promotion of pressure difference, when using the ceramic membrane of modification to remove sulfuric acid in the alkylation reaction product, oil is because of the strong avidity on itself and oleophilic drainage surface, preferentially arrive per-meate side by film, and the ceramic membrane surface that the polar sulfuric acid droplets can not wetting hydrophobically modified, and in the emergent pressure scope, sulfuric acid droplets can not permeation ceramic membrane, so be trapped.
Concrete technical scheme of the present invention is: a kind of method of alkylation reaction product depickling, its concrete steps are as follows: alkylation reaction product and vitriolic mix emulsion fluid are through gravity settling after 1～6 hour, go into to be equipped with infusion in the membrane module of modified ceramic film, regulate service temperature at 0 ℃～40 ℃, adopt the cross flow filter mode to filter; Acid content is lower than 100ppm in the oil that obtains; Oil after the processing enters subsequent disposal, and the realization vitriolic is removed fully; Wherein said modified ceramic film is surperficial oleophilic drainage, and the contact angle of water droplet on the film surface is 70 °～160 °.
Alkylation reaction product of the present invention is the mixture of multiple hydrocarbon-type oil.One is 5～70wt% for an acid solution content in the mix emulsion fluid.
Gravity settling operation of the present invention is standing sedimentation, and oil and acid realize initial gross separation by the immiscible property of density difference and oil and acid.Acid content is 0.5～10wt% in the oil behind gravity settling.
During cross flow filter, the control crossflow velocity is 0.01～5m/s, and the control transmembrane pressure is at 0.01～0.3Mpa.
The separating layer of the ceramic membrane of surface modification of the present invention is at least a kind of in aluminum oxide, zirconium white, titanium oxide or the silicon oxide.The mean pore size of the ceramic membrane of surface modification is 0.01～1.4 μ m.
The surface modification of ceramic membrane of the present invention is to pass through chemical process, at organism such as ceramic membrane surface grafting organochlorosilane, methoxy silane, concrete method of modifying is with reference to the inventor patent CN101280241A in early stage, and the contact angle on the film surface of water droplet after modification is 70 °～160 °.
Acid content is lower than 100ppm in the oil product of gained of the present invention, has significantly reduced the consumption of alkali in the acid-alkali refining system of alkylation process and the generation of waste water, and has reduced the use of electrostatic precipitation.
Service temperature of the present invention one at 0 ℃～40 ℃, be suitable for too for the feed liquid of higher temperature.
Concentrated solution behind the ceramic membrane filter of the present invention turns back in the settling bowl, has realized separating and collection of sulfuric acid and alkylation reaction product.
The subsequent disposal operation of per-meate side oil of the present invention is to remove the middle dissolved minute quantity sulfuric acid that deoils, and can be methods such as soda lye wash.
Technology of the present invention also can be used for the subtractive process of other oil product Semi-polarity drop, as: the stock oil acid number of biodiesel synthesis is higher, removes the acid in the stock oil oil; Removal of water or sour water etc. in the synthetic oil technology.
Beneficial effect:
(1) the present invention does not use operations such as centrifugal, electrostatic precipitation, distillation, has saved energy consumption largely.
(2) to have the ceramic membrane chemical stability good for the ceramic membrane that uses of the present invention, and physical strength is big, and advantages such as anti-microbe ability is strong, long service life are green friendly economic parting materials.
(3) the present invention carries out chemical modification to ceramic membrane surface, makes ceramic membrane surface have hydrophobic lipophilicity, is beneficial to the infiltration of oil and the interception of acid solution.
(4) separation accuracy height of the present invention, acid content is lower than 100ppm in the oil after the processing, has significantly reduced the consumption of alkali in the acid-alkali refining system of alkylation process and the generation of waste water, has reduced the use of electrostatic precipitation.
(5) the present invention is simple to operate, less investment, practical value height.
Description of drawings
Fig. 1 is the present invention carries out oil dehydrating with ceramic membrane a cross flow filter process flow sheet; 1-settling bowl wherein, 2-charging stock tank, 3-fresh feed pump, 4,8-variable valve, 5,7-tensimeter, 6-ceramic film component, 9-spinner-type flowmeter, 10-tapping valve, A-subsequent disposal.
Embodiment
Below the present invention is described in detail with specific embodiment, but do not limit use range of the present invention.
Embodiment 1
Adopt process flow sheet shown in Figure 1.
Selecting supporting layer for use is Alpha-alumina, and separating layer is zirconic tubular ceramic membrane, and mean pore size is 0.05 μ m, adopts the modification of hexadecyl Trimethoxy silane.Concrete method of modifying is: ceramic membrane is soaked 4 hours in the ethanol that is dissolved with the hexadecyl Trimethoxy silane after, cleans repeatedly 5 times with ethanol, and 120 ℃ of dryings 3 hours down in baking oven at last, water droplet ceramic membrane surface contact angle after modification is 140 °.
Use alkylation reaction product acid stripping method of the present invention, separating oil/sulfuric acid mix emulsion fluid.After the 5L mix emulsion fluid left standstill 4 hours, supernatant liquid was poured in the charging stock tank; Use pump the oil in the charging stock tank/sulfuric acid mixture liquid to be injected the membrane module that the surface modification ceramic membrane is housed, service temperature is 30 ℃, regulated valve 4 and 8 aperture, making manometric average reading is that transmembrane pressure is 0.1MPa, the reading of spinner-type flowmeter is 5L/min, be that crossflow velocity is 1.67m/s, carry out cross flow filter; Experiment is opened valve after finishing, and feed liquid is discharged collect in the container for storing liquid of sealing.It is 1938L/ (m that experiment records the steady seepage flux
2H), the per-meate side acid content is 95ppm.Oil after ceramic membrane is handled adopts soda lye wash again, and acid content is 5ppm.
Adopt process flow sheet shown in Figure 1.
Petrochemical plant can produce a large amount of vitriolated waste oil in process of production, and the main component in these waste oil is an oil, but owing to contain a large amount of sulfuric acid, can't directly use.If sulfuric acid composition wherein can be removed, remaining oil composition wherein still can be used.
Use alkylation reaction product acid stripping method of the present invention, separate sulphur acid oil, selecting supporting layer for use is beta-alumina, separating layer is the tubular ceramic membrane of aluminum oxide, mean pore size is 0.2 μ m, adopt the modification of octadecyl trichlorosilane, all the other modification procedure are with embodiment 1, and water droplet ceramic membrane surface contact angle after modification is 130 °; Service temperature is 40 ℃, and other are operated with embodiment 1.The steady seepage flux that obtains is 1080L/ (m
2H), acid content is 90ppm in the per-meate side oil.Oil after ceramic membrane is handled adopts soda lye wash again, and acid content is 7ppm.
Adopt process flow sheet shown in Figure 1.
Can produce a large amount of waste oil in the production of propylene oxide, present waste oil tripping device causes acid water to enter the waste oil groove through regular meeting, thereby has influenced the quality of waste oil product and strengthened the extent of corrosion of pipeline, equipment.
Use alkylation reaction product acid stripping method of the present invention, separate the production of propylene oxide waste oil that contains sour water, selecting supporting layer for use is Alpha-alumina, separating layer is the tubular ceramic membrane of titanium oxide, mean pore size is 0.05 μ m, adopts the modification of normal-butyl dimethylchlorosilane, soaks 10 hours, all the other modification procedure are with embodiment 1, and water droplet ceramic membrane surface contact angle after modification is 95 °; Working pressure is 0.03MPa, and the feed liquid flow is 0.3L/min, and promptly crossflow velocity is 0.1m/s, and other are operated with embodiment 1.The steady seepage flux that obtains is 600L/ (m
2H), sour water content is 30ppm in the per-meate side waste oil.Oil after ceramic membrane is handled adopts soda lye wash again, and acid content is 8ppm.
Embodiment 4
Adopt process flow sheet shown in Figure 1.
Refinery adopts caustic washing electric refining technology to fraction oil deacidification more, but this method investment and process cost height, and waste lye quantity discharged height.
Use alkylation reaction product acid stripping method of the present invention, separate the refinery distillate, selecting supporting layer for use is Alpha-alumina, separating layer is the tubular ceramic membrane of aluminum oxide, mean pore size is 0.05 μ m, adopts the modification of hexadecyl Trimethoxy silane, soaks 6 hours, all the other modification procedure are with embodiment 1, and water droplet ceramic membrane surface contact angle after modification is 135 °; Working pressure is 0.15MPa, and other are operated with embodiment 1.The steady seepage flux that obtains is 1220L/ (m
2H), per-meate side sour water content is 88ppm.Oil after ceramic membrane is handled adopts soda lye wash again, and acid content is 10ppm.
Adopt process flow sheet shown in Figure 1.
In the widely used ester-interchange method biodiesel synthesis technology, the existence of water can impel fat hydrolysis and generate soap with alkali, therefore, when being catalyzer with the mineral alkali, usually requires the middle moisture of stock oil (as the plant wet goods) to be lower than 0.06%.
Use alkylation reaction product acid stripping method of the present invention, remove the moisture in the vegetables oil, selecting supporting layer for use is Alpha-alumina, separating layer is zirconic tubular ceramic membrane, mean pore size is 0.2 μ m, adopts the trimethylchlorosilane modification, soaks 6 hours, all the other modification procedure are with embodiment 1, and water droplet ceramic membrane surface contact angle after modification is 130 °; Other operations are with embodiment 1.The steady seepage flux that obtains is 1420L/ (m
2H), water-content is 75ppm in the per-meate side vegetables oil.
Embodiment 6
Adopt process flow sheet shown in Figure 1.
Engine oil is in the continuous working cycle of oiling system; the effective constituent of self can constantly be consumed; also have some foreign matters such as moisture, fuel oil, sand-dust impurity etc. simultaneously and sneak into, the use properties of machine oil will descend like this, even loses the protectiveness to engine.When containing excess water in the machine oil, the use properties of machine oil will descend, excessive moisture can make reduction of portions additive use properties even inefficacy in the machine oil under certain condition, can destroy the viscosity of machine oil, make machine oil on motion friction fit pair, form good lubricating oil film, thereby make machinery produce inordinate wear, even cause mechanical fault.
Use alkylation reaction product acid stripping method of the present invention, separate moisture engine motor oil, selecting supporting layer for use is Alpha-alumina, separating layer is the tubular ceramic membrane of silicon oxide, mean pore size is 0.1 μ m, adopt the modification of octyl group trichlorosilane, all the other modification procedure are with embodiment 1, and water droplet ceramic membrane surface contact angle after modification is 130 °; Working pressure is 0.08MPa, and the feed liquid flow is 0.6L/min, and promptly crossflow velocity is 0.2m/s, and other are operated with embodiment 1.The steady seepage flux that obtains is 1100L/ (m
2H), water-content is 70ppm in the per-meate side machine oil.
Embodiment 7
Adopt process flow sheet shown in Figure 1.
In the used oil pipe of hydraulic efficiency installation oily-water seperating equipment is installed, the moisture in the oil return and oil content is opened in time drained, to preventing oil emulsion, it is significant work-ing life to prolong oil product.
Use alkylation reaction product acid stripping method of the present invention, separate moisture hydraulic efficiency oil, select for use supporting layer and separating layer to be zirconic tubular ceramic membrane, mean pore size is 0.2 μ m, adopt the trimethylchlorosilane modification, soaked 7 hours, all the other modification procedure are with embodiment 1, and water droplet ceramic membrane surface contact angle after modification is 105 °; Service temperature is that working pressure is 0.05MPa, and the feed liquid flow is 0.1L/min, and promptly crossflow velocity is 0.033m/s, and other are operated with embodiment 1.The steady seepage flux that obtains is 800L/ (m
2H), per-meate side W/O content is 60ppm.
Embodiment 8
Adopt process flow sheet shown in Figure 1.
The oil product of service station and pours in the process of service station's oil reservoir through long-distance transport, can mix the water of part in the fuel oil, and quality of gasoline is descended, can not perfect combustion, engine knock and engine knock phenomenon easily take place.Therefore, gasoline needs purifying treatment before using.
Use alkylation reaction product acid stripping method of the present invention, separate aqueous 93# gasoline, selecting supporting layer for use is Alpha-alumina, separating layer is zirconic tubular ceramic membrane, mean pore size is 0.02 μ m, adopts the KH570 modification, soaks 10 hours, all the other modification procedure are with embodiment 1, and water droplet ceramic membrane surface contact angle after modification is 105 °; Working pressure is 0.2MPa, and other are operated with embodiment 1.The steady seepage flux that obtains is 950L/ (m
2H), water-content is 65ppm in the per-meate side gasoline.
Claims (5)
1. the method for an alkylation reaction product depickling, its concrete steps are as follows: alkylation reaction product and vitriolic mix emulsion fluid are through gravity settling after 1～6 hour, go into to be equipped with infusion in the membrane module of modified ceramic film, regulate service temperature at 0 ℃～40 ℃, adopt the cross flow filter mode to filter; Acid content is lower than 100ppm in the oil that obtains; Oil after the processing enters subsequent disposal, and the realization vitriolic is removed fully; Wherein said modified ceramic film is surperficial oleophilic drainage, and the contact angle of water droplet on the film surface is 70 ° 160 °.
2. method according to claim 1, when it is characterized in that cross flow filter, the control crossflow velocity is 0.01～5m/s, the control transmembrane pressure is at 0.01～0.3Mpa.
3. method according to claim 1, the separating layer that it is characterized in that the ceramic membrane of described surface modification are at least a kind of in aluminum oxide, zirconium white, titanium oxide or the silicon oxide.
4. method according to claim 1, the mean pore size that it is characterized in that the ceramic membrane of described surface modification are 0.01～1.4 μ m.
5. alkylation reaction product acid stripping method according to claim 1, the ceramic membrane that it is characterized in that described surface modification is by chemical process, at ceramic membrane surface grafting organism, the contact angle on the film surface of water droplet after modification is 70 °～160 °.
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Cited By (9)
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| CN102229850A (en) * | 2011-06-08 | 2011-11-02 | 南京工业大学 | Waste hydraulic oil regenerating method and equipment |
| CN104857742A (en) * | 2015-05-28 | 2015-08-26 | 重庆理工大学 | Water removal method of dichloromethane |
| CN105670686A (en) * | 2016-03-04 | 2016-06-15 | 华东理工大学 | Alkylation reaction effluent pickling method and device |
| CN106861436A (en) * | 2017-03-16 | 2017-06-20 | 安阳工学院 | One kind is using nano ceramics hyperfiltration treatment alkylation spent acid technique |
| CN108070400A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of alkylation |
| CN108070401A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of separation method of alkylation reaction product |
| CN109485192A (en) * | 2017-09-12 | 2019-03-19 | 江苏赛瑞迈科新材料有限公司 | It is alkylated spent acid ceramic membrane filter device |
| CN114588844A (en) * | 2022-03-18 | 2022-06-07 | 杭州师范大学 | Application of Shuangshen hollow fiber membrane reactor in Suzuki-Miyaura reaction and membrane reactor thereof |
| CN115364670A (en) * | 2021-05-21 | 2022-11-22 | 三达膜科技（厦门）有限公司 | Preparation method of oil-water separation modified spherical alumina ceramic microfiltration membrane |
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| CN101070507A (en) * | 2007-06-05 | 2007-11-14 | 天津新膜科技有限责任公司 | Regeneration method for waste lubricant and apparatus |
| CN101280241A (en) * | 2008-05-22 | 2008-10-08 | 南京工业大学 | Method for purifying waste lubricant oil |
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| CN102229850A (en) * | 2011-06-08 | 2011-11-02 | 南京工业大学 | Waste hydraulic oil regenerating method and equipment |
| CN102229850B (en) * | 2011-06-08 | 2013-05-08 | 南京工业大学 | Waste hydraulic oil regenerating method and equipment |
| CN104857742A (en) * | 2015-05-28 | 2015-08-26 | 重庆理工大学 | Water removal method of dichloromethane |
| CN105670686A (en) * | 2016-03-04 | 2016-06-15 | 华东理工大学 | Alkylation reaction effluent pickling method and device |
| CN108070401A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of separation method of alkylation reaction product |
| CN108070400A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of alkylation |
| CN108070400B (en) * | 2016-11-15 | 2020-03-17 | 中国石油化工股份有限公司 | Alkylation method |
| CN108070401B (en) * | 2016-11-15 | 2020-03-17 | 中国石油化工股份有限公司 | Separation method of alkylation reaction product |
| CN106861436A (en) * | 2017-03-16 | 2017-06-20 | 安阳工学院 | One kind is using nano ceramics hyperfiltration treatment alkylation spent acid technique |
| CN109485192A (en) * | 2017-09-12 | 2019-03-19 | 江苏赛瑞迈科新材料有限公司 | It is alkylated spent acid ceramic membrane filter device |
| CN115364670A (en) * | 2021-05-21 | 2022-11-22 | 三达膜科技（厦门）有限公司 | Preparation method of oil-water separation modified spherical alumina ceramic microfiltration membrane |
| CN115364670B (en) * | 2021-05-21 | 2024-04-19 | 三达膜科技（厦门）有限公司 | Preparation method of oil-water separation modified spherical alumina ceramic microfiltration membrane |
| CN114588844A (en) * | 2022-03-18 | 2022-06-07 | 杭州师范大学 | Application of Shuangshen hollow fiber membrane reactor in Suzuki-Miyaura reaction and membrane reactor thereof |
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