Method for realizing separation of organic matters and water by utilizing oleophylic hydrophobic and hydrophilic oleophobic materials

Abstract

The invention relates to the technical field of oil-water separation, in particular to a method for achieving organic matter and water separation through oleophylic, hydrophobic, hydrophilic and oleophobic materials. Comprising the following steps: carrying out heat exchange and temperature regulation on raw materials, carrying out oil-water separation on an organic matter aqueous solution through a modified filler separation tower, and further removing organic matters from a lean oil-water phase at the bottom of the modified filler separation tower through a stripping tower. The upper part of the inlet of the modified filler separation tower is oleophylic and hydrophobic modified filler, the lower part of the inlet is hydrophilic and oleophobic modified filler, and a product oil liquid is obtained at the top of the modified filler separation tower. And further removing organic matters from the tower bottom lean oil water phase obtained by the modified filler separation tower through a stripping tower to obtain a product water liquid. According to the present invention, by using the oleophylic, hydrophobic, hydrophilic and oleophobic characteristics of the modified filler, the separation of the insoluble, slightly soluble and soluble organic matter aqueous solutions is achieved, the separation energy consumption is substantially reduced, and the low water content requirement of the product oil liquid and the low oil content requirement of the product water liquid are met.

Description

Technical Field

[0001] The present invention relates to the technical field of oil-water separation, and more specifically, to a method for separating insoluble, slightly soluble, soluble organic matter and water by utilizing oleophilic-hydrophobic or hydrophilic-oleophobic modified materials. Background Art

[0002] Crude oil extraction, petrochemical industry, catering industry, shipping industry, and oil pressing production all produce various organic aqueous solutions that need to be treated.

[0003] At present, there are various methods for treating such organic aqueous solutions, mainly physical methods such as precipitation, filtration, centrifugal separation, membrane method, extraction method, distillation method; chemical methods such as neutralization method, coagulation sedimentation method, oxidation-reduction method; biological methods such as activated sludge method.

[0004] She Yue mentioned in "Research on the Design of Oily Wastewater Treatment and Recycled Water Treatment Process in Petrochemical Enterprises" that oil substances usually exist in wastewater in the form of floating oil, dispersed oil, emulsified oil, and dissolved oil. In addition, it may also contain free caustic soda, phenol, sulfur, cyanide, etc. The treatment methods are pretreatment, biochemical treatment, and deep treatment. If reused, ultrafiltration and reverse osmosis technology are used. According to this scheme, the treatment of wastewater containing oil has the problems of high cost and short life of reverse osmosis membrane.

[0005] Patent CN115209973 "System for continuous oil / water separation using super-hydrophilic oil / water separation filter" invented the use of super-hydrophilic oil / water separation filter to achieve continuous oil / water separation, but the filter is still prone to clogging and contamination.

[0006] Patent CN117467190 "A super-hydrophobic and super-oleophilic sponge and its preparation method and application in oil-water separation" invented a super-hydrophobic and super-oleophilic modification using polyurethane sponge as the matrix. It is suitable for treating oil spills and marine oil spills.

[0007] Patent CN209890404 "An emulsion oil-water separation system" invented an emulsion oil-water separation system, which uses quartz sand and anthracite for primary filtration, then adds flocculants, and then uses walnut shells and fiber balls for fine filtration. However, walnut shells and fiber balls cannot be regenerated and have high cost of use.

[0008] Patent CN116063687 "A hydrophobic quartz sand and its preparation method and application" invented a hydrophobic oleophilic quartz sand for treating oily wastewater and filtering and removing oil from oil-in-water emulsions.

[0009] Patent WO94 / 15702 "METHOD AND DEVICE FOR SEPARATING OIL / WATER MIXTURES" invented a method for oil-water separation using hydrophilic and hydrophobic filter membranes. Summary of the invention

[0010] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for separating organic matter and water by using lipophilic and hydrophobic materials or hydrophilic and oleophobic materials. By utilizing the lipophilic and hydrophobic properties of modified fillers, the separation of insoluble, slightly soluble and soluble organic aqueous solutions is achieved, the separation energy consumption is greatly reduced, and the low water content requirements of the product oil liquid and the low oil content requirements of the product water liquid are met.

[0011] In order to achieve the above-mentioned purpose, a method for separating organic matter and water using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials is provided, comprising: raw material pretreatment, raw material heat exchange and temperature adjustment, organic aqueous solution passing through a modified filler separation tower for oil and water separation, and the oil-poor water phase at the bottom of the modified filler separation tower passing through a stripping tower to further remove organic matter.

[0012] Water is the source of human life. About 10% of the world's population lives in water-scarce countries. Oily wastewater, as a common wastewater, is generated in industry, food processing and kitchen waste. Untreated or improperly treated oily wastewater can cause air pollution, surface water and groundwater pollution.

[0013] Oily wastewater usually exists in three forms due to the different sizes of oil droplets. Free oil with a diameter of >150μm can be separated by gravity separation. Dispersed oil with a diameter between 20-150μm can be removed by gravity and adding stabilizers. Emulsified oil with a diameter of <20μm is relatively stable and needs to be removed by adding flocculants.

[0014] For slightly soluble or soluble organic aqueous solutions, distillation, extraction and membrane separation are usually used for separation.

[0015] When the organic aqueous solution contains both insoluble oil droplets and soluble organic matter, the current treatment methods are incineration, biochemical treatment, distillation, and membrane method.

[0016] The insoluble, slightly soluble, soluble organic aqueous solution of the present invention refers to an aqueous solution containing n kinds of insoluble, slightly soluble, soluble pure substances, where n≥1. The mass ratio of water in the aqueous solution is not a fixed value, and includes both oil-in-water (W / O) and water-in-oil (O / W) solutions of insoluble organic solutions; and solvent water in slightly soluble and soluble organic solutions.

[0017] Based on the above analysis, the present invention is implemented by the following steps, each of which has the following characteristics:

[0018] (1) Before step S1, the organic aqueous solution is first passed into a raw material pre-separator, and the raw material pre-separator is a combination of one or more of filter cake filtration, deep filtration, and centrifugal filtration.

[0019] Organic aqueous solutions usually contain a variety of impurities, such as organic polymers, large sand and gravel particles, large iron filings, large oil droplets, etc., which need to be removed before entering the modified packing separation tower to avoid clogging the packing. Large oil droplets are usually larger than 150μm in diameter and can be easily removed by primary filtration.

[0020] Cake filtration can be carried out by filter press, filter, etc.; deep filtration can be carried out by quartz sand, anthracite, fixed bed reactor, etc.; centrifugal filtration can be carried out by centrifuge, cyclone separator, etc.

[0021] (2) Heat exchange and temperature adjustment of the organic aqueous solution to ensure that the temperature is greater than 3°C and lower than the temperature at which the organic matter reacts.

[0022] Increasing the temperature is conducive to destroying the emulsified state of organic aqueous solution. As the temperature increases, the solubility of most organics will increase. At the same time, increasing the temperature weakens the strength of the oil-water interface film, reduces the viscosity of the oil phase and the water phase, and is conducive to coalescence separation. Therefore, for the separation of oil and water using modified fillers, appropriately increasing the temperature is conducive to the separation process. Different organic aqueous solutions have different viscosities. In order to ensure the normal operation of the modified packing tower, it is necessary to ensure that the temperature of the organic aqueous solution is greater than 3°C. If the temperature of the organic aqueous solution is too high, obvious chemical reactions will occur between the organic matter and water. For example: propylene oxide and water will have an obvious reaction to generate propylene glycol at 90°C, and basically no chemical reaction will occur when the temperature is lowered to 40°C; acetic anhydride and water will have an obvious reaction to generate acetic acid at 50°C. The aqueous solution needs to be cooled as much as possible, but the temperature must be greater than 3°C.

[0023] Generally speaking, when the temperature rises by 10℃, the liquid viscosity decreases by 50%, and the reduced viscosity is beneficial to the separation of the modified packed tower. However, increasing the temperature consumes energy. Taking water as an example, it takes 12kw of energy to heat 1 ton of water from 20℃ to 30℃. Therefore, it is necessary to reasonably determine the heat exchange temperature of the organic aqueous solution according to the viscosity requirements in the modified packed tower.

[0024] (3) The temperature-adjusted organic aqueous solution is passed into a modified packed tower for oil-water separation, and an organic-rich oil phase is obtained at the top of the tower, and an oil-poor aqueous phase is obtained at the bottom of the tower.

[0025] The packing is modified to be oleophilic and hydrophobic, or hydrophilic and oleophobic, which changes the original characteristics of the packing, achieves an unexpected separation effect, and greatly improves the oil-water separation efficiency. The feed position of the modified packing tower, the height of the packing section above the feed position, and the height of the packing section below the feed position are set according to the water content requirements of the product oil liquid and the oil content requirements of the product water liquid. The product oil liquid is obtained at the top of the modified packing tower, and the oil-poor water phase is obtained at the bottom of the modified packing tower.

[0026] (4) Detecting the organic matter content in the oil-poor water phase obtained at the bottom of the tower in step S2:

[0027] If the organic matter content in the oil-poor water phase is within the specified range, the oil-water separation is completed;

[0028] If the organic matter content in the oil-lean water phase is not within the specified range, it is passed into a stripping tower to further remove the organic matter, and water liquid is obtained at the bottom of the tower; or the oil-lean water phase is filtered with a modified hydrophilic oleophobic membrane to obtain a product water liquid; or the oil-lean water phase is first filtered with a modified hydrophilic oleophobic membrane and then passed through a stripping tower to obtain a product water liquid.

[0029] When the oil-poor water phase at the bottom of the modified packing tower still contains a small amount of insoluble emulsified oil and a part of slightly soluble organic matter and soluble organic matter, further removal is required. The modified hydrophilic oleophobic membrane, stripping tower, or a modified hydrophilic oleophobic membrane and stripping tower in series can be used to further remove the organic matter.

[0030] Membrane filtration is a membrane separation technology driven by pressure. Under a certain pressure, the micropores on the membrane surface only allow water and small molecules to pass through, and the micropores larger than the membrane surface are retained on the membrane inlet side to achieve the separation function. When there is still a small amount of organic matter in the oil-poor water phase at the bottom of the modified packing tower, membrane filtration can be used as the final treatment method to obtain product water liquid, or membrane filtration can be used as a pre-treatment process for the stripping tower to further reduce the separation requirements of the stripping tower and reduce the separation energy consumption of the stripping tower.

[0031] Furthermore, in step S2, a modified packing section is set in the modified packing tower, and the lipophilic and hydrophobic modified packing is to introduce oil and / or wax non-polar substances on the packing surface; the hydrophilic and lipophobic modified packing is to introduce hydroxyl and / or carboxyl polar groups on the packing surface.

[0032] Further, in step S2, the filler material is one or a combination of ceramic, metal, plastic, quartz, and fruit shell. The filler is the core part of the work of the packed tower and affects the heat transfer and mass transfer performance. Ceramics, metals, and plastics as traditional fillers have mature performance parameters and mature processing and manufacturing characteristics. According to the shape, there are: Raschig rings, ball rings, rectangular saddles, step rings, etc. Unmodified ceramics are hydrophilic and oleophilic, most unmodified metals are hydrophilic and oleophilic, and most unmodified plastics are oleophobic and hydrophobic. At present, quartz is rarely used as a filler, mainly because quartz processing is difficult, and unmodified quartz is hydrophilic and oleophobic. Fruit shells are usually used as adsorbents, not as fillers. Unmodified fruit shells are lipophilic and hydrophilic. After the fruit shell is modified, it can achieve lipophilic and hydrophobic, hydrophilic and oleophobic, and the modified material seals the internal gaps of the fruit shell, and the modified fruit shell does not have the problem of difficulty in gap regeneration.

[0033] Further, in step S2, the water-in-oil (W / O) section in the modified packing tower uses an oleophilic hydrophobic modified packing, and the oil-in-water (O / W) section in the modified packing tower uses a hydrophilic oleophobic modified packing. Through the examples, it is believed that the water-in-oil (W / O) section uses an oleophilic hydrophobic modified packing, and the oil-in-water (O / W) section uses a hydrophilic oleophobic modified packing, and the packing tower separation effect is the best. There is currently no relevant in-depth theoretical research results.

[0034] Further, in step S2, when the soluble organic matter content in the poor oil water phase at the bottom of the modified packing tower is high, part of the top product oil liquid is returned to the modified packing tower entrance and / or the modified packing tower entrance is injected into other oil phases as the extractant of soluble organic matter. According to the similar compatible principle, the solute composed of non-polar molecules is soluble in the solvent composed of non-polar molecules and is insoluble in the solvent composed of polar molecules. Therefore, part of the modified packing tower top product oil liquid returns to the modified packing tower entrance, which can increase the oil phase ratio in the modified packing tower, so that more slightly soluble organic matter and soluble organic matter are dissolved in the oil phase, and reduce the soluble organic matter content in the poor oil water phase at the bottom of the modified packing tower. Injecting other oil phase extractants at the modified packing tower entrance also utilizes the similar compatible principle, and the difference is that the similar compatible effect of injecting other oil phase extractants is better, such as: methyl isobutyl ketone (MIBK).

[0035] Further, the modified packing separation tower of step S2 is optimized as follows: the hydrophilic oleophobic packing section has n layers, n≥1, the oleophilic hydrophobic packing section has m layers, m≥1, and the water-in-oil (W / O) oil phase in any section returns to the oleophilic hydrophobic packing layer through the return line, and / or the oil-in-water (O / W) water phase returns to the hydrophilic oleophobic packing layer through the return line. Returning the water-in-oil (W / O) oil phase through the return line can reduce the oil impact of the oil on the upper hydrophilic oleophobic packing layer and improve the separation efficiency of the modified packing layer; returning the oil-in-water (O / W) water phase through the return line can reduce the water impact of the water on the lower oleophilic hydrophobic packing layer and improve the separation efficiency of the modified packing layer.

[0036] Further, in step S3, the stripping tower uses a packing and / or a plate tower, and the packing uses a modified and / or non-modified packing. The stripping tower is based on the principle of phase equilibrium, and steam or gas can be used as a stripping agent. The equilibrium partial pressure of the solute in the liquid phase is greater than the partial pressure of the solute in the gas phase. When using a packing, using a modified packing can reduce the height of the mass transfer unit, but increase the cost.

[0037] The beneficial effects of the present invention are:

[0038] 1. Using the lipophilic and hydrophobic, hydrophilic and lipophobic properties of modified fillers, a modified filler tower is used to separate aqueous solutions of insoluble organic matter;

[0039] 2. Using the principle of like dissolves like, a modified packed tower is used to separate slightly soluble and soluble organic aqueous solutions;

[0040] 3. The modified packed tower is used for liquid-liquid separation, which greatly reduces the energy consumption of separation of insoluble, slightly soluble and soluble organic aqueous solutions. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0042] Figure 1 This is a process flow diagram of washing the oil field ground sludge to obtain an organic aqueous solution according to Example 1 of the present invention, and using oleophilic and hydrophobic, hydrophilic and oleophobic modified materials to separate insoluble, slightly soluble and soluble organic aqueous solutions;

[0043] Wherein: 1-pre-separator, 2-1-heat exchanger (one), 2-2-heat exchanger (two), 2-3-heat exchanger (three), 3-modified packing tower, 4-stripping tower, 5-centrifugal pump;

[0044] Figure 2 This is a process flow diagram of separating insoluble, slightly soluble and soluble organic aqueous solutions using oleophilic and hydrophobic or hydrophilic and oleophobic modified materials from the organic aqueous solution produced during the low-temperature dry distillation of coal according to Example 2 of the present invention;

[0045] Wherein: 1-pre-separator, 2-1-heat exchanger (one), 3-modified packing tower, 5-centrifugal pump, 6-modified membrane filter;

[0046] Figure 3This is a process flow diagram of separating insoluble, slightly soluble and soluble organic aqueous solutions from organic aqueous solutions produced in the propylene oxide production process according to Example 3 of the present invention using lipophilic and hydrophobic or hydrophilic and lipophilic modified materials;

[0047] Among them: 2-1-heat exchanger (one), 3-modified packed tower. DETAILED DESCRIPTION

[0048] The technical solution of the present invention is further described in detail below in conjunction with the accompanying drawings, but the scope of protection of the present invention is not limited to the following. Any feature disclosed in this specification (including any additional claims, abstract and drawings) can be replaced by other equivalent or alternative features with similar purposes unless otherwise stated. That is, unless otherwise stated, each feature is only an example of a series of equivalent or similar features.

[0049] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0050] Various terms appearing in the present application are only used for the purpose of describing specific embodiments and are not intended to be limiting of the present invention; unless the context clearly indicates otherwise, the singular form is intended to include the plural form as well.

[0051] When the terms "include" and / or "comprising" are used in this specification, these terms indicate the existence of the stated features, integers, steps, operations, elements and / or parts, but do not exclude the existence and / or addition of one or more other features, integers, steps, operations, elements, parts and / or groups thereof.

[0052] As described in the background art, the existing hydraulic turbine pressure energy recovery technology does not involve the pressure energy recovery of easily vaporized high-pressure liquid. In order to solve the above problem, the present invention proposes the following technical solution.

[0053] The present invention utilizes the lipophilic and hydrophobic, hydrophilic and lipophobic properties of the modified filler to achieve the separation of insoluble, slightly soluble and soluble organic aqueous solutions, greatly reduces separation energy consumption, and meets the low water content requirements of the product oil liquid and the low oil content requirements of the product water liquid.

[0054] The method comprises the following steps: raw material heat exchange and temperature adjustment, organic aqueous solution passes through a modified packing separation tower to separate oil and water, and the oil-poor water phase at the bottom of the modified packing separation tower passes through a stripping tower to further remove organic matter.

[0055] Specifically, the separation method comprises the following steps:

[0056] S1. Heat exchange and temperature adjustment of the organic aqueous solution to ensure that the temperature is greater than 3°C and lower than the temperature at which the organic matter reacts;

[0057] S2, passing the temperature-adjusted organic aqueous solution into a modified packed tower for oil-water separation, obtaining an organic-rich oil phase at the top of the tower and an oil-poor aqueous phase at the bottom of the tower;

[0058] S3, detecting the organic matter content in the oil-poor water phase obtained at the bottom of the tower in step S2:

[0059] If the organic matter content in the oil-poor water phase is within the specified range, the oil-water separation is completed;

[0060] If the organic matter content in the oil-lean water phase is not within the specified range, it is passed into a stripping tower to further remove the organic matter, and water liquid is obtained at the bottom of the tower; or the oil-lean water phase is filtered with a modified hydrophilic oleophobic membrane to obtain a product water liquid; or the oil-lean water phase is first filtered with a modified hydrophilic oleophobic membrane and then passed through a stripping tower to obtain a product water liquid.

[0061] Before step S1, the organic aqueous solution is first passed into a raw material pre-separator, and the raw material pre-separator is a combination of one or more of filter cake filtration, deep filtration, and centrifugal filtration.

[0062] In step S2, a modified packing section is arranged in the modified packing tower. The lipophilic and hydrophobic modified packing is to introduce oil and / or wax non-polar substances on the packing surface; the hydrophilic and lipophobic modified packing is to introduce hydroxyl and / or carboxyl polar groups on the packing surface.

[0063] In step S2, the filler material is one or a combination of ceramic, metal, plastic, quartz, and fruit shell.

[0064] In step S2, the water-in-oil (W / O) section in the modified packing tower uses oleophilic and hydrophobic modified packing, and the oil-in-water (O / W) section in the modified packing tower uses hydrophilic and oleophobic modified packing.

[0065] In step S2, when the content of soluble organic matter in the oil-poor water phase at the bottom of the modified packed tower is high, part of the top product oil liquid is returned to the inlet of the modified packed tower, and / or other oil phases are injected into the inlet of the modified packed tower as an extractant for soluble organic matter.

[0066] The modified packing separation tower of step S2 is optimized as follows: the hydrophilic oleophobic packing section has n layers, n≥1, the oleophilic hydrophobic packing section has m layers, m≥1, and the water-in-oil (W / O) oil phase in any section returns to the oleophilic hydrophobic packing layer through a return line, and / or the oil-in-water (O / W) water phase returns to the hydrophilic oleophobic packing layer through a return line.

[0067] In step S3, the stripping tower uses a packing and / or a plate tower, and the packing uses a modified and / or non-modified packing.

[0068] Embodiment 1, as Figure 1 As shown, the oil field sludge is washed to obtain an organic aqueous solution, and the insoluble, slightly soluble and soluble organic aqueous solutions are separated by using lipophilic and hydrophobic, hydrophilic and lipophobic modified materials. The components of the oil field sludge are complex, and the pyrolysis temperature is between 400℃ and 700℃. In this embodiment, a certain surfactant is used when washing the oil field sludge. The following steps are included:

[0069] Step (1), washing 30°C, containing 10% organic matter and a small amount of suspended sediment to obtain 1 t / h organic aqueous solution, and using a horizontal pusher centrifuge to remove large particles of solids.

[0070] Step (2), the organic aqueous solution from which the large solid particles have been removed is sequentially passed into heat exchangers 2-1, 2-2, and 2-3 for heat exchange and temperature increase from 30°C to 60°C.

[0071] Step (3), passing the organic aqueous solution at 60°C into the modified packed tower 3. The modified packed tower feed port uses a modified oleophilic hydrophobic ceramic packing with a packing height of 1m; the feed port uses a modified hydrophilic oleophobic quartz packing with a packing height of 1.5m. The top product oil liquid parameters are: temperature 60°C, flow rate 98.8kg / h, water content 0.05wt%. The bottom oil-poor water phase parameters are: temperature 60°C, flow rate 1001.2kg / h, oil content 0.1wt%.

[0072] When the oil-poor water phase at the bottom of the modified packing tower is reused as ground sludge washing water, it does not need to be further processed by the stripping tower and can be directly reused as product water liquid.

[0073] Step (4), when the oil-poor water phase at the bottom of the modified packing tower is used as water injection for oil field reservoirs, it needs to be further processed. The poor oil at the bottom of the modified packing tower is passed into the stripping tower 4. The stripping tower adopts a plate tower with a steam parameter of 60kg / h. The product water liquid parameters obtained at the bottom of the tower are: temperature 81°C, flow rate 1033kg / h, and oil content trace. The gas phase stream at the top of the tower passes through the heat exchanger 2-2 to obtain an organic aqueous solution 1 with the parameters of: temperature 40°C, flow rate 28kg / h, and oil content 4wt%.

[0074] The replacement step of step (4) is: when the oil-poor water phase at the bottom of the modified packing tower is used as water injection for oil field reservoirs, it needs to be further processed. The oil-poor water phase at the bottom of the modified packing tower is passed through a modified hydrophilic oleophobic ceramic membrane for filtration. The pore size of the modified ceramic membrane is 0.1 μm, and the operating temperature is 60°C. The product water parameters after passing through the modified hydrophilic oleophobic ceramic membrane are: temperature 60°C, flow rate 1013 kg / h, and oil content 40 ppm. The oil-rich water phase throttled by the modified hydrophilic oleophobic ceramic membrane returns to the modified packing tower 3.

[0075] Comparative Example 1 is to add flocculants, precipitate, and then filter and remove oil with an organic membrane. The oil content in the product water liquid is 35ppm. However, the organic membrane has a limited number of uses, and the oil cannot be recycled after adding the flocculants.

[0076] Embodiment 2, as Figure 2 As shown, the organic aqueous solution produced during the low-temperature carbonization of coal is separated into insoluble, slightly soluble and soluble organic aqueous solutions using oleophilic and hydrophobic, hydrophilic and oleophobic modified materials. The organic aqueous solution produced in this process is also called blue carbon wastewater. The components of this organic aqueous solution are complex. The organic aqueous solution in a certain place is classified according to its characteristics as: ammonia 3700mg / L, phenols 2800mg / L, oils 1182mg / L, and pH 9. It includes the following steps:

[0077] Step (1), using a 400-mesh hydrophilic-oleophobic modified stainless steel wire basket filter to remove large solid particles and large oil droplets from a 30° C., 2 t / h organic aqueous solution.

[0078] Step (2), the organic aqueous solution from which large solid particles and large oil droplets have been removed is passed into the heat exchanger 2-1 for heat exchange and temperature increase from 30°C to 60°C. The heat source is 0.5MPa, 210°C steam.

[0079] Step (3), passing the 60°C organic aqueous solution into the modified packed tower 3. The upper part of the feed inlet of the modified packed tower is filled with modified oleophilic and hydrophobic plastic fillers, with a packing height of 1m; the lower part of the feed inlet is filled with modified hydrophilic and oleophobic fruit shell fillers, with a packing height of 2m. The oil phase at the top of the modified packed tower returns 97kg / h to the modified packed tower for feeding, and 20kg / h of methyl isobutyl ketone (MIBK) extractant is injected before the modified packed tower is fed. The parameters of the top product oil liquid are: temperature 60°C, flow rate 118kg / h, water content 0.3wt%. The parameters of the bottom lean oil water phase are: temperature 60°C, flow rate 2015kg / h, oil content 0.8wt%. The extractant injected before the modified packed tower is fed is recovered during the subsequent treatment of the product oil liquid.

[0080] Step (4), the oil-poor water phase at the bottom of the modified packing tower is passed into the modified hydrophilic oleophobic membrane filter 6 to further remove organic matter. The modified membrane pore size is 0.01 μm, and the operating temperature is 60°C. The parameters of the product water after passing through the modified hydrophilic oleophobic membrane are: temperature 60°C, flow rate 1995 kg / h, and oil content 150 ppm. The oil-rich water phase throttled by the modified hydrophilic oleophobic membrane returns to the modified packing tower. Because phenols are slightly soluble in water, the product water after passing through the modified hydrophilic oleophobic membrane still contains phenols, ammonia, etc., and needs to be processed in the subsequent treatment process.

[0081] Comparative Example 2 uses cyclone coalescence in a tank to remove oil, a deamination tower to remove ammonia, and an extraction tower to extract phenols. The oil content in the product water liquid is greater than 300ppm. The oil and dust content in the deamination tower and the extraction tower is high and cannot be operated continuously.

[0082] Embodiment 3, as Figure 3 As shown, the organic aqueous solution produced in the propylene oxide production process uses lipophilic-hydrophobic and hydrophilic-oleophobic modified materials to separate insoluble, slightly soluble and soluble organic aqueous solutions. The components of the organic aqueous solution produced in this process are complex. The organic aqueous solution of a certain propylene oxide production process has a typical component ratio of: water 0.212wt%, propylene oxide 0.072wt%, ethylbenzene 0.448wt%, acetophenone 0.028%, and phenylethanol 0.239wt%. It includes the following steps:

[0083] In step (1), large solid particles have been removed in the propylene oxide reaction step, and a certain process uses a heterogeneous fixed bed reactor to perform deep filtration. Therefore, the filtration step is not repeated in this step.

[0084] Step (2), the 90°C, 10t / h organic aqueous solution is cooled to 40°C using a circulating water heat exchanger 2-1. The reason for cooling is that propylene oxide reacts with water at 90°C to generate propylene glycol, and lowering the temperature to 40°C can avoid the reaction of generating propylene glycol, and the viscosity at this time is 0.7mPa*S, which meets the parameter requirements of the modified filler.

[0085] Step (3), passing the 40°C organic aqueous solution into the modified packed tower 3. The modified packed tower feed port uses a modified oleophilic hydrophobic ceramic filler at the upper part, the filler height is 3m, 3 filler layers are set, each layer is 1m high, and a liquid redistributor is set between the layers; the lower part of the feed port uses a modified hydrophilic oleophobic quartz filler, the filler height is 2m, 2 filler layers are set, each layer is 1m high, and a liquid redistributor is set between the layers. An oil phase return line is set on the upper part of the first layer of filler at the bottom of the modified hydrophilic oleophobic filler, and the oil-in-water (W / O) oil phase is returned to the oleophilic hydrophobic filler layer at the top of the modified packed tower through the return line. The return line can be placed in the tower or outside the tower. The liquid parameters of the top product oil are: temperature 40°C, flow rate 7900kg / h, water content 0.4wt%. The parameters of the oil-poor water phase at the bottom of the tower are: temperature 40°C, flow rate 2100kg / h, oil content 2.4wt%.

[0086] Step (4) does not further separate organic matter from the bottom oil-poor water phase through a modified hydrophilic oleophobic membrane or a stripping tower. For a certain propylene oxide production process, the oil content in the bottom oil-poor water phase meets the requirements of subsequent processes, and the bottom oil-poor water phase with an oil content of 2.4 wt% is returned to the alkali washing process as a product water liquid for reuse.

[0087] Comparative Example 3 is an oil-water separation tank using an inclined plate coalescer for separation of organic matter and water. The separation effect is more than 20% lower than that of Example 3, and the residence time of the organic matter and water solution in the tank exceeds 40 minutes.

[0088] Through the above steps, the present invention can utilize the lipophilic and hydrophobic, hydrophilic and lipophobic properties of the modified filler to achieve the separation of insoluble, slightly soluble and soluble organic aqueous solutions, greatly reduce the separation energy consumption, and meet the low water content requirements of the product oil liquid and the low oil content requirements of the product water liquid.

[0089] The remaining technical features in this embodiment can be flexibly selected by those skilled in the art according to actual conditions to meet different specific practical needs. However, it is obvious to those of ordinary skill in the art that it is not necessary to adopt these specific details to implement the present invention. In other examples, in order to avoid confusing the present invention, the well-known components, structures or parts are not specifically described, all of which are within the technical protection scope defined by the technical solution claimed for protection in the claims of the present invention. The expression of the textual language (including the drawings) of the specification of the present invention does not constitute any single restrictive interpretation of the claims.

[0090] Modifications and changes made by those skilled in the art that do not depart from the spirit and scope of the present invention should be within the scope of protection of the claims attached to the present invention. In the above description, a large number of specific details are set forth in order to provide a thorough understanding of the present invention. However, it is obvious to those of ordinary skill in the art that these specific details are not necessary to practice the present invention. In other examples, in order to avoid confusing the present invention, well-known technologies, such as specific construction details, operating conditions and other technical conditions, are not specifically described.

Claims

1. A method for separating organic matter and water by using lipophilic and hydrophobic materials or hydrophilic and oleophobic materials, characterized in that: The following steps are involved: S1. Heat exchange and temperature adjustment of the organic aqueous solution to ensure that the temperature is greater than 3°C and lower than the temperature at which the organic matter reacts; S2, passing the temperature-adjusted organic aqueous solution into a modified packed tower for oil-water separation, obtaining an organic-rich oil phase at the top of the tower and an oil-poor aqueous phase at the bottom of the tower; S3, detecting the organic matter content in the oil-poor water phase obtained at the bottom of the tower in step S2: If the organic matter content in the oil-poor water phase is within the specified range, the oil-water separation is completed; If the organic matter content in the oil-lean water phase is not within the specified range, it is passed into a stripping tower to further remove the organic matter, and water liquid is obtained at the bottom of the tower; or the oil-lean water phase is filtered with a modified hydrophilic oleophobic membrane to obtain a product water liquid; or the oil-lean water phase is first filtered with a modified hydrophilic oleophobic membrane and then passed through a stripping tower to obtain a product water liquid.

2. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 1, characterized in that: Before step S1, the organic aqueous solution is first passed into a raw material pre-separator, and the raw material pre-separator is a combination of one or more of filter cake filtration, deep filtration, and centrifugal filtration.

3. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 1, characterized in that: In step S2, a modified packing section is arranged in the modified packing tower, and the lipophilic and hydrophobic modified packing is a packing surface on which non-polar substances such as oils and fats and / or waxes are introduced.

4. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 2, characterized in that: In step S2, the hydrophilic and oleophobic modified filler is to introduce hydroxyl and / or carboxyl polar groups on the surface of the filler.

5. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 1, characterized in that: In step S2, the filler material is one or a combination of ceramic, metal, plastic, quartz, and fruit shell.

6. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 1, characterized in that: In step S2, the water-in-oil (W / O) section in the modified packing tower uses oleophilic and hydrophobic modified packing, and the oil-in-water (O / W) section in the modified packing tower uses hydrophilic and oleophobic modified packing.

7. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 1, characterized in that: In step S2, when the content of soluble organic matter in the oil-poor water phase at the bottom of the modified packed tower is high, part of the top product oil liquid is returned to the inlet of the modified packed tower, and / or other oil phases are injected into the inlet of the modified packed tower as an extractant for soluble organic matter.

8. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 1, characterized in that: The modified packing separation tower of step S2 is optimized as follows: the hydrophilic oleophobic packing section has n layers, n≥1, the oleophilic hydrophobic packing section has m layers, m≥1, and the water-in-oil (W / O) oil phase in any section returns to the oleophilic hydrophobic packing layer through a return line, and / or the oil-in-water (O / W) water phase returns to the hydrophilic oleophobic packing layer through a return line.

9. The method for separating organic matter and water by using oleophilic and hydrophobic materials or hydrophilic and oleophobic materials according to claim 1, characterized in that: In step S3, the stripping tower uses a packing and / or a plate tower, and the packing uses a modified and / or non-modified packing.

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