A method for demulsification, dewatering, and resource recovery of oily sludge

Abstract

This invention discloses a method for demulsification, dewatering, and resource recovery of oily sludge. This invention relates to the field of hazardous waste treatment and resource utilization technology. The method involves adding a demulsifier containing CO2-responsive functional groups to the oily sludge. VOCs are driven out in the liquid phase reaction zone of an integrated reactor. The VOCs are oxidized to CO2 by a noble metal catalyst in the top gas phase catalytic zone. The CO2 is circulated into the liquid phase zone to activate the demulsifier, causing it to protonate and penetrate the oil-water interface film. After N2 removes the CO2, the demulsifier returns to its hydrophobic state and tears the interface film. Alternating cycles achieve a dewatering rate of not less than 85%. After demulsification, the sludge is separated by a three-phase horizontal screw centrifuge. The solid residue is then treated with a biodegradable amino acid chelating agent and low-frequency ultrasound to synergistically remove heavy metals before preparing geopolymer aggregate. This invention achieves in-situ elimination of VOCs and closed-loop demulsification, enabling the resource recovery of all components of the oily sludge without the secondary generation of hazardous waste.

Description

Technical Field

[0001] This invention relates to the field of hazardous waste treatment and resource utilization technology, specifically a method for demulsifying, dewatering, and recycling oily sludge. Background Technology

[0002] Oily sludge is a typical hazardous waste associated with the petroleum industry (HW08). It is essentially a highly stable three-phase emulsion system composed of crude oil, water and solid particles. In oily sludge, asphaltenes contain acidic functional groups (carboxyl groups, phenolic hydroxyl groups) and fused aromatic rings, which spontaneously adsorb at the oil-water interface and form a viscoelastic network interfacial film with high mechanical strength and self-healing ability through π-π stacking, hydrogen bonding and dipole interaction. Colloidal molecules, as synergistic components, further enhance the network structure, making the oily sludge system extremely stable and difficult to achieve efficient separation of oil, water, and solid phases through conventional methods.

[0003] Currently, the closest existing technology for treating oily sludge in industry is a combination of high-temperature hot washing, chemical demulsification, and centrifugal separation. This process involves adding hot water (80-95°C), traditional nonionic surfactants (such as polyoxyethylene-polyoxypropylene block copolymers), and inorganic acids to the oily sludge. After high-temperature stirring and conditioning, the sludge undergoes gravity sedimentation and is then separated into solid and liquid components by a horizontal screw centrifuge. Volatile organic compounds (VOCs) that are released are treated by end-of-pipe activated carbon adsorption devices or regenerative thermal incinerators. Solid mud cakes are usually disposed of through pyrolysis incineration or solidification and landfill. The equipment in these processes operates independently and there is no internal linkage mechanism.

[0004] The existing technology has the following three core defects: Firstly, the demulsification efficiency is low. Traditional nonionic surfactants have low molecular weight and weak polarity, which cannot effectively penetrate the dense three-dimensional network structure formed by the π-π accumulation of asphaltene. They must rely on high temperature (above 80℃) to soften the interface film as compensation. Even so, the demulsification and dehydration rate can only reach 60% to 75%, and the recovered oil has excessive solid content and poor quality.

[0005] Secondly, the fugitive emissions of VOCs cause serious secondary pollution. The high-temperature hot washing process directly drives a large amount of highly toxic VOCs such as benzene series compounds (BTEX) and hydrogen sulfide to escape from the sludge in an unorganized manner. After the end activated carbon adsorption device is saturated, it itself becomes a new hazardous waste. Incineration generates secondary pollutants such as nitrogen oxides. The pipeline collection system has the risk of leakage, forming a vicious cycle of "pollution control and pollution generation", which cannot solve the VOCs pollution problem at the source.

[0006] Third, the resource utilization rate of solid residue is extremely low. The solid residue after demulsification and separation is enriched with high concentrations of heavy metals (Ni, V, Cr, etc.) and residual organic matter. Existing pyrolysis or solidification landfill methods cannot simultaneously achieve the degradation of organic matter and the safe stripping of heavy metals. The risk of heavy metal leaching toxicity persists, and the solid residue cannot be used as a qualified aggregate for resource utilization. The goal of full component resource utilization is difficult to achieve. Summary of the Invention

[0007] I. Purpose of the Invention The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for demulsification, dewatering and resource recovery of oily sludge and its integrated reactor, so as to achieve synergistic effects of low-temperature and high-efficiency demulsification, in-situ elimination of VOCs and resource recovery of all components.

[0008] II. Technical Solution To achieve the above objectives, the present invention provides the following technical solution: A method for demulsifying, dewatering, and recycling oily sludge includes the following steps: A demulsifier containing CO2-responsive functional groups is added to the oily sludge. The mixture is then fed into the liquid phase reaction zone of an integrated reactor and stirred at 40–60°C. This allows the volatile organic compounds in the oily sludge to escape from the liquid phase to the gas phase space of the reactor under heat. The volatile organic compounds that escape rise to the gas-phase catalytic zone at the top of the integrated reactor, where they are catalytically oxidized to CO2 at 200–300°C under the action of a noble metal catalyst supported by a hydrophobic molecular sieve. The CO2 generated in the catalytic zone is collected and enriched in the gas-liquid buffer zone, and then pumped into the liquid phase reaction zone by the gas circulation pump and the gas distributor. This causes the CO2-responsive functional groups in the demulsifier to be protonated, and the demulsifier changes from a hydrophobic state to a hydrophilic state. The hydrophilic segments penetrate the oil-water interface film of the oily sludge. N2 is then introduced into the liquid phase reaction zone to remove CO2, causing the CO2-responsive functional groups of the demulsifier to be deprotonated, the demulsifier to return to its hydrophobic state, and the oil-water interface film to be torn apart. The CO2 blowing step and the N2 removal step are alternately repeated until the demulsification and dewatering rate of the oily sludge is not less than 85%. The demulsified material is separated by a three-phase horizontal screw centrifuge to obtain a recovered oil phase, an oily wastewater phase, and solid residue. The solid content of the recovered oil phase is less than 0.5%.

[0009] Furthermore, the method also includes a solid residue resource utilization step: adding the solid residue to a biodegradable amino acid chelating agent eluent with a liquid-to-solid ratio of 5-10 mL / g, simultaneously applying low-frequency ultrasound at a frequency of 20-40 kHz, and eluting at 30-50°C for 30-60 minutes. After elution and filtration, the filtrate containing heavy metal chelates is evaporated and crystallized to recover valuable metals; the inert solid residue is tested for heavy metal leaching toxicity and, after meeting the standards, is combined with alkali-activated materials to prepare geopolymer aggregate.

[0010] The present invention also provides an integrated reactor for implementing the above method, which is a vertical cylindrical structure and is provided with a gas phase catalytic zone, a gas-liquid buffer zone and a liquid phase reaction zone from top to bottom; The gas-phase catalytic zone has a built-in hydrophobic molecular sieve-supported noble metal catalyst bed and is equipped with an independent heating jacket, with an operating temperature of 200-300℃. A temperature-controlled heat insulation baffle is installed between the gas-phase catalytic zone and the liquid-phase reaction zone; The gas-liquid buffer zone is equipped with a gas-liquid separation device and a hydrophobic gas membrane separation component; The liquid phase reaction zone is equipped with a microbubble gas distributor, a stirring paddle and a temperature control device, with an operating temperature of 40-60℃. The gas circulation pump circulates the CO2 enriched in the gas-liquid buffer zone into the liquid phase reaction zone via a microbubble gas distributor.

[0011] III. Beneficial Effects 1. This invention constructs a closed-loop linkage mechanism of in-situ catalytic oxidation of VOCs-CO2 recycling-demulsifier activation, which converts the waste gas VOCs generated during the demulsification process into functional CO2 required to drive demulsification, thereby achieving waste treatment with waste and completely eliminating fugitive emissions of VOCs from the source. No additional end-of-pipe exhaust gas treatment device is required, thus solving the paradox of pollution treatment and pollution generation.

[0012] 2. This invention employs a breathing dynamic demulsification technology, which uses a CO2-responsive demulsifier to repeatedly switch between hydrophilic and hydrophobic states to cumulatively disrupt the asphaltene π-π deposition interface network. Compared with existing technologies, this invention achieves a demulsification and dehydration rate of no less than 85% and a recovered oil phase solid content of less than 0.5% at low temperatures of 40-60℃, which is significantly better than the 60%-75% dehydration rate of existing technologies and significantly reduces processing energy consumption.

[0013] 3. This invention employs a synergistic elution technology combining biodegradable amino acid chelating agents and low-frequency ultrasound. Compared with simple chemical elution, the heavy metal elution efficiency is increased by 30% to 50%. After treatment, the toxicity of heavy metal leaching in the solid residue meets the standards for use as building aggregates, realizing the full-component resource utilization of oily sludge without the secondary generation of hazardous waste. Attached Figure Description

[0014] Figure 1 This is a complete process flow diagram of the oily sludge demulsification, dewatering, and resource recovery method of the present invention; Figure 2 This is a schematic diagram of the synthesis route of the CO2-responsive hyperbranched polyether demulsifier of the present invention; Figure 3 This is a timing diagram of the breathing-type dynamic demulsification mechanism of the present invention; Figure 4 This is a process flow diagram of the solid residue heavy metal elution and building materialization process of the present invention; Figure 5 This is a diagram showing the overall structure of the system of the present invention. Detailed Implementation

[0015] The following is in conjunction with the appendix Figure 1 -Appendix Figure 5 The specific embodiments of the present invention will be further described below. It should be noted that the description of these embodiments is for the purpose of helping to understand the present invention, but does not constitute a limitation of the present invention.

[0016] Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0017] Example 1 1000 kg of oil sludge from the bottom of a tank in a chemical refining plant (oil content 35%, water content 45%, solid content 20%, Ni content 320 mg / kg, V content 580 mg / kg, Cr content 85 mg / kg) was taken as the treatment object.

[0018] Pretreatment stage: The oily sludge raw material is screened by a vibrating screen to remove impurities such as sand and gravel with a particle size greater than 10 mm. A CO2-responsive hyperbranched polyether demulsifier (with pentaerythritol as the core, the hyperbranched polyether skeleton is prepared by one-pot anionic ring-opening polymerization, and the end groups are introduced with N,N-dimethylaminoethyl acrylate functional groups containing tertiary amine groups through amidation reaction, with a number average molecular weight Mn of 10000 g / mol) is added to the pretreated sludge at a dosage of 1 g / L. The mixture is then fed into the liquid phase reaction zone (region C) of the integrated reactor. The temperature of the liquid phase reaction zone is set at 50℃ and the stirring speed is 90 rpm. At this temperature, VOCs such as benzene series compounds (BTEX) and hydrogen sulfide in the sludge are heated and vaporized, moving upward along the central axis of the reactor and entering the top gas phase catalytic zone (region A) through the gas-liquid buffer zone (region B).

[0019] Gas-phase catalytic oxidation stage: A Pt-Pd / ZSM-5 catalyst bed (75 mm thick, Pt loading 0.3 wt%, Pd loading 0.5 wt%) is built into the gas-phase catalytic zone. An independent heating sleeve maintains the temperature of this zone at 250℃. VOCs are completely catalytically oxidized on the catalyst surface. Taking benzene as an example, the catalytic oxidation reaction equation is: ; In the formula, It is a benzene molecule. For oxygen, Pt-Pd / ZSM-5 is a hydrophobic molecular sieve-supported noble metal catalyst. The catalytic oxidation product is carbon dioxide. The catalytic conversion rate of benzene compounds in water reaches over 99% at 250℃. The temperature-controlled heat insulation baffle effectively blocks the heat transfer from the high temperature (250℃) of the gas phase catalytic zone to the liquid phase reaction zone (50℃), ensuring independent operation of the two temperature zones.

[0020] CO2 enrichment and closed-loop recycling stage: The CO2 and H2O mixture generated in the catalytic zone flows downward to the gas-liquid buffer zone (region B), where excess water vapor is removed by a hydrophobic polytetrafluoroethylene (PTFE) gas membrane separation module (0.2 μm pore size), enriching CO2. The enriched CO2 is then recycled by a gas circulation pump (0.5 m³ / h) 3 / h) CO2 is bubbled into the oily sludge system in the liquid phase reaction zone through a bottom microbubble gas distributor (0.2mm aperture). CO2 dissolves in water to form carbonic acid, which promotes the protonation reaction of the tertiary amine groups at the end of the demulsifier. ; In the formula, It is the tertiary amine group in the demulsifier molecule. It is carbon dioxide. For water, It is a protonated tertiary ammonium ion. The demulsifier, being a bicarbonate ion, transforms from a hydrophobic coiled state to a hydrophilic extended state after protonation. The pH of the sludge slurry in the liquid phase reaction zone drops from the initial 7.5 to 6.2, reaching the target range (6.0-6.5) required for the full protonation of the tertiary amine group. The hydrophilic segments then penetrate the weak gaps in the asphaltene π-π stacking network and embed themselves inside the oil-water interface film. The CO2 bubbling stage lasts for 6 minutes.

[0021] Then, the CO2 injection was stopped, and N2 (99% purity, flow rate 0.3 m³ / h) was introduced into the liquid phase reaction zone. 3 (h) Bubbling for 5 minutes to remove CO2, resulting in a reversible deprotonation reaction: ; In the formula, It is a protonated tertiary ammonium ion. It is a bicarbonate ion. To restore the hydrophobic tertiary amine group, For the escape of gas, After CO2 removal, the pH of the liquid phase reaction zone rises to 7.2. The demulsifier returns to its hydrophobic coil state, and the molecular chain contraction generates hydrophobic contraction force, which is like molecular tweezers clamping and tearing the asphaltene network nodes, leaving irreversible cracks on the interface film. The N2 removal stage lasts for 5 minutes.

[0022] The above-mentioned CO2 induction and N2 removal steps are alternated and cycled, with each cycle lasting about 12 minutes. The turbidity of the liquid phase is monitored in real time by an online turbidity meter. After 8 cycles, the turbidity change rate of the liquid phase is less than 5% for 3 consecutive cycles. The system determines that the demulsification has achieved the target and the demulsification and dewatering rate of the oily sludge reaches 88%. The system then enters the three-phase separation stage. Throughout the demulsification process, the pressure difference between the two sides of the hydrophobic membrane separation component in the gas-liquid buffer zone remains below 15 kPa, and the CO2 enrichment efficiency is stable.

[0023] Three-phase separation stage: The demulsified material enters a three-phase horizontal screw centrifuge with a speed set at 2500 rpm. It is separated into an upper layer of recovered oil phase (containing 0.3% solids, meeting the standard for direct recycling), a middle layer of oily wastewater phase (treated by the wastewater treatment unit to meet discharge standards), and a bottom layer of solid residue (containing approximately 20% water).

[0024] Solid residue resource utilization stage: The bottom solid residue (after concentration, Ni content reaches 1200 mg / kg, V content 2100 mg / kg, and Cr content 320 mg / kg) was subjected to heavy metal elution treatment. First, the total amount of Ni, V, and Cr in the solid residue was detected by X-ray fluorescence spectroscopy (XRF). The required concentration of N,N-dicarboxymethyl glutamate tetrasodium (GLDA) eluent was calculated according to the following formula: ; In the formula, The concentration of GLDA eluent is expressed in mol / L. For the first The chelation molar ratio of heavy metals with GLDA, Ni 2+ Take 1.2, V 3+ Take 1.2, Cr 3+ Use a value of 1.5 (a coefficient greater than 1 to ensure sufficient excess of chelating agent). The first in solid slag The total amount of each heavy metal, expressed in mg / kg. The mass of the solid residue used in elution is expressed in kg. For the first Molar mass of each heavy metal, in g / mol (Ni: 58.69, V: 50.94, Cr: 52.00). The volume of the eluent is in liters (L). This represents the summation of calculations performed separately for the three target heavy metals Ni, V, and Cr. The concentration should be controlled within the range of 0.05–0.2 mol / L. If the calculated value exceeds the upper limit, it should be adjusted by increasing the liquid-to-solid ratio.

[0025] In this embodiment, the calculated concentration of GLDA eluent was 0.12 mol / L. The initial pH of the eluent was adjusted to 7.0 using dilute NaOH solution, and the liquid-to-solid ratio was set to 8 mL / g. After adding the solid residue to the eluent, the low-frequency ultrasonic generator was started, with the ultrasonic frequency set to 30 kHz and the power density to 75 W / L. The temperature control device maintained the system temperature at 40°C, and the elution time was 45 minutes. The cavitation effect generated by the low-frequency ultrasound formed strong microjets and shock waves at the solid-liquid interface, which destroyed the co-precipitation bond between heavy metals and mineral particles, significantly increasing the desorption rate of heavy metals. The simultaneously released heavy metal ions rapidly formed stable water-soluble chelates with GLDA, preventing the heavy metals from being re-adsorbed back onto the solid surface.

[0026] After elution, the solution was filtered through a 0.45 μm pore size filter membrane. The heavy metal chelate solution in the filtrate was then recovered by evaporation and crystallization to recover Ni. 2+ V 3+ Valuable metals and inert solid residues were subjected to leaching toxicity testing according to the "Solid Waste Leaching Toxicity Leaching Method - Sulfuric Acid and Nitric Acid Method" (HJ / T299). The results showed that Ni... 2+ The leaching concentration was 0.8 mg / L (below the limit of 5 mg / L), the V leaching concentration was 0.1 mg / L (below the limit of 0.5 mg / L according to EU standards), and the total Cr leaching concentration was 1.2 mg / L (below the limit of 15 mg / L). 6+ No detectable, all meet the standards.

[0027] The qualified solid residue is mixed with fly ash (mass ratio 1:1) and slag (mass ratio 1:0.5), and then geopolymer aggregate is prepared by water glass alkali activation. The compressive strength reaches 42 MPa after 28 days, which meets the requirements for building materials.

[0028] The entire treatment process ultimately achieves the resource utilization of all components of oily sludge: 310 kg of crude oil (containing 0.3% solids) is recovered, the recovery rate of valuable heavy metals (Ni, V) reaches more than 85%, 210 kg of geopolymer aggregate (meets standards) is produced, and 450 L of treated water meets standards. No secondary hazardous waste is generated throughout the entire process.

[0029] Example 2 Aged sludge from the bottom of an oilfield tank (oil content 28%, water content 50%, solid content 22%) was used as the treatment target. The demulsifier dosage was adjusted to 1.5 g / L, the liquid phase reaction zone temperature was set to 55℃, the gas phase catalytic zone temperature was set to 260℃, the CO2 blowing stage lasted for 7 minutes, and the N2 removal stage lasted for 6 minutes. After 10 demulsification cycles, the demulsification and dehydration rate reached 86%, and the recovered oil phase solid content was 0.4%. The solid residue was treated with GLDA eluent (concentration 0.10 mol / L, initial pH 6.5, liquid-to-solid ratio 10 mL / g) and low-frequency ultrasound (frequency 25 kHz, power density 60 W / L, temperature 35℃, elution time 50 minutes). The heavy metal leaching toxicity all met the standards. The solid residue was used for co-processing in a cement kiln, realizing the resource utilization of building materials.

[0030] Comparative Example An existing high-temperature hot washing-chemical demulsification-centrifugal separation process was used to treat oily sludge from the same source: hot washing temperature was 90℃, a nonionic surfactant of polyoxyethylene-polyoxypropylene block copolymer was added, the horizontal screw centrifuge speed was 3000 rpm, and VOCs were treated at the end of the process by an activated carbon adsorption device. The results showed that the demulsification and dewatering rate was only 68%, the solid content of the recovered oil was 1.8%, and the fugitive emission concentration of VOCs (calculated as benzene) reached 45 mg / m³. 3 The emissions exceeded the relevant emission standards, and the leaching toxicity of heavy metals in the solid residue exceeded the standards. It can only be disposed of as hazardous waste through landfill. Each ton of sludge produces 2.5 kg of activated carbon saturated waste, forming new hazardous waste.

[0031] Compared with the comparative example, the demulsification and dehydration rate of Example 1 of the present invention is increased by about 20 percentage points, VOCs are completely eliminated in situ, all solid residues are utilized as resources, and no hazardous waste is generated in the entire process, which fully verifies the advanced nature and effectiveness of the technical solution of the present invention.

[0032] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make possible changes and modifications without departing from the spirit and scope of the present invention. Therefore, any modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention shall fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for demulsifying, dewatering, and recycling oily sludge, characterized in that, Includes the following steps: A demulsifier containing CO2-responsive functional groups is added to the oily sludge. The mixture is then fed into the liquid phase reaction zone of an integrated reactor and stirred at 40–60°C. This allows the volatile organic compounds in the oily sludge to escape from the liquid phase to the gas phase space of the reactor under heat. The volatile organic compounds that escape rise to the gas-phase catalytic zone at the top of the integrated reactor and are catalytically oxidized to CO2 at 200–300°C under the action of a noble metal catalyst supported on a hydrophobic molecular sieve. The CO2 generated in the catalytic zone is collected and enriched in the gas-liquid buffer zone, and then blown into the liquid phase reaction zone by the gas circulation pump through the gas distributor. This causes the CO2-responsive functional groups in the demulsifier to be protonated, and the demulsifier changes from a hydrophobic state to a hydrophilic state. The hydrophilic segments penetrate the oil-water interface film of the oily sludge. N2 is then introduced into the liquid phase reaction zone to remove CO2, causing the CO2-responsive functional groups of the demulsifier to be deprotonated, the demulsifier to return to its hydrophobic state, and the oil-water interface film to be torn apart. The CO2 induction step and the N2 removal step are alternately repeated; The demulsified material is separated by a three-phase horizontal screw centrifuge to obtain the recovered oil phase, oily wastewater phase, and solid residue.

2. The method according to claim 1, characterized in that, It also includes a solid residue resource utilization step: the solid residue is added to a biodegradable amino acid chelating agent eluent with a liquid-to-solid ratio of 5-10 mL / g, and low-frequency ultrasound at a frequency of 20-40 kHz is applied simultaneously for elution at 30-50℃ for 30-60 minutes; after elution, the residue is filtered and separated, and the filtrate containing heavy metal chelates is evaporated and crystallized to recover valuable metals; after the inert solid residue passes the heavy metal leaching toxicity test, it is combined with alkali-activated materials to prepare geopolymer aggregate.

3. The method according to claim 1, characterized in that, The demulsifier containing CO2-responsive functional groups is a hyperbranched polyether demulsifier with polyol as the core, the end group contains tertiary amine groups, the number average molecular weight is 5000-20000 g / mol, and the amount added to oily sludge is 0.5-2 g / L.

4. The method according to claim 1, characterized in that, The hydrophobic molecular sieve supported noble metal catalyst is a catalyst with hydrophobic ZSM-5 zeolite molecular sieve as support and platinum and palladium dual active components supported.

5. The method according to claim 1, characterized in that, During the CO2 induction step, the pH of the sludge slurry in the liquid phase reaction zone drops to 6.0-6.5; during the N2 removal step, the pH of the sludge slurry in the liquid phase reaction zone rises back to above 7.

0. Each complete cycle of CO2 injection and N2 removal takes 10 to 15 minutes.

6. The method according to claim 1, characterized in that, A pretreatment step is also included before the mixture is fed into the liquid phase reaction zone: The oily sludge is screened by a vibrating screen to remove impurities with a particle size greater than 10 mm; The separation speed of the three-phase horizontal screw centrifuge is 2000-3000 rpm.

7. The method according to claim 2, characterized in that, The biodegradable amino acid chelating agent is tetrasodium N,N-dicarboxymethyl glutamate, with an eluent concentration of 0.05–0.2 mol / L and an initial pH of 6.0–8.

0.

8. The method according to claim 2, characterized in that, The power density of the low-frequency ultrasound is 50–100 W / L; the biodegradable amino acid chelating agent and Ni in the solid residue 2+ The chelation molar ratio is 1.2:1, with V 3+ The chelation molar ratio is 1.2:1, with Cr 3+ The chelation molar ratio is 1.5:

1.

9. An integrated reactor for use in the method of claim 1, characterized in that, It has a vertical cylindrical structure, and from top to bottom, it is provided with a gas phase catalytic zone, a gas-liquid buffer zone and a liquid phase reaction zone; The gas-phase catalytic zone contains a hydrophobic molecular sieve-supported noble metal catalyst bed and is equipped with an independent heating sleeve, with an operating temperature of 200-300℃. A temperature-controlled heat insulation baffle is provided between the gas-phase catalytic zone and the liquid-phase reaction zone; The gas-liquid buffer zone is equipped with a gas-liquid separation device and a hydrophobic gas membrane separation component for collecting and enriching CO2 generated in the gas-phase catalytic zone; The liquid phase reaction zone is equipped with a microbubble gas distributor, a stirring paddle and a temperature control device, and the working temperature is 40-60℃. The integrated reactor also includes a gas circulation pump, which circulates the CO2 enriched in the gas-liquid buffer zone into the liquid phase reaction zone via the microbubble gas distributor.

10. The integrated reactor according to claim 9, characterized in that, It also includes an online monitoring module, which includes a VOCs concentration sensor located at the inlet of the gas phase catalytic zone, a CO2 concentration sensor located at the outlet of the gas phase catalytic zone, a pH probe and a turbidity meter located in the liquid phase reaction zone, and pressure sensors located on both sides of the hydrophobic gas membrane separation component in the gas-liquid buffer zone.

Images