CN111253032A - Device and process for harmless treatment of waste oil-based mud - Google Patents
Device and process for harmless treatment of waste oil-based mud Download PDFInfo
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- CN111253032A CN111253032A CN202010165943.5A CN202010165943A CN111253032A CN 111253032 A CN111253032 A CN 111253032A CN 202010165943 A CN202010165943 A CN 202010165943A CN 111253032 A CN111253032 A CN 111253032A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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Abstract
The invention relates to waste oil-based mud treatment, in particular to a device and a process for harmless treatment of waste oil-based mud. The device comprises a feeding grinding device, a homogenizing tank, a mortar pump, a fine grinding device, a slurry intermediate storage tank, a high-pressure slurry pump, a pressure regulation and control system, a heat exchanger, an auxiliary heater, a hydrothermal oxidation reactor, a centrifugal machine, a water storage tank and a water pump which are sequentially connected through a pipeline; the hydrothermal decomposition oxidation reactor comprises a hydrothermal decomposition section and a water oxidation section; the hydrothermal decomposition section and the water oxidation section respectively comprise at least one tubular reactor; the starting end of the water oxidation section is provided with an oxidant inlet; the oxidant inlet is connected with an oxidant manufacturing device through a pipeline. The device is used for treating the waste oil-based mud, has low energy consumption, does not need chemical agents, does not generate gas leakage, can continuously treat the waste oil-based mud, and does not have secondary pollution.
Description
Technical Field
The invention relates to the technical field of harmless treatment of waste oil-based mud generated in the oil and gas drilling and exploitation process, in particular to a device and a process for harmless treatment of waste oil-based mud.
Background
At present, in the process of oil and gas drilling and development, oil-based mud is widely applied to the process of exploiting deep wells, ultra-deep wells, horizontal wells and shale gas. Base containing a large amount of mineral oil in oil-based mudOils, including diesel, white oil, or other synthetic mineral oils. Along with mud circulation in the drilling process, a large amount of waste oil-based mud and oil-containing drill cuttings are generated, and the single-well yield is about 400m3-800m3. The waste oil-based mud is a mixture of drilling fluid, rock debris and dirty oil, is a relatively stable colloidal suspension system, contains a large amount of chemical treatment agents, dirty oil, rock debris and the like, and main pollutants such as petroleum, salts, heavy metals and the like, wherein organic matters are derived from base oil and various organic additives for preparing the drilling fluid, and the main components are alkane, polycyclic aromatic hydrocarbon, benzene series and olefin.
In 2016, China issued a new "Ministry of hazardous waste", wherein in "HW 08 waste mineral oil and mineral oil-containing waste", it was specified that "mineral oil as continuous phase was used to set drilling mud for waste drilling mud generated in oil exploitation" (071-.
At present, the main treatment methods of the waste oil-based drilling fluid comprise: pyrolysis method, incineration method, conventional extraction method and supercritical CO2Extraction, chemical hot washing-mechanical dewatering, microbiological methods, etc. Wherein, the pyrolysis method has high operation temperature, large heat consumption, high energy consumption and large equipment investment. In the burning method, expensive oil base, main milk, auxiliary milk and other slurry additives cannot be recovered due to high temperature, so that a large amount of resources are wasted, and meanwhile, the flue gas discharged by burning contains sulfide, heavy metal and dioxin, so that secondary pollution is serious. Environmental protection departments in Sichuan, Chongqing and the like clearly stipulate that the waste oil-based mud is not treated by adopting an incineration method. The extraction method has the defects of high cost of an extractant, need of adding extractant recovery equipment, large equipment investment, complex process control and the like. Supercritical CO2The extraction method can only be operated intermittently at present, heavy hydrocarbons can be subjected to condensation coking at high temperature in a laboratory research and development stage and a pyrolysis process, oil loss is large, and the performance of a chemical additive in the drilling fluid can be easily damaged due to overhigh temperature, so that the drilling fluid can not be recycled. Biological method byThe oil-based mud contains organic matters which are difficult to biodegrade, such as polycyclic aromatic hydrocarbon and the like, so that the biodegradation difficulty and the environmental risk are high, and the consumed time is long.
Therefore, for the waste oil-based mud generated in the oil and gas drilling and exploitation process, a method which is reasonable in technology, free of secondary pollution, economical and effective to carry out harmless treatment is urgently needed to be developed, so that the waste oil-based mud meets increasingly strict environmental protection requirements.
Disclosure of Invention
The invention provides a continuous harmless treatment device for waste oil-based mud based on a hydrothermal oxidation technology, and solves the problems that the existing treatment method is easy to generate secondary pollution (such as a burning method), large in energy consumption (a pyrolysis method, and easy to generate gas leakage), long in period (a microbiological method), and incapable of continuously producing (supercritical CO)2Extraction), use of a large amount of chemical agents (chemical hot washing), and the like.
On one hand, the invention provides a harmless treatment device for waste oil-based mud, which is characterized in that: the device comprises a feeding grinding device 1, a homogenizing tank 2, a mortar pump 3, a fine grinding device 4, a slurry intermediate storage tank 5, a high-pressure slurry pump 6, a pressure regulation and control system 7, a heat exchanger 8, an auxiliary heater 9, a hydrothermal decomposition and oxidation reactor 10, a centrifuge 11, a water storage tank 12 and a water pump 13 which are sequentially connected through a pipeline; a discharge hole of the hydrothermal decomposition and oxidation reactor 10 is connected with a hot material inlet of the heat exchanger 8, and a hot material outlet of the heat exchanger 8 is connected with a feed hole of the centrifuge 11; the water outlet of the water pump 13 is connected with the water inlet of the homogenizing tank 2; the hydrothermal oxidation reactor 10 comprises a hydrothermal decomposition section and a water oxidation section; the hydrothermolysis section comprises at least one tubular reactor, and the water oxidation section comprises at least one tubular reactor; the starting end of the water oxidation section is provided with an oxidant inlet 14; an oxidizing agent producing device 15; the oxidant inlet 14 is connected to the oxidant producing device 15 through a pipe.
The innocent treatment device can be divided into a pretreatment unit (a feeding grinding device 1, a homogenizing tank 2, a mortar pump 3 and a fine grinding device 4), a temperature and pressure regulation and control unit (a pressure regulation and control system 7 and an auxiliary heater 9), a hydrothermal decomposition and oxidation treatment unit (a hydrothermal decomposition and oxidation reactor 10), an oxidant manufacturing unit (an oxidant manufacturing device 15) and a heat recovery unit (a heat exchanger 8). The device utilizes hydrothermal oxidation technology to carry out continuous type to abandonment oil base mud (drill chip), and its theory of operation is as follows:
slurry pretreatment: the solid phase of the waste oil-based mud generated after being recovered by the drilling mud recovery system is crushed and ground by the feeding grinding device 1, and then enters the homogenizing tank 2 to be homogenized by adding water (which can be sewage generated in the drilling process). The homogenized material is conveyed to a fine grinding device 4 through a mortar pump 3, particles are further ground to be finer, pretreated slurry is obtained, and the pretreated slurry enters a slurry intermediate storage tank 5. The pre-treated slurry is then delivered by a high pressure slurry pump 6 to a pressure regulation system 7 for pressure regulation.
Heating the slurry: at initial start-up, the slurry is heated by the auxiliary heater 9. After the operation is stable, the slurry is heated by the heat exchanger 8, and insufficient heat heated by the heat exchanger is supplemented by the auxiliary heater 9, so that the preheated slurry is obtained.
Hydrothermal oxidation reaction: the preheated slurry enters a hydrothermal oxidation reactor 10 with certain temperature (150-300 ℃) and pressure (5-20 MPa). The hydrothermally oxidizing reactor 10 includes two sections, a hydrothermally decomposing section and a hydrothermally oxidizing section. The main functions of the hydrothermolysis stage include: (1) dissolving organic matters on the surface of solid-phase particles, (2) converting macromolecular organic matters into micromolecular organic matters, and (3) stably solidifying heavy metals. The hydrothermal oxidation section carries out oxidative decomposition on organic matters dissolved in water under the condition of adding an oxidant (preferably oxygen or oxygen-enriched air) and generates a large amount of heat.
And (3) heat recovery: the material after the oxidation in the hydrothermal oxidation section enters a heat exchanger 8, and heat is recovered by the heat exchanger 8 and used for heating the pretreatment slurry. The invention utilizes the heat released by the hydrothermal oxidation reaction to heat the import material of the hydrothermal hydrolysis oxidation reactor 10, thereby realizing heat balance. The whole treatment device does not need to additionally increase a heat source in the normal operation process, and the process operation cost is reduced.
Solid-liquid separation: the oxidized material is subjected to heat recovery by a heat exchanger 8, then enters a centrifuge 11 for solid-liquid separation, and the separated water enters a water storage tank 12 and is conveyed to a homogenizing tank 2 by a water pump 13.
According to the invention, the hydro-thermal oxidation reactor 10 is adopted for carrying out hydro-thermal oxidation on the pretreated oil-based mud at a lower temperature (120-300 ℃) for the first time. Under the conditions that the temperature of water is 150-300 ℃ and the pressure is 5-20 MPa, the water is called as near-critical water or subcritical water (the critical state of the water is that the temperature is more than 374 ℃ and the pressure is more than 22MPa), the water has more excellent properties than normal-temperature normal-pressure water in the near-critical state, and the characteristics of large ionization constant and small dielectric constant enable the water to have the acid-base catalysis function and the characteristic of dissolving organic matters. These characteristics make subcritical water useful as both a catalyst for organic chemical reactions and as a reactant and solvent. In the stage of hydrothermolysis, organic matters in the oil-based mud (oil-based drilling cuttings), mainly macromolecular organic matters consisting of alkane, epoxy alkane, polycyclic aromatic hydrocarbon (benzene series and derivatives thereof), aldehydes and the like, are converted into micromolecular organic matters and dissolved into subcritical water; meanwhile, part of organic matters can generate organic carbon through anaerobic pyrolysis and remain on the surface of solid particles, so that the stable solidification effect of heavy metals is enhanced. In the hydrothermal oxidation stage, the material after hydrothermal decomposition is subjected to hydrothermal oxidation reaction under the condition of adding an oxidant (for example, introducing oxygen or oxygen-enriched air), so that organic components (mainly dissolved in subcritical water) in the material are converted into water and carbon dioxide, and simultaneously, a large amount of heat is released.
In a preferred embodiment of the invention, the tubular reactor comprises a tubular body 16 and a stirring device 17; a feed inlet and a discharge outlet are respectively arranged at two ends of the pipe body 16; the discharge hole of the tubular reactor at the tail end of the hydrothermal section is connected with the feed hole of the tubular reactor at the starting end of the water oxidation section; the oxidant inlet 14 is located near the feed inlet of the tubular reactor at the beginning of the water oxidation stage.
The hydrothermal oxidation reactor 10 can be configured to have reaction times of the hydrothermal oxidation section and the hydrothermal hydrolysis section or a volume of the reactor according to the amount of the material to be treated and the properties of the material. The tubular reactors with stirring devices are preferably adopted in the hydrothermal decomposition section and the hydrothermal oxidation section, so that the heat transfer effect of materials in the reactors and the mass transfer effect of the materials and the oxygen-enriched air are enhanced, the continuous operation is conveniently realized, the point-by-point oxygen supply mode is conveniently adopted, and the consumption of oxygen is saved.
In some embodiments of the present invention, the stirring device 17 comprises a stirring shaft 18 extending into the pipe body 16, and the stirring shaft 18 is uniformly provided with halved paddles 19.
In a preferred embodiment of the invention, the hydrothermolysis stage comprises two or more tubular reactors, and the water oxidation stage comprises two or more tubular reactors; the two or more tubular reactors are connected end to end through the feed inlets and the discharge outlets at the two ends of the tube body 16.
In some embodiments of the present invention, the discharge port of the fine grinding device 4 is respectively connected with the slurry intermediate storage tank 5 and the homogenizing tank 2; the centrifuge 11 is provided with a feed inlet, a water outlet and a solid phase discharge outlet, and the water outlet of the centrifuge 11 is connected with the water storage tank 12.
In a preferred embodiment of the invention, said heat exchanger 8 is a double pipe heat exchanger; the oxidizing agent production apparatus 15 is an oxygen-enriched air production apparatus. The heat recovery preferably employs a double pipe heat exchanger capable of withstanding a certain pressure and temperature, depending on the characteristics of the outlet material of the hydrothermolysis oxidation reactor 10 containing a solid phase. The double-pipe heat exchanger is one kind of pipe heat exchanger, and has two kinds of standard pipes in different sizes connected to form one concentric sleeve, the outer shell side and the inner pipe side. The two different media can flow in the shell side and the tube side in the opposite directions (or in the same direction) to achieve the effect of heat exchange. And the two ends of the tube side of the double-tube heat exchanger are respectively provided with a cold material inlet and a cold material outlet, and the two ends of the shell side of the double-tube heat exchanger are respectively provided with a hot material inlet and a hot material outlet. The cold material inlet and the cold material outlet are respectively connected with the pressure regulating system 7 and the auxiliary heater 9; the hot material inlet and the hot material outlet are respectively connected with the hydrothermal decomposition oxidation reactor 10 and the centrifuge 11. The oxidant producing device 15 preferably uses oxygen-enriched air (oxygen content is 90-95%) produced by oxygen-enriched air producing equipment as an oxidant for a harmless treatment process.
In a preferred embodiment of the invention, the harmless treatment device for the waste oil-based mud is of a skid type. Specifically, the functional components of the innocent treatment device are integrated on the integrated base, so that the innocent treatment device can be integrally installed and moved, the field installation workload is low, and the operation can be realized only by completing the connection of an interface pipeline and external electric connection.
The skid-mounted continuous waste oil-based mud harmless treatment device based on the hydrothermal oxidation technology provides a clear and practicable process route for oil-based mud harmless treatment, and is suitable for single-well or centralized station building treatment and land and offshore drilling platforms.
The application of any one of the devices in the harmless treatment of the waste oil-based mud also belongs to the protection scope of the invention.
On the other hand, the invention also provides a harmless treatment process for the waste oil-based mud, which is characterized in that any one device is adopted to treat the waste oil-based mud, and the harmless treatment process comprises the following steps:
s1, pretreatment: recovering the solid phase of the oil-based mud, and carrying out coarse grinding, water adding homogenization and fine grinding on the solid phase of the mud to obtain pretreated mud;
s2, heating: during initial operation, the pre-treated slurry is heated by the auxiliary heater 9; after the operation is stable, the pretreated slurry is heated by a heat exchanger 8 to obtain preheated slurry;
s3, hydrothermal oxidation reaction: the preheated slurry enters a hydrothermal decomposition section of a hydrothermal decomposition oxidation reactor 10, and is subjected to pyrolysis at the temperature of 150-350 ℃ and under the pressure of 5-20 MPa; the pyrolysis product enters a hydrothermal oxidation section of a hydrothermal pyrolysis oxidation reactor 10, an oxidant is introduced into the hydrothermal oxidation section through an oxidant manufacturing device 15, and oxidation reaction is carried out at the temperature of 150-350 ℃ and under the pressure of 5-20 MPa, so that an oxidation product is obtained;
s4, heat recovery: the oxidation product heats the pretreated slurry through a heat exchanger 8;
s5, solid-liquid separation: the oxidation product after heat exchange enters a centrifuge 11 for solid-liquid separation, and the separated water enters a water storage tank 12 and is conveyed to the homogenizing tank 2 through a water pump 13.
In the preferred embodiment of the present invention, in the step S1, the slurry solid phase enters the feed grinding device 1 and is ground into particles with a particle size of less than 5 mm; then the mixture enters a homogenizing tank 2, water is added to adjust the mixture into slurry with the liquid content of 87-90 percent, and the slurry is fully and uniformly stirred; then the mixture is conveyed into a fine grinding device 4 through a mortar pump 3 and is further ground into particles with the particle size smaller than 1 mm; the finely ground slurry is partly returned to the homogenization tank 2 and partly to the intermediate slurry storage tank 5.
In the preferred embodiment of the invention, in the step S2, when the heat provided by the heat exchanger 8 is insufficient, the auxiliary heater 9 is used for supplementing heat to heat the pretreated slurry to 250-300 ℃; in the step S3, keeping the pressure of the hydrothermal decomposition section at 10-20 MPa, and allowing the slurry to stay in the hydrothermal decomposition section for 30-60 minutes to obtain a pyrolysis product; keeping the pressure of the hydrothermal oxidation section at 10-20 MPa, introducing oxygen or oxygen-enriched air, keeping the peroxide coefficient at 1.2-2.0, and allowing the pyrolysis product to stay in the hydrothermal oxidation section for 30-60 minutes to obtain an oxidation product.
The harmless treatment process comprises the steps of slurry pretreatment, slurry heating, hydrothermal oxidation reaction, heat recovery and solid-liquid separation. In the pretreatment stage, the solid phase generated after the oil-based mud (oil-based drilling cuttings) is dried and recovered is subjected to coarse grinding, water adding homogenization (preferably to obtain mud with the liquid content of 90 percent) and fine grinding to obtain mud with fine particles (the particle size is preferably less than 1 mm). In the heating stage, when the initial start-up, the pretreated slurry is heated by an auxiliary heater 9; after the operation is stable, the pretreated slurry is heated by the heat exchanger 8, so that the temperature of the slurry is increased to 250-300 ℃, and the preheated slurry is obtained. In the hydrothermal oxidation stage, the preheated slurry firstly enters a hydrothermal section of a hydrothermal oxidation reactor 10, and macromolecular organic matters in subcritical water (under the conditions of high temperature and high pressure, water is heated to a temperature higher than a boiling point and lower than a critical point, the pressure of a system is controlled to keep the water in a liquid state, and the water in the state is called critical water) dissolved in organic matters on the surfaces of material particles are converted into micromolecular organic matters, and meanwhile, heavy metals are stably solidified; the pyrolyzed material is then fed into the hydrothermal oxidation section of the hydrothermal oxidation reactor 10, and the hydrothermal oxidation process converts the organic matter in the water into water and carbon dioxide in the subcritical state of the water under the condition of introducing an oxidant (preferably oxygen or oxygen-enriched air) and simultaneously generates a large amount of heat. The heat generated in the oxidation process is exchanged by the heat exchanger 8, so that the temperature of the pretreated slurry is raised to 250-300 ℃ before the pretreated slurry enters the water pyrolysis oxidation reactor 10.
Compared with the prior treatment process, the process has the following advantages:
(1) the whole reaction is carried out in a closed reactor and the medium of the reaction is subcritical water, so that gas pollution caused by a traditional incineration method and gas leakage caused by a traditional pyrolysis method are avoided.
(2) The hydrothermal decomposition section is favorable for rapid proceeding of subsequent oxidation reaction, and can play a role in stably solidifying heavy metal (compared with the traditional incineration method, a solidifying agent needs to be added).
(3) A large amount of heat released by hydrothermal oxidation reaction is directly recycled, heat balance of the whole system can be realized, an external heating source is not needed after operation is stable, and operation cost is reduced. The traditional pyrolysis method needs continuous heat supply (such as fuel oil, gas or electromagnetic heating) to keep high temperature (500-650 ℃).
(4) The low-temperature operation is adopted, the operation temperature is generally 150-350 ℃, and the high-temperature operation is adopted in the traditional pyrolysis furnace and is generally 500-650 ℃.
(5) The sewage generated in the well site can be treated simultaneously, and the whole treatment process does not need to add any chemical agent, thereby realizing green production.
Drawings
FIG. 1: the waste oil-based mud innocent treatment device in the exemplary embodiment of the invention;
FIG. 2: a tubular hydrothermally oxidizing reactor in an exemplary embodiment of the present invention;
reference numerals: 1-feeding grinding device, 2-homogenizing tank, 3-mortar pump, 4-fine grinding device, 5-slurry intermediate storage tank, 6-high pressure slurry pump, 7-pressure regulation system, 8-heat exchanger, 9-auxiliary heater, 10-hydrothermal decomposition and oxidation reactor (A + B section is hydrothermal decomposition section, C + D section is hydrothermal oxidation section), 11-centrifuge, 12-water storage tank, 13-water pump, 14-oxidant inlet, 15-oxidant manufacturing device, 16-tube body, 17-stirring device, 18-stirring shaft and 19-halving paddle.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples. The following examples are given by way of illustration and description of the present invention and are not intended to limit the scope of the present invention.
As shown in fig. 1, the harmless treatment device for waste oil-based mud provided by the invention comprises a feeding grinding device 1, a homogenizing tank 2, a mortar pump 3, a fine grinding device 4, a mud intermediate storage tank 5, a high-pressure mud pump 6, a pressure regulation and control system 7, a heat exchanger 8, an auxiliary heater 9, a hydrothermal oxidation reactor 10, a centrifuge 11, a water storage tank 12 and a water pump 13 which are sequentially connected through a pipeline; a discharge hole of the hydrothermal decomposition and oxidation reactor 10 is connected with a hot material inlet of the heat exchanger 8, and a hot material outlet of the heat exchanger 8 is connected with a feed hole of the centrifuge 11; the water outlet of the water pump 13 is connected with the water inlet of the homogenizing tank 2; the hydrothermal oxidation reactor 10 comprises a hydrothermal decomposition section and a water oxidation section; the hydrothermolysis section comprises at least one tubular reactor, and the water oxidation section comprises at least one tubular reactor; the starting end of the water oxidation section is provided with an oxidant inlet 14; an oxidizing agent producing device 15; the oxidant inlet 14 is connected to the oxidant producing device 15 through a pipe.
In a preferred embodiment of the invention, the tubular reactor comprises a tubular body 16 and a stirring device 17; a feed inlet and a discharge outlet are respectively arranged at two ends of the pipe body 16; the discharge hole of the tubular reactor at the tail end of the hydrothermal section is connected with the feed hole of the tubular reactor at the starting end of the water oxidation section; the oxidant inlet 14 is located near the feed inlet of the tubular reactor at the beginning of the water oxidation stage.
In some embodiments of the invention, the stirring device 17 comprises a stirring shaft 18 extending into the tubular body 16, on which half-reduced blades 19 are uniformly arranged.
In some embodiments of the invention, the hydrothermolysis stage comprises two or more tubular reactors, and the water oxidation stage comprises two or more tubular reactors; the two or more tubular reactors are connected end to end through the feed inlets and the discharge outlets at the two ends of the tube body 16.
In some embodiments of the present invention, the discharge port of the fine grinding device 4 is respectively connected with the slurry intermediate storage tank 5 and the homogenizing tank 2; the centrifuge 11 is provided with a feed inlet, a water outlet and a solid phase discharge outlet, and the water outlet of the centrifuge 11 is connected with the water storage tank 12.
In a preferred embodiment of the invention, said heat exchanger 8 is a double pipe heat exchanger; the oxidizing agent production apparatus 15 is an oxygen-enriched air production apparatus.
In a preferred embodiment of the invention, the harmless treatment device for the waste oil-based mud is of a skid type.
In some embodiments of the invention, the waste oil-based mud innocent treatment device comprises: the device comprises a feeding grinding device 1, a homogenizing tank 2, a mortar pump 3, a fine grinding device 4, a slurry intermediate storage tank 5, a high-pressure slurry pump 6, a pressure regulation and control system 7, a heat exchanger 8, an auxiliary heater 9, a hydrothermal decomposition and oxidation reactor 10, an oxygen-enriched air manufacturing device, a centrifugal machine 11, a water storage tank 12 and a water pump 13. Waste oil-based mud generated after the oil-based mud generated by drilling is recycled by a drilling mud recycling system enters a feeding grinding device 1, large particles or rock debris are crushed and ground and then enter a homogenizing tank 2, and certain water (which can be sewage generated by a drilling well site) is added for homogenizing. And grinding the homogenized slurry again by using a fine grinding device 4 by using a mortar pump 3, circulating part of the homogenized slurry to a homogenizing tank 2, feeding part of the homogenized slurry to a slurry intermediate storage tank 5, pressurizing and conveying the part of the homogenized slurry to a pressure regulation and control system 7 by using a high-pressure slurry pump 6, heating the slurry by using a heat exchanger 8 and an auxiliary heater 9, and heating the heated slurry to enter a hydrothermal pyrolysis oxidation reactor 10. As shown in fig. 1, in the hydrothermal oxidation reactor 10, the sections a + B and C + D are hydrothermal oxidation sections, and oxygen-enriched air generated by the oxygen-enriched air producing apparatus is introduced into the sections C + D. The hydrothermal hydrolysis section (A + B) and the hydrothermal oxidation section (C + D) can be added according to the material amount to be treated. In the hydrothermal oxidation reactor 10, water as a reaction medium is in a subcritical state (temperature: 120 to 350 ℃ and pressure: 5 to 20 MPa). The purpose of making the water in the hydrothermal decomposition section and the hydrothermal oxidation section in a subcritical state is to reduce the corrosion to equipment and reduce the manufacturing cost and the operating cost of the equipment. The purpose of arranging the hydrothermal decomposition section is to convert macromolecular organic matters in the material into micromolecular organic matters and play a role in stably solidifying heavy metals; the purpose of setting up hydrothermal oxidation section is with the quick water and carbon dioxide of turning into of micromolecule organic matter. The hot materials fully reacted by the hydrothermal-hydrolysis-oxidation reactor 10 enter the heat exchanger 8 for heating the imported materials, the materials discharged from the heat exchanger 8 are subjected to solid-liquid separation by the centrifuge 11, the separated solid phase is common materials meeting the national relevant standards, the separated water enters the water storage tank 12, and is pressurized by the water pump 13 to enter the homogenizing tank 2 for recycling.
The invention provides a harmless treatment process for waste oil-based mud, which adopts any one of the harmless treatment devices to treat the waste oil-based mud, and comprises the following steps:
s1, pretreatment: recovering the solid phase of the oil-based mud, and carrying out coarse grinding, water adding homogenization and fine grinding on the solid phase of the mud to obtain pretreated mud;
s2, heating: during initial operation, the pre-treated slurry is heated by the auxiliary heater 9; after the operation is stable, the pretreated slurry is heated by a heat exchanger 8 to obtain preheated slurry;
s3, hydrothermal oxidation reaction: the preheated slurry enters a hydrothermal decomposition section of a hydrothermal decomposition oxidation reactor 10, and is subjected to pyrolysis at the temperature of 150-350 ℃ and under the pressure of 5-20 MPa; the pyrolysis product enters a hydrothermal oxidation section of a hydrothermal pyrolysis oxidation reactor 10, an oxidant is introduced into the hydrothermal oxidation section through an oxidant manufacturing device 15, and oxidation reaction is carried out at the temperature of 150-350 ℃ and under the pressure of 5-20 MPa, so that an oxidation product is obtained;
s4, heat recovery: the oxidation product heats the pretreated slurry through a heat exchanger 8;
s5, solid-liquid separation: the oxidation product after heat exchange enters a centrifuge 11 for solid-liquid separation, and the separated water enters a water storage tank 12 and is conveyed to the homogenizing tank 2 through a water pump 13.
In the preferred embodiment of the present invention, in the step S1, the slurry solid phase enters the feed grinding device 1 and is ground into particles with a particle size of less than 5 mm; then the mixture enters a homogenizing tank 2, water is added to adjust the mixture into slurry with the liquid content of 87-90 percent, and the slurry is fully and uniformly stirred; then the mixture is conveyed into a fine grinding device 4 through a mortar pump 3 and is further ground into particles with the particle size smaller than 1 mm; the finely ground slurry is partly returned to the homogenization tank 2 and partly to the intermediate slurry storage tank 5.
In the preferred embodiment of the invention, in the step S2, when the heat provided by the heat exchanger 8 is insufficient, the auxiliary heater 9 is used for supplementing heat to heat the pretreated slurry to 250-300 ℃; in the step S3, keeping the pressure of the hydrothermal decomposition section at 10-20 MPa, and allowing the slurry to stay in the hydrothermal decomposition section for 30-60 minutes to obtain a pyrolysis product; keeping the pressure of the hydrothermal oxidation section at 10-20 MPa, introducing oxygen or oxygen-enriched air, keeping the peroxide coefficient at 1.2-2.0, and allowing the pyrolysis product to stay in the hydrothermal oxidation section for 30-60 minutes to obtain an oxidation product.
Application example：
The oil content of the waste oil-based mud generated after the diesel-oil-based mud drilling waste generated by drilling in a certain gas field in southwest is recovered by a drilling mud recovery system (through a vibrating screen → a drying machine → a centrifugal machine) is 5 percent and is far greater than the national standard (the oil content is less than 1 percent). The largest diameter of the rock debris in the waste oil-based mud is about 3-4 cm. The harmless treatment device for the waste oil-based mud is adopted for treatment, and comprises the following steps:
(1) pretreatment: the waste oil-based mud (oil-based drilling cuttings) enters a feeding grinding device 1 through a feeding system, the materials are ground into fine particles with the particle size of less than 5mm and then enter a homogenizing tank 2, proper water is added, the liquid content of the materials is adjusted to be about 90%, and the materials are fully and uniformly stirred; the uniformly stirred materials are pressurized and sent into a fine grinding device 4 by a mortar pump 3, and further ground into particles with the particle size of less than 1mm, then one part of the particles enters a homogenizing tank 2 again, and the other part of the particles enters a slurry intermediate storage tank 5. The pretreated slurry enters a pressure regulation system 7 by pressurizing through a high-pressure slurry pump 6, and enters a heat exchanger 8 after the pressure is regulated.
(2) Heating: during initial operation, the pre-treated slurry is heated by the auxiliary heater 9; after the operation is stable, the pretreated slurry is heated by the heat exchanger 8, and when the heat provided by the heat exchanger 8 is insufficient, the auxiliary heater 9 is used for supplementing. And heating the pretreated slurry to 250-300 ℃.
(3) Hydrothermal oxidation reaction: the hot slurry enters a hydrothermal decomposition oxidation reactor 10, and the pressure of the reactor is kept at 10-20 MPa through a pressure regulation system 7; the retention time of the oil-based mud in a hydrothermal decomposition section is about 30-60 minutes, the dielectric constant of water is only 27 at 250 ℃, the dissolving capacity of the oil-based mud on organic matters is greatly enhanced, most of organic components in the oil-based mud are dissolved in water in the hydrothermal decomposition section, and a part of macromolecular organic matters are converted into micromolecular organic matters; the retention time of the hydrothermal oxidation section is 30-60 minutes, oxygen-enriched air generated by the oxygen-enriched air manufacturing device is introduced, the peroxide coefficient is 1.5, and small molecular organic components in water and oxygen are subjected to oxidation reaction and converted into water and carbon dioxide.
(4) And (3) heat recovery: the reacted material is heat exchanged by a heat exchanger 8 and used for heating the pretreated slurry.
(5) Solid-liquid separation: after the heat exchange reaction, the solid-liquid separation is carried out on the material through the centrifuge 11, the solid phase is discharged from a solid phase discharge port of the centrifuge 11, and the water phase enters the water storage tank 12 and is then conveyed to the homogenizing tank 2 through the water pump 13 for recycling.
The detection shows that the oil content of the obtained solid phase is about 0.7 percent and meets the national standard of less than 1 percent.
Claims (10)
1. The utility model provides a abandonment oil base mud innocent treatment device which characterized in that: the device comprises a feeding grinding device (1), a homogenizing tank (2), a mortar pump (3), a fine grinding device (4), a slurry intermediate storage tank (5), a high-pressure slurry pump (6), a pressure regulating system (7), a heat exchanger (8), an auxiliary heater (9), a hydrothermal oxidation reactor (10), a centrifuge (11), a water storage tank (12) and a water pump (13) which are sequentially connected through a pipeline;
a discharge hole of the hydrothermal decomposition oxidation reactor (10) is connected with a hot material inlet of the heat exchanger (8), and a hot material outlet of the heat exchanger (8) is connected with a feed hole of the centrifuge (11); the water outlet of the water pump (13) is connected with the water inlet of the homogenizing tank (2);
the hydrothermal oxidation reactor (10) comprises a hydrothermal decomposition section and a water oxidation section; the hydrothermolysis section comprises at least one tubular reactor, and the water oxidation section comprises at least one tubular reactor; the starting end of the water oxidation section is provided with an oxidant inlet (14);
further comprising an oxidant production device (15); the oxidant inlet (14) is connected to the oxidant producing device (15) through a pipe.
2. The apparatus of claim 1, wherein: the tubular reactor comprises a tube body (16) and a stirring device (17); a feed inlet and a discharge outlet are respectively arranged at two ends of the pipe body (16); the discharge hole of the tubular reactor at the tail end of the hydrothermal section is connected with the feed hole of the tubular reactor at the starting end of the water oxidation section; the oxidant inlet (14) is arranged near the feed inlet of the tubular reactor at the beginning of the water oxidation section;
preferably, the stirring device (17) comprises a stirring shaft (18) extending into the pipe body (16), and halving blades (19) are uniformly arranged on the stirring shaft (18).
3. The apparatus of claim 2, wherein: the hydrothermal decomposition section comprises two or more tubular reactors, and the water oxidation section comprises two or more tubular reactors; the two or more tubular reactors are connected end to end through the feed inlet and the discharge outlet at the two ends of the tube body (16).
4. The apparatus of claim 1, wherein: the discharge hole of the fine grinding device (4) is respectively connected with the slurry intermediate storage tank (5) and the homogenizing tank (2); the centrifuge (11) is provided with a feed inlet, a water outlet and a solid phase discharge outlet, and the water outlet of the centrifuge (11) is connected with the water storage tank (12).
5. The apparatus of claim 1, wherein: the heat exchanger (8) is a double-pipe heat exchanger; the oxidizing agent production device (15) is an oxygen-enriched air production device.
6. The apparatus of any of claims 1-5, wherein: the harmless treatment device for the waste oil-based mud is of a skid-mounted type.
7. Use of the apparatus of any one of claims 1 to 6 in the innocent treatment of waste oil-based muds.
8. A process for the innocent treatment of waste oil-based mud, characterized in that the waste oil-based mud is treated by the device of any one of claims 1 to 6, comprising the following steps:
s1, pretreatment: recovering the solid phase of the oil-based mud, and carrying out coarse grinding, water adding homogenization and fine grinding on the solid phase of the mud to obtain pretreated mud;
s2, heating: during initial operation, heating the pretreated slurry by an auxiliary heater; after the operation is stable, the pretreated slurry is heated by a heat exchanger to obtain preheated slurry;
s3, hydrothermal oxidation reaction: the preheated slurry enters a hydrothermal decomposition section of a hydrothermal decomposition oxidation reactor, and is subjected to pyrolysis at the temperature of 150-350 ℃ and under the pressure of 5-20 MPa; the pyrolysis product enters a hydrothermal oxidation section of a hydrothermal pyrolysis oxidation reactor, an oxidant is introduced into the hydrothermal oxidation section through an oxidant manufacturing device, and oxidation reaction is carried out at the temperature of 150-350 ℃ and under the pressure of 5-20 MPa, so that an oxidation product is obtained;
s4, heat recovery: the oxidation product heats the pretreated slurry through a heat exchanger;
s5, solid-liquid separation: and (4) feeding the oxidation product subjected to heat exchange into a centrifugal machine for solid-liquid separation, feeding the separated water into a water storage tank, and conveying the water into a homogenizing tank through a water pump.
9. The process according to claim 8, characterized in that:
in the step S1, the slurry solid phase enters a feeding grinding device and is ground into particles with the particle size of less than 5 mm; then the mixture enters a homogenizing tank, water is added to adjust the mixture into slurry with the liquid content of 87-90 percent, and the slurry is fully and uniformly stirred; then the mixture is conveyed into a fine grinding device through a mortar pump and is further ground into particles with the particle size of less than 1 mm; and returning one part of the finely ground slurry to the homogenizing tank, and feeding the other part of the finely ground slurry to a slurry intermediate storage tank.
10. The process according to claim 8 or 9, characterized in that:
in the step S2, when the heat provided by the heat exchanger is insufficient, an auxiliary heater is used for supplementing heat, and the pretreated slurry is heated to 250-300 ℃;
in the step S3, keeping the pressure of the hydrothermal decomposition section at 10-20 MPa, and allowing the slurry to stay in the hydrothermal decomposition section for 30-60 minutes to obtain a pyrolysis product; keeping the pressure of the hydrothermal oxidation section at 10-20 MPa, introducing oxygen or oxygen-enriched air, keeping the peroxide coefficient at 1.2-2.0, and allowing the pyrolysis product to stay in the hydrothermal oxidation section for 30-60 minutes to obtain an oxidation product.
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| CN202010165943.5A CN111253032A (en) | 2020-03-11 | 2020-03-11 | Device and process for harmless treatment of waste oil-based mud |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115231686A (en) * | 2022-08-25 | 2022-10-25 | 广州茂华环境发展有限公司 | Controllable wet catalytic oxidation closed-loop tubular reaction system for treating organic waste |
| CN116159521A (en) * | 2023-03-20 | 2023-05-26 | 菲立智能装备(浙江)有限公司 | Novel high-efficient dynamic reactor |
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2020
- 2020-03-11 CN CN202010165943.5A patent/CN111253032A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115231686A (en) * | 2022-08-25 | 2022-10-25 | 广州茂华环境发展有限公司 | Controllable wet catalytic oxidation closed-loop tubular reaction system for treating organic waste |
| CN116159521A (en) * | 2023-03-20 | 2023-05-26 | 菲立智能装备(浙江)有限公司 | Novel high-efficient dynamic reactor |
| CN116159521B (en) * | 2023-03-20 | 2023-09-01 | 菲立智能装备(浙江)有限公司 | Dynamic reactor |
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