CN102874998A - Method for reducing oil content of oil-containing sludge, and processing method of oil-containing sludge - Google Patents
Method for reducing oil content of oil-containing sludge, and processing method of oil-containing sludge Download PDFInfo
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Abstract
The invention discloses a method for reducing the oil content of oil-containing sludge. The reducing method comprises a step that the oil-containing sludge contacts with an aquathermolytic catalyst in a closed container at a temperature which is higher than 100DEG C and not higher than 374DEG C. The invention further discloses a processing method of the oil-containing sludge. The processing method comprises the following steps: allowing the oil-containing sludge to contact with the aquathermolytic catalyst according to the reducing method; separating out an oil phase and a water phase in contact products to obtain a solid phase; respectively purifying the oil phase and the water phase to make the mass fraction of water in the oil phase be less than 0.5% and the oil content in the water phase be less than 10mg/L; and removing volatile components in the solid phase to make the mass fraction of water in the solid phase be less than 30%. The methods disclosed in the invention have the advantages of simplicity, easy implementation, low operation cost, effective reduction of the oil content in the oil-containing sludge, and easy realization of the separation of the water phase, a sludge phase and the water phase.
Description
Technical field
The present invention relates to a kind of method of the oil-contg that reduces oily sludge and the treatment process of oily sludge.
Background technology
Oily sludge is the product of following of oil production, is one of primary pollution source in the process of oil production.The complicated component of oily sludge can not directly utilize or efflux, and usually as waste, is stacked air-dry or buries undergroundly, and so both contaminate environment was wasted again resource, returned enterprise and brought huge financial loss.Oil and water contained in the oily sludge form stable milk sap, be adsorbed on securely in the surface and hole of silt particle, and adhesive power strengthen with the average molecular mass of oil and the increase of viscosity.The method of conventional processing oily sludge comprises at present: burning method, hot washing method, vaporizing extract process, solvent extration, chemical demulsification method and biological treatment etc., aforesaid method is comparatively effective for the oily sludge that is formed by the lower oil of average molecular mass, and the treatment effect of the oily sludge that forms for oil higher by average molecular mass and that viscosity is higher is undesirable, and processing cost is higher.
High temperature re-treating process (the high temperature re-treating process of oily sludge, W.J.Hahn, oil production technology information, 1996 (2): 22～27) be a kind of method of processing oily sludge that developed recently gets up, the method comprises milky liquid liquid or mud is heated to more than the boiling point of water, then enter and carry out flash separation in the knockout tower, in flashing tower, steam and light hydrocarbon are extracted, heavy hydrocarbon and mud take out from knockout tower with the form of mud, described steam and light hydrocarbon reclaim by the method for condensation, and described mud is separated into heavy hydrocarbon and mud by after the solid-liquid separation.The high temperature re-treating process mainly is that the mode by heating reduces oil viscosity in the oily sludge; Increase the collision rate of dispersed phase drop, thereby improve the molecular motion speed of disperse phase; The density difference that weakens the active of emulsifying agent and increase between oil, the water is separated into oil phase, water and solid phase with oily sludge, and by water is in time separated, and prevent from again occuring emulsification.Therefore, the high temperature re-treating process is in fact a kind of physical method.And, although the high temperature re-treating process is comparatively effective for the oily sludge that is formed by the lower oil of average molecular mass, but the treatment effect of the oily sludge that forms for oil higher by average molecular mass and that viscosity is higher is still undesirable, and processing cost is higher.In addition, although the high temperature re-treating process can be processed oily sludge effectively, this arts demand carries out flash distillation with the oily sludge of heating in knockout tower, so equipment is comparatively huge and complicated, has improved running cost.
Summary of the invention
The object of the present invention is to provide a kind of new process for treating oil-containing sludge, the method can remove the oil in the oily sludge effectively, and easy and simple to handle, running cost is low.
The present inventor is surprised to find that in research process: in encloses container, oily sludge and hydrothermal cracking catalyst are being higher than 100 ℃ and be not higher than under 374 ℃ the temperature and contact, only needing that product of contact is carried out solid-liquid separation in the equipment for separating liquid from solid of routine can be with the most of oil phase in the oily sludge and aqueous phase separation out, and then realizes the separation of oil, mud, water three-phase.Finished thus the present invention.
A first aspect of the present invention provides a kind of method that reduces the oil-contg of oily sludge, and the method is included in the encloses container, and oily sludge is contacted with hydrothermal cracking catalyst, and the temperature of described contact is for being higher than 100 ℃ and be not higher than 374 ℃.
A second aspect of the present invention provides a kind of method that oily sludge is processed, and the method comprises:
Adopt method provided by the invention that described oily sludge is contacted with hydrothermal cracking catalyst;
Isolate oil phase and water in the product of contact, to obtain solid phase;
Described oil phase and water are purified separately, so that the massfraction of water is lower than 0.5% in the described oil phase, the oil-contg of described aqueous phase is lower than 10mg/L; And
Remove the volatile matter in the described solid phase, so that the massfraction of water is lower than 30% in the described solid phase.
The method according to this invention is in encloses container, oily sludge and hydrothermal cracking catalyst are being higher than 100 ℃ and be not higher than under 374 ℃ the temperature and contact, oily sludge after the contact is in the conventional equipment for separating liquid from solid of for example triphase separator, can realize the separation of oil, mud, water three-phase, the oil recovery rate is high, and the mud that obtains and the oleaginousness in the water significantly reduce, and can satisfy the requirement of discharging or reuse.
Particularly, adopt the method according to this invention that oily sludge is processed, in mass, the decreasing ratio of oil can reach more than 98% in the oily sludge, and the oil recovery rate can reach more than 95%; And the mud that obtains and water can meet respectively the standard of reuse or discharging, wherein, the oleaginousness in the water of recovery can be lower than 10mg/L, and the oil-contg in the mud that obtains can be lower than the dried mud of 3g/kg (namely, with respect to the dried mud of 1kg, the oil-contg in the mud that obtains is for being lower than 3g).
In addition, the method according to this invention is simple and easy to do, and running cost is low, adopts existing equipment to implement.
Embodiment
The invention provides a kind of method that reduces the oil-contg of oily sludge, the method is included in the encloses container, and oily sludge is contacted with hydrothermal cracking catalyst, and the temperature of described contact is for being higher than 100 ℃ and be not higher than 374 ℃.
Among the present invention, term " oil " refers to the hydrophobic nature material that produces in crude oil and the Crude Oil Processing, comprise being liquid hydrophobic nature material under the normal temperature, and be the hydrophobic nature material of colloidal state under the normal temperature, for example: the various oil soluble surfactants that use in hydrocarbons, the oil recovery process.
The method according to this invention, described hydrothermal cracking catalyst can have for various aquathermolysis to oil the material of katalysis.Preferably, described hydrothermal cracking catalyst is one or more in transition metal salt, organic acid transition metal salt, organometallic complex, heteropolyacid and the heteropolyacid salt of mineral acid.
Among the present invention, transition metal comprises: IIB family metal, IIIB family metal, IVB family metal, VB family metal, group vib metal, VIIB family metal, group VIII metal, I B-group metal and IIB family metal.
Among the present invention, described mineral acid can be the various mineral acids that can form with the positively charged ion of transition metal chemical bond, for example: sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.Described organic acid can be the various organic acids that can form with transition metal chemical bond, for example: aliphatic carboxylic acid (as: C
1～C
20Carboxylic acid) and aromatic carboxylic acid (as: C
6～C
20Replacement or unsubstituted aromatic carboxylic acid).
Among the present invention, described organometallic complex refers to the material that atoms metal and organic ligand form by coordinate bond, described organic ligand can be the various organic compound that can form with atoms metal coordinate bond, for example: the compound (as: α-diketone, beta-diketon, γ-diketone) that contains carbonyl.Preferably, described carbonyl containing compound is the beta-diketon shown in the formula I,
Among the formula I, R
1And R
2Can be C separately
1～C
6The straight or branched alkyl.
Among the present invention, C
1～C
6The straight or branched alkyl example can for but be not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl and n-hexyl.
The example of described carbonyl containing compound can for but be not limited to: 2,4-diacetylmethane (that is, methyl ethyl diketone), 2,4-hexanedione, 2,4-heptadione, 6-methyl-2,4-heptadione, 5-methyl-2,4-hexanedione, 2,4-acetyl caproyl, 3,5-heptadione, 3,5-acetyl caproyl, 4,6-diketone in the ninth of the ten Heavenly Stems, 3-methyl-2,4-diketone in the ninth of the ten Heavenly Stems, 2,2,7-trimethylammonium-3,5-acetyl caproyl, 2,2,6,6-tetramethyl--3,5-acetyl caproyl, 2,2,6,6-tetramethyl--3,5-heptadione, dimethyl diketone and 2,5-hexanedione.From the angle of being easy to get property of raw material, described beta-diketon is 2,4-diacetylmethane.
Among the present invention, described heteropolyacid refers to contain oxygen polyacid by certain structure by the class that the oxygen atom ligand bridging forms by heteroatoms and polyatom.Heteropolyacid salt refers to that at least part of hydrogen ion in the heteropolyacid is replaced and the compound of formation by ammonium radical ion or metallic cation.
According to the present invention, the example of described hydrothermal cracking catalyst includes but not limited to: ferric sulfate, rose vitriol, single nickel salt, zinc sulfate, iron oleate, cobalt oleate, oleic acid nickel, copper naphthenate, zinc naphthenate, iron naphthenate, cobalt naphthenate, aluminium acetylacetonate, acetylacetonate nickel, vanadium acetylacetonate, acetylacetone cobalt, the phosphorus aluminic acid, phospho-wolframic acid, the phosphorus vanadic acid, silicoaluminate, silicotungstic acid, silicon molybdenum wolframic acid, P-Mo-Wo acid, the sulfo-molybdic acid, the phosphorus ammonium aluminate, ammonium phosphowolframate, the phosphorus ammonium vanadate, the silicoaluminate ammonium, ammonium silicotungstic, ammonium thiomolybdate, the phosphorus sodium aluminate, Tungstophosphoric acid, sodium salt, the phosphorus vanadic acid sodium, sodium silicoaluminate and silicotungstic sodium.
More preferably, described hydrothermal cracking catalyst is the group VIII metal-salt of mineral acid, the IIB family metal-salt of mineral acid, organic acid group VIII metal-salt, the VIIB family metal-salt of mineral acid, organic acid VIIB family metal-salt, organic acid I B-group metal salt, the I B-group metal salt of mineral acid, organic acid I B-group metal salt, the organometallic complex of group III A metal, the organometallic complex of IIB family metal, the organometallic complex of IIA family metal, the organometallic complex of group VIII metal, take the group vib metal as polyatomic heteropolyacid, take the group vib metal as polyatomic heteropolyacid salt, take the group III A metal as polyatomic heteropolyacid, take the group III A metal as polyatomic heteropolyacid salt, take VB family metal as polyatomic heteropolyacid and in take VB family metal as polyatomic heteropolyacid salt one or more.
More preferably, described hydrothermal cracking catalyst be the organometallic complex of organometallic complex, the group VIII metal of IIB family metal-salt, organic acid VIIB family metal-salt, organic acid I B-group metal salt, the group III A metal of mineral acid, take the group vib metal as polyatomic heteropolyacid salt and in take the group III A metal as polyatomic heteropolyacid salt one or more.
Further preferably, described hydrothermal cracking catalyst is: one or more in acetylacetonate, an alkali metal salt take the group vib metal as polyatomic heteropolyacid and the ammonium salt take the group III A metal as polyatomic heteropolyacid of the salt of the I B-group metal of the IIB family metal-salt of sulfuric acid, the VIIB family metal-salt of oleic acid, naphthenic acid, the acetylacetonate of group VIII metal, group III A metal.
Among the present invention, naphthenic acid can be this area various compounds that can form with metal ion salt commonly used.Preferably, described naphthenic acid is the compound shown in the formula II,
Among the formula II, m can be 1～10 integer, is preferably 2～6 integer, for example can be 2,3,4,5 or 6.
Most preferably, described hydrothermal cracking catalyst is one or more in zinc sulfate, acetylacetonate nickel, manganese oleate, copper naphthenate, aluminium acetylacetonate, Tungstophosphoric acid, sodium salt and the silicoaluminate ammonium.
Be not particularly limited according to the consumption of the inventive method for described catalyzer, can carry out appropriate selection according to the character of oily sludge.Usually, the mass ratio of oil can be 0.0005～0.1: 100 in described hydrothermal cracking catalyst and the described oily sludge.Preferably, the mass ratio of oil is 0.001～0.05: 100 in described hydrothermal cracking catalyst and the described oily sludge.Further preferably, the mass ratio of oil is 0.005～0.05: 100 in described hydrothermal cracking catalyst and the described oily sludge.
The method according to this invention comprises oily sludge is contacted with hydrothermal cracking catalyst that described contact is generally carried out in the presence of water.Generally speaking, oily sludge itself contains a certain amount of water, and wherein, water-content is according to its source and different.The present inventor finds in research process, in described oily sludge the massfraction of water be more than 20% (for example: in the time of 20%～90%), need not in this oily sludge, to replenish and add water, directly described oily sludge is contacted with hydrothermal cracking catalyst and can realize purpose of the present invention.When the massfraction of water in the described oily sludge when being lower than 20%, can add water by in described oily sludge, replenishing, and oily sludge and water mixed, the addition of water makes total amount take described oily sludge as benchmark, and the massfraction of water (for example: 20%～90%) is at least more than 20% in the described oily sludge.
That is, the method according to this invention, take the total amount of described oily sludge as benchmark, in the described oily sludge massfraction of water be more than 20% (for example: in the time of 20%～90%), the water that the source of described water can be contained for oily sludge itself; Take the total amount of described oily sludge as benchmark, the massfraction of water is when being lower than 20% in the described oily sludge, described water comprises the water that oily sludge itself contains and replenish the water that adds in oily sludge, the amount of the water of described additional interpolation is so that take the total amount of described oily sludge as benchmark, the massfraction of water (for example: 20%～90%) is at least 20%.
The method according to this invention can adopt the whole bag of tricks of this area routine that oily sludge is mixed with water, for example can be by oily sludge and water be stirred in mixing tank, and oily sludge is mixed with water.
The method according to this invention is not particularly limited for described hydrothermal cracking condition, as long as described hydrothermal cracking condition can be so that the oil in the oily sludge be easy to desorption from the mud.Usually, contacting of described hydrothermal cracking catalyst and described oily sludge can be higher than 100 ℃ and be not higher than under 374 ℃ the temperature and carry out.Preferably, described hydrothermal cracking catalyst is 150～350 ℃ with the temperature that contacts of described oily sludge.Take into account simultaneously the angle of energy consumption from the oil-contg of further reduction oily sludge, the temperature of described contact is 180～300 ℃.
The method according to this invention, the present inventor is surprised to find that in research process, under equal conditions, when described hydrothermal cracking catalyst carries out in the presence of one or more beta-diketons with contacting of described oily sludge, can further reduce the Contact Temperature of described hydrothermal cracking catalyst and described oily sludge.The method according to this invention, when described hydrothermal cracking catalyst carried out in the presence of one or more beta-diketons with contacting of described oily sludge, described hydrothermal cracking catalyst can carry out under 120～200 ℃ condition with contacting of described oily sludge.
Described beta-diketon can between two common carbonyls by a methylene radical (CH
2) or the various dione compounds that separate of methyne (CH).Preferably, described beta-diketon is the beta-diketon shown in the formula III,
In the formula III, R
3And R
4Can be C separately
1～C
6The straight or branched alkyl.
The method according to this invention, the example of described beta-diketon can for but be not limited to: 2,4-diacetylmethane, 2,4-hexanedione, 2,4-heptadione, 6-methyl-2,4-heptadione, 5-methyl-2,4-hexanedione, 2,4-acetyl caproyl, 3,5-heptadione, 3,5-acetyl caproyl, 4,6-diketone in the ninth of the ten Heavenly Stems, 3-methyl-2,4-diketone in the ninth of the ten Heavenly Stems, 2,2,7-trimethylammonium-3,5-acetyl caproyl, 2,2,6,6-tetramethyl--3,5-acetyl caproyl and 2,2,6,6-tetramethyl--3, the 5-heptadione.
From the angle of being easy to get property of raw material, described beta-diketon is 2,4-diacetylmethane and/or 2,4-hexanedione.
The method according to this invention, the consumption of described beta-diketon can carry out appropriate selection according to the oil-contg of described oily sludge.Preferably, the ratio of the quality of the oil in the total mass of described beta-diketon and the described oily sludge is 0.3～3: 100.Further preferably, the mass ratio of oil is 0.5～2: 100 in the total mass of described beta-diketon and the described oily sludge.
The method according to this invention, be not particularly limited the duration of contact of described oily sludge and hydrothermal cracking catalyst, can carry out appropriate selection according to the character of oily sludge.Usually, the time of described contact can be 12～48h.Under the prerequisite of the oil-contg that guarantees effectively to reduce oily sludge, from the further shortening angle of duration of contact, the time of described contact is preferably 12～36h.
The method according to this invention, the atmosphere when contacting with hydrothermal cracking catalyst for described oily sludge is not particularly limited.Described contact can (that is, oxygen-containing atmosphere) be carried out in the presence of oxygen, also can carry out in non-oxygen atmosphere.The method according to this invention when described contact is carried out, can further reduce the running cost of the method according to this invention in the presence of oxygen.That is to say that when contact of the present invention was carried out, described oxygen can be the oxygen that carries in reactor and/or the reaction raw materials in the presence of oxygen.
The method according to this invention, described contact can additionally not exerted pressure (that is, except the autogenous pressure of reactor, no longer additionally exert pressure) condition under carry out, also can under the condition of pressurization, carry out (that is, except the autogenous pressure of reactor, also additionally exerting pressure).When described contact was carried out under pressurized conditions, applied pressure can be 0.01～2MPa in the encloses container that contacts, and is preferably 0.1～1MPa.
The method according to this invention, described contact is carried out in encloses container.The present invention is not particularly limited for the kind of described encloses container, can be the various containers that can realize sealing function of routine.For example: the reactor that can realize sealing function.
The method according to this invention is not particularly limited for the oil-contg of described oily sludge.Usually, the content of oil can be the dried mud of 100～1000g/kg in the described oily sludge.
The method according to this invention, described oily sludge can be the oily sludge in various sources.Usually, described oily sludge can be the various oily sludges that produce in the Oil extraction process, such as: the oily sludge that produces in the oily sludge of the oily sludge that produces in the oilfield transportation system, refinery's Bottom Plate of Crude Oil Storage and the refinery's Sewage treatment systems etc.
The present invention also provides a kind of method that oily sludge is processed, and the method comprises:
Adopt the method for the oil-contg of reduction oily sludge provided by the invention that described oily sludge is contacted with hydrothermal cracking catalyst;
Isolate oil phase and water in the product of contact, to obtain solid phase;
Described oil phase and/or water are purified separately, so that the massfraction of water is lower than 0.5% in the described oil phase, the oil-contg of described aqueous phase is lower than 10mg/L; And
Remove the volatile matter in the described solid phase, so that the massfraction of water is lower than 30% in the described solid phase.
The method that oily sludge is processed according to the present invention comprises first oily sludge is contacted with hydrothermal cracking catalyst, so that the desorption from the mud of the oil in the described oily sludge, wherein, described oily sludge is contacted with hydrothermal cracking catalyst, method with the oil-contg that reduces described oily sludge is described in detail at preamble, does not repeat them here.
The method of oily sludge being processed according to the present invention also comprises to be isolated by oily sludge is contacted oil phase and the water in the product of contact that obtains with hydrothermal cracking catalyst, to obtain solid phase.
According to the method that oily sludge is processed of the present invention, by oily sludge and hydrothermal cracking catalyst are being higher than 100 ℃ and be not higher than under 374 ℃ the temperature and contact, be easy to surface desorption from mud so that be adsorbed on the oil of Sludge Surface, oily sludge after the contact need not to carry out flash distillation in flashing tower, just can be separated into oil phase, solid phase and water in the equipment for separating liquid from solid of this area routine.Therefore, the method that oily sludge is processed according to the present invention is not particularly limited for the method for isolating oil phase and water from product of contact, can be this area the whole bag of tricks commonly used.
According to a kind of embodiment of method that oily sludge is processed of the present invention, isolate oil phase and water in the product of contact, comprise with the method that obtains solid phase: isolate the liquid phase in the described product of contact, and described liquid phase separation is become water and oil phase.
The whole bag of tricks that can adopt this area to commonly use is isolated the liquid phase in the described product of contact.For example: the method for isolating the liquid phase in the described product of contact comprises: described product of contact is carried out gravity settling or centrifugation, to isolate the liquid phase in the described product of contact.The employed equipment of described gravity settling and centrifugation and method are known in the field.For example, described product of contact gravity settling chamber or gravity settling tank be can be placed, mud and the liquid phase separation that contains oil and water made by action of gravitation; Described product of contact can also be made mud and the liquid phase separation that contains oil and water by means of centrifugal force in centrifugation apparatus.
In this embodiment, can according to the character of the liquid phase that obtains, adopt this area the whole bag of tricks commonly used that described liquid phase separation is become water and oil phase.For example: under the air supporting condition, this liquid phase separation is become water and oil phase, and tell described oil phase and water.
By under the air supporting condition, when described liquid phase separation was become water and oil phase, described air supporting condition can be the normal condition of this area.For example: described air supporting condition can comprise: air flow quantity can be preferably 50～200std-L/h for 30～300std-L/h (that is, standard l/h), and hydraulic detention time can be 5～100min, is preferably 10～60min.
The method that oily sludge is processed according to the present invention also comprises: isolated oil phase and/or isolated water are purified respectively, so that the massfraction of water is lower than 0.5% in the described oil phase, the oil-contg of described aqueous phase is lower than 10mg/L.
Can adopt this area the whole bag of tricks commonly used to come isolated water and isolated oil phase are purified.
Usually, the method that isolated water is purified can comprise: throw in coagulating agent, isolated water is carried out biochemical treatment or isolated water is filtered to isolated aqueous phase.Aforesaid method can also be used in combination.
Described coagulating agent can be this area various coagulating agent commonly used, for example: one or more in the salt of the salt of aluminium, the polymkeric substance of aluminium, iron and the compound of iron.Among the present invention, the example of described coagulating agent can for but be not limited to: the hydrate of Tai-Ace S 150, alum, iron trichloride, the hydrate of ferrous sulfate, polyaluminium sulfate, polymerize aluminum chloride, polymerization chlorine sulphur aluminium, polymerised sulphur sial, polyacrylamide, sodium polyacrylate, polyvinyl pyridine and polymine.The method according to this invention, described coagulating agent is preferably polymerize aluminum chloride and polyacrylamide.
The consumption of described coagulating agent can be the conventional amount used of this area.Usually, with respect to the isolated water of 1L, the consumption of described coagulating agent can be 50～2000mg, is preferably 150～800mg.
The present invention is not particularly limited for the method for described biochemical treatment, can adopt this area method commonly used to carry out under the condition of this area routine.For example, the method for described biochemical treatment can for but be not limited to: activated sludge process, BAF (BAF) method, sequencing batch activated sludge (SBR) method, oxidation ditch process and Crouse (Kraus) method.
The present invention also is not particularly limited for the method for described filtration, and for example, what described filtration can be in sand filtration, micro-filtration, ultrafiltration, nanofiltration and the reverse osmosis is a kind of.Above-mentioned filter method can also be used in combination.
Usually, the method that isolated oil phase is purified comprises: isolated oil phase is carried out electric desalting.Described electric desalting can be carried out under normal condition in the electric desalting equipment that this area is commonly used.For example the condition of described electric desalting can for: temperature can be 60～150 ℃; Voltage can be 500～5000V, is preferably 2000～4000V; Time can be 10～240min, is preferably 40～200min.
Described electric desalting can be carried out in the presence of emulsion splitter, and described emulsion splitter can be this area various emulsion splitters commonly used, and for example, described emulsion splitter can be non-ionic demulsifier.More preferably, described emulsion splitter is that polyethers is emulsion splitter.Among the present invention, the example of described emulsion splitter can for but be not limited to: the polyoxypropylene-polyoxyethylene copolymer take alcohol (as: glycerol, propylene glycol or ethylene glycol) as the polyoxypropylene-polyoxyethylene copolymer of initiator, take amine (as: polyethylene polyamine) as initiator, Pluronic F68 take resol and/or phenol-amine resin as the polyoxypropylene-polyoxyethylene copolymer of initiator, take tolylene diisocyanate as chainextender.The present invention is not particularly limited for the consumption of described emulsion splitter, can be the conventional amount used of this area.Usually, take the quality of described oil phase as benchmark, the massfraction of described emulsion splitter can be 0.0001%～0.1%, is preferably 0.001%～0.05%.
The method according to this invention can also remove the volatile matter in the described solid phase (that is, the mud that obtains), and will remove behind the described volatile matter the solid phase drying so that in the mud massfraction of water be lower than 30% (that is, the mud that obtains being carried out minimizing processes).Can adopt method well known in the art to remove volatile matter in the solid phase that obtains, this paper repeats no more.
Describe the present invention in detail below in conjunction with embodiment.
The testing method that relates in following examples comprises:
The mensuration of oleaginousness in the mud: adopt infrared spectrophotometry, divide the method mensuration of regulation according to the determination part of " the CJ/T 221-2005 sludge from wastewater treatment plant method of inspection " mineral oil in fluid.
The mensuration of water content in the mud: adopt mass method, divide the method mensuration of regulation according to the determination part of water ratio in " the CJ/T 221-2005 sludge from wastewater treatment plant method of inspection ".
The mensuration of oleaginousness in the water: adopt infrared spectrophotometry, measure according to the method for regulation in " GB/T 16488-1996 water-quality petroleum and animals and plants Determination of oil ".
The mensuration of Water in oil amount: the method according to the regulation in " GB/T 260-1977 (1988) petroleum products aquametry " is measured.
Embodiment 1
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge that uses in the present embodiment: as benchmark, this oily sludge contains 600.0g oil with the dried mud of 1kg; Take the total amount of oily sludge as benchmark, the massfraction of water is 45% in this oily sludge.
(1) in oily sludge, adds ZnSO
4(wherein, ZnSO
4With the mass ratio of oil in the described oily sludge be 0.005: 100), then with mixture at N
2In the atmosphere, additionally in the situation of pressurization, in being 240 ℃ closed reactor, temperature do not react 30h; Reaction product is carried out gravity settling in gravity settling tank, separate the liquid phase that obtains mud and contain oil and water, adopt By Bubble-floating Method (wherein, the air supporting condition is: air flow quantity is 100std-L/h, hydraulic detention time 20min) to be separated into oil phase and water the liquid phase that obtains.Measure the oil-contg in the isolated mud, the result is shown in the table 1.
(2) add in the isolated oil phase and (be purchased from chemical plant, Liaoyuan, Jilin with the polyoxyethylene polyoxypropylene ether emulsion splitter of stearyl alcohol as initiator, the trade mark is SP169), take the quality of described oil phase as benchmark, the massfraction of described emulsion splitter is 0.001%.Be 80 ℃ in temperature, voltage is in the electric field of 2000V, carries out the oily water separation of 60min.Measure the water-content in the oil phase after processing.The result is shown in the table 1.
(3) adopt the BAF method that isolated water is processed.Wherein, the condition of BAF method comprises: temperature is 35 ℃, and the air water volume ratio is 3: 1, and hydraulic detention time is 6h.Measure the oil-contg of the aqueous phase after processing, the result is shown in the table 1.
(4) mud that separation is obtained is in revolver drier (be purchased from North China drying plant factory, model is GZT10), at 150 ℃ of lower dry 30min.The massfraction of the water in the dried mud is shown in the table 1.
Comparative Examples 1
Adopt the method identical with step (1) among the embodiment 1 that oily sludge is processed, different is not use ZnSO
4
Comparative Examples 2
Adopt the method identical with step (1) among the embodiment 1 that oily sludge is processed, different is that the interior temperature of closed reactor is 80 ℃.
Comparative Examples 3
Adopt the method identical with step (1) among the embodiment 1 that oily sludge is processed, different is, in order to polyoxyethylene polyoxypropylene ether emulsion splitter (be purchased from Sinopec Nanjing branch office chemical industry two factories, the trade mark be F3111) the replacement ZnSO of propylene glycol as initiator
4, the quality of the oil in the described oily sludge is as benchmark, and the massfraction of described emulsion splitter is 0.005%.
Embodiment 2
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Adopt the method identical with embodiment 1 that oily sludge is processed, different is that use acetylacetonate nickel (being purchased from Beijing Yili Fine Chemicals Co., Ltd.) is as catalyzer.The result is shown in the table 1.
Embodiment 3
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge that uses in the present embodiment: as benchmark, this oily sludge contains 200.0g oil with the dried mud of 1kg; Take the total amount of oily sludge as benchmark, the massfraction of water is 10% in this oily sludge.
(1) in oily sludge, adds entry, make the massfraction of water in the oily sludge that adds behind the water reach 20%, oily sludge and water are mixed, in the mixture that obtains, add manganese oleate (being purchased from Beijing Yili Fine Chemicals Co., Ltd.) (wherein, the mass ratio of the oil in manganese oleate and the described oily sludge is 0.01: 100), then with mixture in air atmosphere, additionally in the situation of pressurization, in temperature is 200 ℃ closed reactor, do not react 36h; Reaction product is carried out gravity settling in gravity settling tank, separate the liquid phase that obtains mud and contain oil and water, adopt By Bubble-floating Method (wherein, the air supporting condition is: air flow quantity is 150std-L/h, hydraulic detention time 30min) to be separated into oil phase and water the liquid phase that obtains.Measure the oil-contg in the isolated mud, the result is shown in the table 1.
(2) under 100 ℃, isolated oil phase is applied electric field, carry out oily water separation, wherein, the voltage of the electric field that applies is 2000V, the time that applies electric field is 60min.Measure the water-content in the oil phase after processing.The result is shown in the table 1.
(3) adopt the method for nanofiltration (nanofiltration membrane of use is purchased from DOW Chemical (China) company limited, and model is NF90-4040) that isolated water is filtered.Measure the oil-contg of the aqueous phase after processing, the result is shown in the table 1.
(4) mud that separation is obtained is indirect sludge drying machine (be purchased from the Sanmenxia Gorge hundred dry Engineering Co., Ltd), at 160 ℃ of lower dry 20min.The massfraction of the water in the dried mud is shown in the table 1.
Comparative Examples 4
Adopt the method identical with step (1) among the embodiment 3 that oily sludge is processed, different is, be that the polyoxyethylene polyoxypropylene ether emulsion splitter of initiator (is purchased from Binzhou Chemical Plant, Shandong Prov. in order to resol, the trade mark is BSE311) the replacement manganese oleate, the quality of the oil in the described oily sludge is as benchmark, and the massfraction of described emulsion splitter is 0.01%.
Embodiment 4
Present embodiment is used for illustrating according to the method for the oil-contg in the reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge that uses in the present embodiment: as benchmark, this oily sludge contains 300.0g oil with the dried mud of 1kg; Take the total amount of oily sludge as benchmark, the massfraction of water is 35% in this oily sludge.
(1) add in the oily sludge copper naphthenate (
M is 6, is purchased from Gansu Provincial Chemical Industry Inst.) (wherein, the mass ratio of the oil in copper naphthenate and the described oily sludge is 0.015: 100), then mixture is placed autoclave, the enclosed high pressure reactor; And in this autoclave, be filled with N
2, so that the gauge pressure in this autoclave is 1MPa; Then, the temperature in the autoclave is increased to 300 ℃, and under this temperature, reacts 24h.Place separating centrifuge to carry out centrifugation reaction product, obtain mud and the liquid phase that contains oil and water.Adopt By Bubble-floating Method (wherein, the air supporting condition is: air flow quantity is 50std-L/h, hydraulic detention time 50min) to be separated into oil phase and water the liquid phase that obtains.Measure the oil-contg in the isolated mud, the result is shown in the table 1.
(2) add in the isolated oil phase with resol and (be purchased from upper seapeak dimension chemical industry company limited as the polyoxyethylene polyoxypropylene ether emulsion splitter of initiator, the trade mark is AR36), take the total amount of described oil phase as benchmark, the massfraction of described emulsion splitter is 0.003%.Be 100 ℃ with the oil phase that is added with described emulsion splitter in temperature, voltage is in the electric field of 3000V, carries out the oily water separation of 40min, to remove the water in the oil phase.Measure the water-content in the oil phase after processing, the result is shown in the table 1.
(3) add polymerize aluminum chloride (being purchased pool, section sky water-purifying material company limited in Shandong) to isolated aqueous phase, with respect to the water of 1L, the addition of polymerize aluminum chloride is 300mg; Then stirred 10 minutes, and left standstill after 30 minutes and filter, to remove the oil of aqueous phase.Measure the oil-contg of the aqueous phase after processing, the result is shown in the table 1.
(4) mud that separation is obtained is in revolver drier (be purchased from North China drying plant factory, model is GZT10), at 200 ℃ of lower dry 30min.The massfraction of the water in the dried mud is shown in the table 1.
Comparative Examples 5
Adopt the method identical with step (1) among the embodiment 4 that oily sludge is processed, different is, use (is purchased from chemical plant, Liaoyuan, Jilin with the polyoxyethylene polyoxypropylene ether emulsion splitter of stearyl alcohol as initiator, the trade mark is SP169) the replacement copper naphthenate, the total amount of the oil in the described oily sludge is as benchmark, and the massfraction of described emulsion splitter is 0.015%.
Embodiment 5
Present embodiment is used for illustrating according to the method for the oil-contg in the reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge that uses in the present embodiment: as benchmark, this oily sludge contains 360.0g oil with the dried mud of 1kg; Take the total amount of oily sludge as benchmark, the massfraction of water is 15% in this oily sludge.
(1) in oily sludge, adds entry, making the massfraction of water in the oily sludge that adds behind the water is 30%, oily sludge and water are mixed, in the mixture that obtains, add aluminium acetylacetonate (being purchased from Hangzhou chemical reagent company limited) (wherein, the mass ratio of the oil in aluminium acetylacetonate and the described oily sludge is 0.02: 100), then mixture is placed autoclave, the enclosed high pressure reactor; And be filled with air in this autoclave, so that the gauge pressure in this autoclave is 0.5MPa; Then, the temperature in the autoclave is risen to 220 ℃, and under this temperature, react 28h.Place separating centrifuge to carry out centrifugation reaction product, thereby will be the mud and the liquid phase separation that contains oil and water of solid phase, the liquid phase that obtains is adopted By Bubble-floating Method (wherein, the air supporting condition is: air flow quantity is 120std-L/h, hydraulic detention time 15min) be separated into oil phase and water.Measure the oil-contg in the isolated mud, the result is shown in the table 1.
(2) isolated oil phase is applied electric field, to remove the water in the oil phase.Wherein: temperature is 80 ℃, and the voltage of the electric field that applies is 3000V, and the time that applies electric field is 120min.Measure the water-content in the oil phase after processing.The result is shown in the table 1.
(3) adopt activated sludge process that isolated water is processed, to remove the oil of aqueous phase.The condition of activated sludge process comprises: mud age is 4d; Volume load is 0.5kgBOD
5/ (M
3D); The mass concentration of active sludge is 2300mg/L; Hydraulic detention time is 6h; Reflux ratio is 0.3.Measure the oil-contg of the aqueous phase after processing, the result is shown in the table 1.
(4) mud that separation is obtained is in blade drying machine (be purchased the dry Engineering Co., Ltd from Luoyang Rui Dao, model is RD-80), at 180 ℃ of lower dry 30min.The massfraction of the water in the dried mud is shown in the table 1.
Comparative Examples 6
Adopt the method identical with step (1) among the embodiment 5 that oily sludge is processed, different is, be that the polyoxyethylene polyoxypropylene ether emulsion splitter of initiator (is purchased from Sinopec Jing Zhou branch office in order to polyethylene polyamine, the trade mark is AE121) the replacement aluminium acetylacetonate, total amount with respect to the oil in the described oily sludge is benchmark, and the massfraction of described emulsion splitter is 0.002%.
Embodiment 6
Present embodiment is used for illustrating according to the method for the oil-contg in the reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge that uses in the present embodiment: as benchmark, this oily sludge contains 250.0g oil with the dried mud of 1kg; Take the total amount of oily sludge as benchmark, the massfraction of water is 90% in this oily sludge.
(1) adds Tungstophosphoric acid, sodium salt (be purchased congratulate from Shanghai precious chemical industry company limited) (wherein, the mass ratio of the oil in Tungstophosphoric acid, sodium salt and the described oily sludge is 0.03: 100) in the oily sludge.Mixture is placed autoclave, and with the air in the argon replaces autoclave, then in the situation of additionally not exerting pressure, under 180 ℃ temperature, react 20h.Place gravity settling tank to carry out gravity settling reaction product, with the mud that is isolated as solid phase and the liquid phase that contains oil and water.Adopt By Bubble-floating Method (wherein, the air supporting condition is: air flow quantity is 200std-L/h, and hydraulic detention time is 10min) to be separated into oil phase and water the liquid phase that obtains.Measure the oil-contg in the isolated mud, the result is shown in the table 1.
(2) add in the isolated oil phase and (be purchased from BASF AG with the polyoxyethylene polyoxypropylene ether emulsion splitter of propylene glycol as initiator, the trade mark is Pluronic 6200), take the total amount of described oil phase as benchmark, the massfraction of described emulsion splitter is 0.004%.Be 90 ℃ with the oil phase that is added with described emulsion splitter in temperature, voltage is in the electric field of 2300V, carries out the oily water separation of 200min, to remove the water in the oil phase.Measure the water-content in the oil phase after processing.The result is shown in the table 1.
(3) adopt microfiltration membrane (be purchased from Hydranautics company, model is ESPA1-4040) that isolated water is carried out micro-filtration, to remove the oil of aqueous phase.Measure the oil-contg of the aqueous phase after processing, the result is shown in the table 1.
(4) mud that separation is obtained is in indirect sludge drying machine (be purchased from the Sanmenxia Gorge hundred and get dry Engineering Co., Ltd), at 120 ℃ of lower dry 50min.The massfraction of the water in the dried mud is shown in the table 1.
Comparative Examples 7
Adopt the method identical with step (1) among the embodiment 6 that oily sludge is processed, different is, (be purchased chemical industry two factories from Sinopec Nanjing branch office in order to propylene glycol as the polyoxyethylene polyoxypropylene ether emulsion splitter of initiator, the trade mark is F3111) the replacement Tungstophosphoric acid, sodium salt, with respect to the amount of the oil in the described oily sludge, the massfraction of described emulsion splitter is 0.03%.
Embodiment 7
Present embodiment is used for illustrating according to the method for the oil-contg in the reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge that uses in the present embodiment: as benchmark, this oily sludge contains 150.0g oil with the dried mud of 1kg; Take the total amount of oily sludge as benchmark, the massfraction of water is 65% in this oily sludge.
(1) adds silicoaluminate ammonium (be purchased congratulate from Shanghai precious chemical industry company limited) (wherein, the mass ratio of the oil in silicoaluminate ammonium and the described oily sludge is 0.05: 100) in the oily sludge, mixture is placed autoclave, and use N
2Then air in the displacement autoclave in the situation of additionally not exerting pressure, reacts 32h under 240 ℃ temperature; Place gravity settling tank to carry out gravity settling reaction product, with the mud that is isolated as solid phase and the liquid phase that contains oil and water.Adopt By Bubble-floating Method (wherein, the air supporting condition is: air flow quantity is 180std-L/h, and hydraulic detention time is 10min) to be separated into oil phase and water the liquid phase that obtains.Measure the oil-contg in the isolated mud, the result is shown in the table 1.
(2) add polyoxypropylene take phenol-amine resin as initiator-Soxylat A 25-7 emulsion splitter (be purchased from upper seapeak dimension chemical industry company limited, model is TA1031) in the isolated oil phase, to remove the water in the oil phase.Take the total amount of described oil phase as benchmark, the massfraction of described emulsion splitter is 0.001%.Then apply electric field to described oil phase, to carry out oily water separation, wherein, the voltage of the electric field that applies is 4000V, and the time that applies electric field is 90min.Measure the water-content in the oil phase after processing.The result is shown in the table 1.
(3) adopt hollow fiber ultrafiltration membrane (be purchased from OKumei Environment Engineering Co., Ltd., Zhejiang, model is SFP-2860S) that isolated water is carried out ultrafiltration, to remove the oil of aqueous phase.Measure the oil-contg of the aqueous phase after processing, the result is shown in the table 1.
(4) mud that separation is obtained is in blade drying machine (be purchased the dry Engineering Co., Ltd from Luoyang Rui Dao, model is RD-30), at 230 ℃ of lower dry 45min.The massfraction of the water in the dried mud is shown in the table 1.
Comparative Examples 8
Adopt method identical in the step (1) with embodiment 7 that oily sludge is processed, different is, use with the ethylidene polyamines and (be purchased and forever believe Fine Chemical Co., Ltd from Liaoning as the polyoxypropylene of initiator-Soxylat A 25-7 emulsion splitter, the trade mark is AP221) replacement silicoaluminate ammonium, the total amount of the oil in the described oily sludge is as benchmark, and the massfraction of described emulsion splitter is 0.05%.
Embodiment 8
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Employing is processed oily sludge with the identical method among the embodiment 5, different is, step (1), in mixture, add methyl ethyl diketone (being purchased from the wide chemical industry of Nanjing moral company limited), the mass ratio of the oil in methyl ethyl diketone and the described oily sludge is 2: 100, and the temperature in the autoclave is 160 ℃.The result is shown in the table 1.
Embodiment 9
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Employing is processed oily sludge with the identical method among the embodiment 5, and different is that in the step (1), the temperature in the autoclave is 160 ℃.The result is shown in the table 1.
Embodiment 10
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Adopt the method identical with embodiment 6 that oily sludge is processed, different is, in the step (1), in mixture, add 2,4-hexanedione (be purchased from triumphant side's medical sci-tech (Shanghai) Co., Ltd.), the mass ratio of the oil in 2,4-hexanedione and the described oily sludge is 1: 100, and the temperature in the autoclave is 120 ℃.The result is shown in the table 1.
Embodiment 11
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Adopt the method identical with embodiment 6 that oily sludge is processed, different is that in the step (1), the interior temperature of autoclave is 120 ℃.The result is shown in the table 1.
Embodiment 12
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Adopt the method identical with embodiment 7 that oily sludge is processed, different is in the step (1), to add methyl ethyl diketone in mixture, the mass ratio of the oil in methyl ethyl diketone and the described oily sludge is 0.5: 100, and the temperature in the autoclave is 200 ℃.The result is shown in the table 1.
Embodiment 13
Present embodiment is used for illustrating according to the method for the oil-contg of reduction oily sludge of the present invention and the treatment process of oily sludge.
Adopt the method identical with embodiment 7 that oily sludge is processed, different is that in the step (1), the interior temperature of autoclave is 200 ℃.The result is shown in the table 1.
Table 1
*Oil recovery rate=(quality of the oil in the quality/oily sludge of the oil phase after the purification) * 100%
From the results shown in Table 1, the method according to this invention can reduce the oil-contg of oily sludge effectively, adopts method of the present invention to come oily sludge is processed, and can reclaim with high yield the oil in the described oily sludge.And, adopt according to of the present invention that oily sludge is processed the mud and the oil-contg in the water that obtain is low, can satisfy emission standard.
Embodiment 8 and embodiment 5 and embodiment 9, embodiment 10 and embodiment 6 and embodiment 11 and embodiment 12 are compared and can find out with embodiment 7 and embodiment 13, oily sludge is contacted in the presence of beta-diketon with hydrothermal cracking catalyst, not only can effectively reduce the oil-contg in the oily sludge, but also can reduce temperature of reaction, thereby further reduce the running cost of the method according to this invention.
Claims (22)
1. method that reduces the oil-contg of oily sludge, the method is included in the encloses container, and oily sludge is contacted with hydrothermal cracking catalyst, and the temperature of described contact is for being higher than 100 ℃ and be not higher than 374 ℃.
2. method according to claim 1, wherein, the mass ratio of the oil in described hydrothermal cracking catalyst and the described oily sludge is 0.0005～0.1: 100.
3. method according to claim 2, wherein, the mass ratio of the oil in described hydrothermal cracking catalyst and the described oily sludge is 0.001～0.05: 100.
4. the described method of any one according to claim 1～3, wherein, described hydrothermal cracking catalyst is one or more in transition metal salt, organic acid transition metal salt, organometallic complex, heteropolyacid and the heteropolyacid salt of mineral acid.
5. method according to claim 4, wherein, described hydrothermal cracking catalyst be the organometallic complex of organometallic complex, the group VIII metal of IIB family metal-salt, organic acid VIIB family metal-salt, organic acid I B-group metal salt, the group III A metal of mineral acid, take the group vib metal as polyatomic heteropolyacid salt and in take the group III A metal as polyatomic heteropolyacid salt one or more.
6. method according to claim 5, wherein, described hydrothermal cracking catalyst is one or more in acetylacetonate, an alkali metal salt take the group vib metal as polyatomic heteropolyacid and the ammonium salt take the group III A metal as polyatomic heteropolyacid of acetylacetonate, group III A metal of I B-group metal salt, the group VIII metal of VIIB family metal-salt, the naphthenic acid of IIB family metal-salt, the oleic acid of sulfuric acid.
7. method according to claim 6, wherein, described hydrothermal cracking catalyst is one or more in zinc sulfate, acetylacetonate nickel, manganese oleate, copper naphthenate, aluminium acetylacetonate, Tungstophosphoric acid, sodium salt and the silicoaluminate ammonium.
8. method according to claim 1, wherein, take the total mass of described oily sludge as benchmark, the massfraction of water is 20%～90% in the described oily sludge.
9. method according to claim 1, wherein, take the total amount of described oily sludge as benchmark, the massfraction of the water in the described oily sludge is for being lower than 20%, the method also is included in described oily sludge with before hydrothermal cracking catalyst contacts, described oily sludge is mixed with water, and the amount of described water is so that take the total amount of described oily sludge as benchmark, the massfraction of water is 20%～90% in the oily sludge.
10. method according to claim 9, wherein, the amount of described water is so that take the total amount of described oily sludge as benchmark, the massfraction of water is 20%～50% in the described oily sludge.
11. according to claim 1 or 9 described methods, wherein, the temperature of described contact is 150～350 ℃.
12. method according to claim 11, wherein, the temperature of described contact is 180～300 ℃.
13. according to claim 1 or 9 described methods, wherein, the temperature of described contact is 120～200 ℃, and described contact is carried out in the presence of the beta-diketon shown in one or more formula IIIs,
In the formula III, R
3And R
4C respectively does for oneself
1～C
6The straight or branched alkyl.
14. method according to claim 13, wherein, the mass ratio of oil is 0.3～3: 100 in the total amount of described beta-diketon and the described oily sludge.
15. method according to claim 14, wherein, the mass ratio of oil is 0.5～2: 100 in the total amount of described beta-diketon and the described oily sludge.
16. method according to claim 13, wherein, described beta-diketon is 2,4-diacetylmethane and/or 2,4-hexanedione.
17. according to claim 1 or 9 described methods, wherein, the time of described contact is 12～48h.
18. the described method of any one according to claim 1～3 and in 8～10, wherein, the content of oil is the dried mud of 100～1000g/kg in the described oily sludge.
19. the method that oily sludge is processed, the method comprises:
The described method of any one contacts described oily sludge in the employing claim 1～18 with hydrothermal cracking catalyst;
Isolate oil phase and water in the product of contact, to obtain solid phase;
Described oil phase and water are purified separately, so that the massfraction of water is lower than 0.5% in the described oil phase, the oil-contg of described aqueous phase is lower than 10mg/L; And
Remove the volatile matter in the described solid phase, so that the massfraction of water is lower than 30% in the described solid phase.
20. method according to claim 19 wherein, is isolated oil phase in the described product of contact and the method for water and is comprised: isolate the liquid phase in the described product of contact, and described liquid phase separation is become water and oil phase.
21. method according to claim 20, wherein, the method for isolating the liquid phase in the described product of contact comprises: described product of contact is carried out gravity settling or centrifugation, to isolate the liquid phase in the described product of contact.
22. method according to claim 21, wherein, the method that described liquid phase separation is become water and oil phase comprises: under the air supporting condition, described liquid phase separation is become water and oil phase, and tell described oil phase and water.
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| CN109293051B (en) * | 2018-10-22 | 2021-12-21 | 四川意德康环保科技有限公司 | Treatment system and method for high-suspended matter oily sewage |
| CN113419048A (en) * | 2021-06-23 | 2021-09-21 | 四川士达特种炭材有限公司 | Method for rapidly identifying oil content of carbon material |
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