CN102874998B - 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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- CN102874998B CN102874998B CN201110196157.2A CN201110196157A CN102874998B CN 102874998 B CN102874998 B CN 102874998B CN 201110196157 A CN201110196157 A CN 201110196157A CN 102874998 B CN102874998 B CN 102874998B
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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 process of oil production.The complicated component of oily sludge, can not directly utilize or row outward, usually used as waste, is stacked air-dry or buries undergroundly, and so both contaminate environment, waste again resource, return enterprise and bring huge financial loss.Oil and water contained in oily sludge form stable milk sap, be adsorbed on securely in the surface and hole of silt particle, and adhesive power strengthen with the increase of oily average molecular mass and 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 being formed by the lower oil of average molecular mass, and the treatment effect of the oily sludge forming 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, more than the method comprises milky liquid liquid or mud is heated to the boiling point of water, then enter and in knockout tower, carry out flash separation, 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, described mud is by after solid-liquid separation, be separated into heavy hydrocarbon and mud.High temperature re-treating process is mainly to reduce the oil viscosity in oily sludge by the mode of heating; Increase the collision rate of dispersed phase drop, thereby improve the molecular motion speed of disperse phase; Weaken the active of emulsifying agent and increase density difference between oil, water that oily sludge is separated into oil phase, water and solid phase, and by water is separated in time, and prevent from again occurring emulsification.Therefore, high temperature re-treating process is in fact a kind of physical method.And, although high temperature re-treating process is comparatively effective for the oily sludge being formed by the lower oil of average molecular mass, but the treatment effect of the oily sludge forming for oil higher by average molecular mass and that viscosity is higher is still undesirable, and processing cost is higher.In addition, although high temperature re-treating process can be processed oily sludge effectively, this technique need to be carried out the oily sludge of heating flash distillation in knockout tower, and therefore 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 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, by oily sludge and hydrothermal cracking catalyst higher than 100 ℃ and not higher than the temperature of 374 ℃ under contact, only product of contact need be carried out in conventional equipment for separating liquid from solid to solid-liquid separation can be by the most of oil phase in oily sludge and aqueous phase separation out, and then realize the separation of oil, mud, water three-phase.Completed thus the present invention.
A first aspect of the present invention provides a kind of method of the oil-contg that reduces oily sludge, and the method is included in encloses container, and oily sludge is contacted with hydrothermal cracking catalyst, and the temperature of described contact is higher than 100 ℃ and 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 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 described oil phase, the oil-contg in described water is lower than 10mg/L; And
Remove the volatile matter in described solid phase so that in described solid phase the massfraction of water lower than 30%.
The method according to this invention is in encloses container, by oily sludge and hydrothermal cracking catalyst higher than 100 ℃ and not higher than the temperature of 374 ℃ under contact, oily sludge after 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, oil recovery rate is high, and the oleaginousness in the mud and the water that obtain significantly reduces, can meet the requirement of discharge or reuse.
Particularly, adopt the method according to this invention to process oily sludge, in mass, in oily sludge, the decreasing ratio of oil can reach more than 98%, and oil recovery rate can reach more than 95%; And the mud obtaining and water can meet respectively the standard of reuse or discharge, wherein, the oleaginousness in the water of recovery can be lower than 10mg/L, and the oil-contg in the mud obtaining can be lower than the dry mud of 3g/kg (, with respect to the dry mud of 1kg, the oil-contg in the mud obtaining is 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 of the oil-contg that reduces oily sludge, the method is included in encloses container, and oily sludge is contacted with hydrothermal cracking catalyst, and the temperature of described contact is higher than 100 ℃ and not higher than 374 ℃.
In the present invention, term " oil " refers to the hydrophobic nature material producing in crude oil and Crude Oil Processing, comprise under normal temperature being liquid hydrophobic nature material, and under normal temperature, be the hydrophobic nature material of colloidal state, for example: the various oil soluble surfactants that use in hydrocarbons, oil recovery process.
The method according to this invention, described hydrothermal cracking catalyst can be the various materials oily aquathermolysis to katalysis.Preferably, one or more in described hydrothermal cracking catalyst is mineral acid transition metal salt, organic acid transition metal salt, organometallic complex, heteropolyacid and heteropolyacid salt.
In 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.
In 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).
In 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: containing the compound (as: α-diketone, beta-diketon, γ-diketone) of carbonyl.Preferably, described carbonyl containing compound is the beta-diketon shown in formula I,
In formula I, R
1and R
2can be C separately
1～C
6straight or branched alkyl.
In the present invention, C
1～C
6straight 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 be 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.
In the present invention, described heteropolyacid refers to that the class being comprised of oxygen atom ligand bridging by certain structure heteroatoms and polyatom is containing oxygen polyacid.Heteropolyacid salt refers to that at least part of hydrogen ion in 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, phosphorus aluminic acid, phospho-wolframic acid, phosphorus vanadic acid, silicoaluminate, silicotungstic acid, silicon molybdenum wolframic acid, P-Mo-Wo acid, sulfo-molybdic acid, phosphorus ammonium aluminate, ammonium phosphowolframate, phosphorus ammonium vanadate, silicoaluminate ammonium, ammonium silicotungstic, ammonium thiomolybdate, phosphorus sodium aluminate, Tungstophosphoric acid, sodium salt, 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 group vib metal as polyatomic heteropolyacid, take group vib metal as polyatomic heteropolyacid salt, take group III A metal as polyatomic heteropolyacid, take group III A metal as polyatomic heteropolyacid salt, one or more in polyatomic heteropolyacid salt take VB family metal as polyatomic heteropolyacid with take VB family metal.
The organometallic complex of IIB family metal-salt that more preferably, described hydrothermal cracking catalyst is mineral acid, organic acid VIIB family metal-salt, organic acid I B-group metal salt, group III A metal, the organometallic complex of group VIII metal, one or more in polyatomic heteropolyacid salt take group vib metal as polyatomic heteropolyacid salt with take group III A metal.
Further preferably, described hydrothermal cracking catalyst is: one or more in acetylacetonate, an alkali metal salt take group vib metal as polyatomic heteropolyacid and the ammonium salt take 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.
In the present invention, naphthenic acid can be the conventional various compounds that can form with metal ion salt in this area.Preferably, described naphthenic acid is the compound shown in formula II,
In 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 silicoaluminate ammonium.
According to the inventive method, for the consumption of described catalyzer, be not particularly limited, can carry out appropriate selection according to the character of oily sludge.Usually, in described hydrothermal cracking catalyst and described oily sludge, the mass ratio of oil can be 0.0005～0.1: 100.Preferably, in described hydrothermal cracking catalyst and described oily sludge, the mass ratio of oil is 0.001～0.05: 100.Further preferably, in described hydrothermal cracking catalyst and described oily sludge, the mass ratio of oil is 0.005～0.05: 100.
The method according to this invention comprises oily sludge contacted with hydrothermal cracking catalyst, and described contact is generally carried out under the existence 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%), without supplementing and add water in this oily sludge, directly described oily sludge is contacted and can realize object of the present invention with hydrothermal cracking catalyst.When the massfraction of water in described oily sludge is lower than 20% time, can add water by supplementing in described oily sludge, and oily sludge is mixed with water, the addition of water makes total amount take described oily sludge as benchmark, and in described oily sludge, the massfraction of water (for example: 20%～90%) is at least more than 20%.
That is, the method according to this invention, is benchmark in the total amount take described oily sludge, in described oily sludge the 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; In the total amount take described oily sludge, it is benchmark, in described oily sludge, the massfraction of water is lower than 20% time, described water comprises the water that oily sludge itself contains and supplement the water adding in oily sludge, the amount of the water of described supplementary interpolation makes total amount take described oily sludge as benchmark, and 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 are 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 make the oil in oily sludge be easy to desorption from mud.Usually, described hydrothermal cracking catalyst and described oily sludge contact can higher than 100 ℃ and not higher than the temperature of 374 ℃ under carry out.Preferably, described hydrothermal cracking catalyst is 150～350 ℃ with the temperature contacting of described oily sludge.From the oil-contg of further reduction oily sludge, take into account the angle of energy consumption, the temperature of described contact is 180～300 ℃ simultaneously.
The method according to this invention, the present inventor is surprised to find that in research process, under equal conditions, when contacting of described hydrothermal cracking catalyst and described oily sludge carried out under the existence at one or more beta-diketons, can further reduce the Contact Temperature of described hydrothermal cracking catalyst and described oily sludge.The method according to this invention, when contacting of described hydrothermal cracking catalyst and described oily sludge carried out under the existence at one or more beta-diketons, described hydrothermal cracking catalyst can carry out with contacting of described oily sludge under the condition of 120～200 ℃.
Described beta-diketon can be by a methylene radical (CH between common two carbonyls
2) or the various dione compounds that separate of methyne (CH).Preferably, described beta-diketon is the beta-diketon shown in formula III,
In formula III, R
3and R
4can be C separately
1～C
6straight or branched alkyl.
The method according to this invention, the example of described beta-diketon can be 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--3,5-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 oily quality in the total mass of described beta-diketon and described oily sludge is 0.3～3: 100.Further preferably, in the total mass of described beta-diketon and described oily sludge, the mass ratio of oil is 0.5～2: 100.
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 while contacting with hydrothermal cracking catalyst for described oily sludge is not particularly limited.Described contact can (that is, oxygen-containing atmosphere) be carried out under oxygen exists, and also can in non-oxygen atmosphere, carry out.The method according to this invention, when described contact is carried out under oxygen exists, can further reduce the running cost of the method according to this invention.That is to say, when contact of the present invention is carried out under oxygen exists, described oxygen can be the oxygen carrying in reactor and/or reaction raw materials.
The method according to this invention, (described contact can additionally not exert pressure, except the autogenous pressure of reactor, no longer additionally exert pressure) condition under carry out, also can under the condition of pressurization, carry out (, except the autogenous pressure of reactor, also additionally exert pressure).When described contact is carried out under pressurized conditions, to applied pressure in the encloses container contacting, can be 0.01～2MPa, be 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 conventional various containers that can realize sealing function.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, in described oily sludge, the content of oil can be the dry mud of 100～1000g/kg.
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 Oil extraction process, for example: the oily sludge producing in the oily sludge producing in oilfield transportation system, the oily sludge of refinery's Bottom Plate of Crude Oil Storage and 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 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 described oil phase, the oil-contg in described water is lower than 10mg/L; And
Remove the volatile matter in described solid phase so that in described solid phase the massfraction of water lower than 30%.
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 mud of the oil in 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 above, 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 to oil phase and the water in the product of contact obtaining with hydrothermal cracking catalyst, to obtain solid phase.
According to the method that oily sludge is processed of the present invention, by by oily sludge and hydrothermal cracking catalyst higher than 100 ℃ and not higher than the temperature of 374 ℃ under contact, make the oil that is adsorbed on Sludge Surface be easy to the surface desorption from mud, oily sludge after contact, without 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 the conventional the whole bag of tricks in this area.
A kind of embodiment of the method that oily sludge is processed according to the present invention, isolates oil phase and water in product of contact, comprises: isolate the liquid phase in described product of contact, and described liquid phase separation is become to water and oil phase with the method that obtains solid phase.
Can adopt the conventional the whole bag of tricks in this area to isolate the liquid phase in described product of contact.For example: the method for isolating the liquid phase in described product of contact comprises: described product of contact is carried out to gravity settling or centrifugation, to isolate the liquid phase in described product of contact.The equipment that described gravity settling and centrifugation are used and method are known in the field.For example, described product of contact can be placed in to gravity settling chamber or gravity settling tank, by the effect of gravity, make mud and the liquid phase separation that contains oil and water; Described product of contact can also be made in centrifugation apparatus to mud and the liquid phase separation that contains oil and water by means of centrifugal force.
In this embodiment, can be according to the character of the liquid phase obtaining, adopt the conventional the whole bag of tricks in this area that described liquid phase separation is become to water and oil phase.For example: under air supporting condition, this liquid phase separation is become to water and oil phase, and separate described oil phase and water.
By under air supporting condition, when described liquid phase separation is become to 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 30～300std-L/h (that is, standard l/h), is preferably 50～200std-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 described oil phase, the oil-contg in described water is lower than 10mg/L.
Can adopt the conventional the whole bag of tricks in this area to purify isolated water and isolated oil phase.
Usually, the method isolated water being purified can comprise: to throwing in coagulating agent in isolated water, isolated water being carried out biochemical treatment or isolated water is filtered.Aforesaid method can also be used in combination.
Described coagulating agent can be the conventional various coagulating agent in this area, for example: one or more in the salt of aluminium, the polymkeric substance of aluminium, the salt of iron and the compound of iron.In the present invention, the example of described coagulating agent can be 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 under the condition of this area routine, adopt the conventional method in this area to carry out.For example, the method for described biochemical treatment can be 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 is also not particularly limited for the method for described filtration, and for example, described filtration can be the one in sand filtration, micro-filtration, ultrafiltration, nanofiltration and reverse osmosis.Above-mentioned filter method can also be used in combination.
Usually, the method isolated oil phase being purified comprises: isolated oil phase is carried out to electric desalting.Described electric desalting can be carried out in the conventional electric desalting equipment in this area under normal condition.The condition of for example described electric desalting can be: 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 under emulsion splitter exists, and described emulsion splitter can be the conventional various emulsion splitters in this area, and for example, described emulsion splitter can be non-ionic demulsifier.More preferably, described emulsion splitter is that polyethers is emulsion splitter.In the present invention, the example of described emulsion splitter can for but be not limited to: the Pluronic F68 take alcohol (as: glycerol, propylene glycol or ethylene glycol) as the polyoxypropylene-polyoxyethylene copolymer of initiator, take amine (as: polyethylene polyamine) as the polyoxypropylene-polyoxyethylene copolymer of initiator, 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 described solid phase (, the mud obtaining) in volatile matter, and by remove solid phase after described volatile matter dry so that in mud the massfraction of water lower than 30% (that is, the mud obtaining being carried out to minimizing processing).Can adopt method well known in the art to remove the volatile matter in the solid phase obtaining, repeat no more herein.
Below in conjunction with embodiment, describe the present invention in detail.
The testing method relating in following examples comprises:
The mensuration of oleaginousness in mud: adopt infrared spectrophotometry, divide the method for regulation to measure according to the determination part of < < CJ/T 221-2005 sludge from wastewater treatment plant method of inspection > > mineral oil in fluid.
The mensuration of water content in mud: adopt mass method, divide the method for regulation to measure according to the determination part of water ratio in < < CJ/T 221-2005 sludge from wastewater treatment plant method of inspection > >.
The mensuration of oleaginousness in water: adopt infrared spectrophotometry, measure according to the method stipulating in the mensuration > > of < < GB/T 16488-1996 water-quality petroleum and vegetable and animals oils.
The mensuration of Water in oil amount: measure according to the method for the regulation in < < GB/T 260-1977 (1988) petroleum products aquametry > >.
Embodiment 1
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Consisting of of the oily sludge using in the present embodiment: take the dry mud of 1kg as benchmark, this oily sludge contains 600.0g oil; Take the total amount of oily sludge as benchmark, in this oily sludge, the massfraction of water is 45%.
(1) in oily sludge, add ZnSO
4(wherein, ZnSO
4with the oily mass ratio in described oily sludge be 0.005: 100), then by mixture at N
2in atmosphere, additionally in the situation of pressurization, in being the closed reactor of 240 ℃, temperature do not react 30h; Reaction product is carried out in gravity settling tank to gravity settling, the liquid phase that separation obtains mud and contains oil and water, adopt By Bubble-floating Method (wherein, 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 obtaining.Measure the oil-contg in isolated mud, result is shown in table 1.
(2) in isolated oil phase, add the polyoxyethylene polyoxypropylene ether emulsion splitter using stearyl alcohol as initiator (to be purchased from chemical plant, Liaoyuan, Jilin, the trade mark is SP169), take the quality of described oil phase as benchmark, the massfraction of described emulsion splitter is 0.001%.In temperature, be 80 ℃, in the electric field that voltage is 2000V, carry out the oily water separation of 60min.Measure the water-content in oil phase after processing.Result is shown in table 1.
(3) adopt BAF method to process isolated water.Wherein, the condition of BAF method comprises: temperature is 35 ℃, and air water volume ratio is 3: 1, and hydraulic detention time is 6h.Measure the oil-contg in water after treatment, result is shown in table 1.
(4) mud separation being obtained, in revolver drier (be purchased from North China drying plant factory, model is GZT10), is dried 30min at 150 ℃.The massfraction of the water in dried mud is shown in table 1.
Comparative example 1
Adopt the method identical with step (1) in embodiment 1 to process oily sludge, different, do not use ZnSO
4.
Comparative example 2
Adopt the method identical with step (1) in embodiment 1 to process oily sludge, different, the temperature in closed reactor is 80 ℃.
Comparative example 3
Adopt the method identical with step (1) in embodiment 1 to process oily sludge, different is, in order to propylene glycol, as the polyoxyethylene polyoxypropylene ether emulsion splitter (be purchased chemical industry two factories from Sinopec Nanjing branch office, the trade mark is F3111) of initiator, replace ZnSO
4, take the oily quality in described oily sludge as benchmark, the massfraction of described emulsion splitter is 0.005%.
Embodiment 2
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Adopt the method identical with embodiment 1 to process oily sludge, different, use acetylacetonate nickel (being purchased from Beijing Yili Fine Chemicals Co., Ltd.) as catalyzer.Result is shown in table 1.
Embodiment 3
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Consisting of of the oily sludge using in the present embodiment: take the dry mud of 1kg as benchmark, this oily sludge contains 200.0g oil; Take the total amount of oily sludge as benchmark, in this oily sludge, the massfraction of water is 10%.
(1) in oily sludge, add water, the massfraction that makes to add water in the oily sludge after water reaches 20%, oily sludge is mixed with water, in the mixture obtaining, add manganese oleate (being purchased from Beijing Yili Fine Chemicals Co., Ltd.) (wherein, oily mass ratio in manganese oleate and described oily sludge is 0.01: 100), then by mixture in air atmosphere, additionally in the situation of pressurization, in being the closed reactor of 200 ℃, temperature do not react 36h; Reaction product is carried out in gravity settling tank to gravity settling, the liquid phase that separation obtains mud and contains oil and water, adopt By Bubble-floating Method (wherein, 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 obtaining.Measure the oil-contg in isolated mud, result is shown in table 1.
(2) at 100 ℃, isolated oil phase is applied to electric field, carry out oily water separation, wherein, the voltage of the electric field applying is 2000V, the time that applies electric field is 60min.Measure the water-content in oil phase after treatment.Result is shown in 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) to filter isolated water.Measure the oil-contg in water after treatment, result is shown in table 1.
(4) mud separation being obtained, indirect sludge drying machine (be purchased from the Sanmenxia Gorge hundred and must be dried Engineering Co., Ltd), is dried 20min at 160 ℃.The massfraction of the water in dried mud is shown in table 1.
Comparative example 4
Adopt the method identical with step (1) in embodiment 3 to process oily sludge, different is, the polyoxyethylene polyoxypropylene ether emulsion splitter that is initiator in order to resol (is purchased from Binzhou Chemical Plant, Shandong Prov., the trade mark is BSE311) replacement manganese oleate, take the oily quality in described oily sludge as benchmark, the massfraction of described emulsion splitter is 0.01%.
Embodiment 4
The present embodiment is used for explanation according to the method for oil-contg in reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge using in the present embodiment: take the dry mud of 1kg as benchmark, this oily sludge contains 300.0g oil; Take the total amount of oily sludge as benchmark, in this oily sludge, the massfraction of water is 35%.
(1) to add in oily sludge copper naphthenate (
m is 6, is purchased from Gansu Provincial Chemical Industry Inst.) (wherein, the oily mass ratio in copper naphthenate and described oily sludge is 0.015: 100), then mixture is placed in to autoclave, enclosed high pressure reactor; And be filled with N in this autoclave
2, making the gauge pressure in this autoclave is 1MPa; Then, the temperature in autoclave is increased to 300 ℃, and reacts 24h at this temperature.Reaction product is placed in to separating centrifuge and carries out centrifugation, the liquid phase that obtains mud and contain oil and water.Adopt By Bubble-floating Method (wherein, 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 obtaining.Measure the oil-contg in isolated mud, result is shown in table 1.
(2) in isolated oil phase, add the polyoxyethylene polyoxypropylene ether emulsion splitter using resol as initiator (to be purchased from upper seapeak and to tie up Chemical Co., Ltd., the trade mark is AR36), take the total amount of described oil phase as benchmark, the massfraction of described emulsion splitter is 0.003%.By the oil phase that is added with described emulsion splitter, in temperature, be 100 ℃, in the electric field that voltage is 3000V, carry out the oily water separation of 40min, to remove the water in oil phase.Measure the water-content in oil phase after treatment, result is shown in table 1.
(3) in isolated water, add polymerize aluminum chloride (being purchased from Shandong Zhong Ketianze water-purifying material company limited), with respect to the water of 1L, the addition of polymerize aluminum chloride is 300mg; Then stir 10 minutes, after standing 30 minutes, filter, to remove the oil in water.Measure the oil-contg in water after treatment, result is shown in table 1.
(4) mud separation being obtained, in revolver drier (be purchased from North China drying plant factory, model is GZT10), is dried 30min at 200 ℃.The massfraction of the water in dried mud is shown in table 1.
Comparative example 5
Adopt the method identical with step (1) in embodiment 4 to process oily sludge, different is, the polyoxyethylene polyoxypropylene ether emulsion splitter of use using stearyl alcohol as initiator (is purchased from chemical plant, Liaoyuan, Jilin, the trade mark is SP169) replacement copper naphthenate, take the oily total amount in described oily sludge as benchmark, the massfraction of described emulsion splitter is 0.015%.
Embodiment 5
The present embodiment is used for explanation according to the method for oil-contg in reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge using in the present embodiment: take the dry mud of 1kg as benchmark, this oily sludge contains 360.0g oil; Take the total amount of oily sludge as benchmark, in this oily sludge, the massfraction of water is 15%.
(1) in oily sludge, add water, the massfraction that makes to add water in the oily sludge after water is 30%, oily sludge is mixed with water, in the mixture obtaining, add aluminium acetylacetonate (being purchased from Hangzhou chemical reagent company limited) (wherein, oily mass ratio in aluminium acetylacetonate and described oily sludge is 0.02: 100), then mixture is placed in to autoclave, enclosed high pressure reactor; And be filled with air in this autoclave, making the gauge pressure in this autoclave is 0.5MPa; Then, the temperature in autoclave is risen to 220 ℃, and react 28h at this temperature.Reaction product is placed in to separating centrifuge and carries out centrifugation, thereby by the mud for solid phase and the liquid phase separation that contains oil and water, the liquid phase obtaining is adopted to By Bubble-floating Method (wherein, 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 isolated mud, result is shown in table 1.
(2) isolated oil phase is applied to electric field, to remove the water in oil phase.Wherein: temperature is 80 ℃, the voltage of the electric field applying is 3000V, and the time that applies electric field is 120min.Measure the water-content in oil phase after treatment.Result is shown in table 1.
(3) adopt activated sludge process to process isolated water, to remove the oil in water.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 in water after treatment, result is shown in table 1.
(4) mud separation being obtained, in blade drying machine (be purchased the dry Engineering Co., Ltd from Luoyang Rui Dao, model is RD-80), is dried 30min at 180 ℃.The massfraction of the water in dried mud is shown in table 1.
Comparative example 6
Adopt the method identical with step (1) in embodiment 5 to process oily sludge, different is, the polyoxyethylene polyoxypropylene ether emulsion splitter that is initiator in order to polyethylene polyamine (is purchased from Sinopec Jing Zhou branch office, the trade mark is AE121) replacement aluminium acetylacetonate, with respect to the oily total amount in described oily sludge, be benchmark, the massfraction of described emulsion splitter is 0.002%.
Embodiment 6
The present embodiment is used for explanation according to the method for oil-contg in reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge using in the present embodiment: take the dry mud of 1kg as benchmark, this oily sludge contains 250.0g oil; Take the total amount of oily sludge as benchmark, in this oily sludge, the massfraction of water is 90%.
(1) in oily sludge, add Tungstophosphoric acid, sodium salt (being purchased from Shanghai He Bao Chemical Co., Ltd.) (wherein, the oily mass ratio in Tungstophosphoric acid, sodium salt and described oily sludge is 0.03: 100).Mixture is placed in to autoclave, and with the air in argon replaces autoclave, then, in the situation that additionally not exerting pressure, at the temperature of 180 ℃, reacts 20h.Reaction product is placed in to gravity settling tank and carries out gravity settling, with the liquid phase that is isolated as the mud of solid phase and contains oil and water.Adopt By Bubble-floating Method (wherein, 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 obtaining.Measure the oil-contg in isolated mud, result is shown in table 1.
(2) in isolated oil phase, add the polyoxyethylene polyoxypropylene ether emulsion splitter using propylene glycol as initiator (to be purchased from BASF AG, 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%.By the oil phase that is added with described emulsion splitter, in temperature, be 90 ℃, in the electric field that voltage is 2300V, carry out the oily water separation of 200min, to remove the water in oil phase.Measure the water-content in oil phase after treatment.Result is shown in table 1.
(3) adopt microfiltration membrane (be purchased from Hydranautics company, model is ESPA1-4040) to carry out micro-filtration to isolated water, to remove the oil in water.Measure the oil-contg in water after treatment, result is shown in table 1.
(4) mud separation being obtained, in indirect sludge drying machine (be purchased from the Sanmenxia Gorge hundred and must be dried Engineering Co., Ltd), is dried 50min at 120 ℃.The massfraction of the water in dried mud is shown in table 1.
Comparative example 7
Adopt the method identical with step (1) in embodiment 6 to process oily sludge, different is, in order to propylene glycol, as the polyoxyethylene polyoxypropylene ether emulsion splitter of initiator, (be purchased chemical industry two factories from Sinopec Nanjing branch office, the trade mark is F3111) replacement Tungstophosphoric acid, sodium salt, with respect to the oily amount in described oily sludge, the massfraction of described emulsion splitter is 0.03%.
Embodiment 7
The present embodiment is used for explanation according to the method for oil-contg in reduction oily sludge of the present invention and the treatment process of oily sludge.
Consisting of of the oily sludge using in the present embodiment: take the dry mud of 1kg as benchmark, this oily sludge contains 150.0g oil; Take the total amount of oily sludge as benchmark, in this oily sludge, the massfraction of water is 65%.
(1) in oily sludge, add silicoaluminate ammonium (being purchased from Shanghai He Bao Chemical Co., Ltd.) (wherein, oily mass ratio in silicoaluminate ammonium and described oily sludge is 0.05: 100), mixture is placed in to autoclave, and uses N
2air in displacement autoclave then, in the situation that additionally not exerting pressure, reacts 32h at the temperature of 240 ℃; Reaction product is placed in to gravity settling tank and carries out gravity settling, with the liquid phase that is isolated as the mud of solid phase and contains oil and water.Adopt By Bubble-floating Method (wherein, 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 obtaining.Measure the oil-contg in isolated mud, result is shown in table 1.
(2) in isolated oil phase, add the polyoxypropylene-Soxylat A 25-7 emulsion splitter (be purchased from upper seapeak and tie up Chemical Co., Ltd., model is TA1031) take phenol-amine resin as initiator, to remove the water in oil phase.Take the total amount of described oil phase as benchmark, the massfraction of described emulsion splitter is 0.001%.Then to described oil phase, apply electric field, to carry out oily water separation, wherein, the voltage of the electric field applying is 4000V, and the time that applies electric field is 90min.Measure the water-content in oil phase after treatment.Result is shown in table 1.
(3) adopt hollow fiber ultrafiltration membrane (be purchased from OKumei Environment Engineering Co., Ltd., Zhejiang, model is SFP-2860S) to carry out ultrafiltration to isolated water, to remove the oil in water.Measure the oil-contg in water after treatment, result is shown in table 1.
(4) mud separation being obtained, in blade drying machine (be purchased the dry Engineering Co., Ltd from Luoyang Rui Dao, model is RD-30), is dried 45min at 230 ℃.The massfraction of the water in dried mud is shown in table 1.
Comparative example 8
Adopt with method identical in the step (1) of embodiment 7 oily sludge is processed, different is, polyoxypropylene-Soxylat A 25-7 the emulsion splitter of use take ethylidene polyamines as initiator (is purchased from Liaoning Yong Xin Fine Chemical Co., Ltd, the trade mark is AP221) replacement silicoaluminate ammonium, take the oily total amount in described oily sludge as benchmark, the massfraction of described emulsion splitter is 0.05%.
Embodiment 8
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Adopt and with the identical method in embodiment 5, oily sludge is processed, different is, step (1), in mixture, add methyl ethyl diketone (being purchased from Nanjing De Guang Chemical Co., Ltd.), oily mass ratio in methyl ethyl diketone and described oily sludge is 2: 100, and the temperature in autoclave is 160 ℃.Result is shown in table 1.
Embodiment 9
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Adopt and with the identical method in embodiment 5, oily sludge is processed, different, in step (1), the temperature in autoclave is 160 ℃.Result is shown in table 1.
Embodiment 10
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Adopt the method identical with embodiment 6 to process oily sludge, different is, in step (1), in mixture, add 2,4-hexanedione (being purchased from Kai Fang medical sci-tech (Shanghai) Co., Ltd.), oily mass ratio in 2,4-hexanedione and described oily sludge is 1: 100, and the temperature in autoclave is 120 ℃.Result is shown in table 1.
Embodiment 11
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Adopt the method identical with embodiment 6 to process oily sludge, different, in step (1), the temperature in autoclave is 120 ℃.Result is shown in table 1.
Embodiment 12
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Adopt the method identical with embodiment 7 to process oily sludge, different, in step (1), in mixture, add methyl ethyl diketone, oily mass ratio in methyl ethyl diketone and described oily sludge is 0.5: 100, and the temperature in autoclave is 200 ℃.Result is shown in table 1.
Embodiment 13
The present embodiment is used for explanation according to the treatment process of the method for the oil-contg of reduction oily sludge of the present invention and oily sludge.
Adopt the method identical with embodiment 7 to process oily sludge, different, in step (1), the temperature in autoclave is 200 ℃.Result is shown in table 1.
Table 1
*oil recovery rate=(the oily quality in the quality/oily sludge of the oil phase after 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 process oily sludge, can reclaim the oil in described oily sludge with high yield.And, adopt according to of the present invention that oily sludge to be processed to oil-contg in mud and the water obtaining low, can meet 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 be found out with embodiment 7 and embodiment 13, oily sludge is contacted under beta-diketon exists with hydrothermal cracking catalyst, not only can effectively reduce the oil-contg in oily sludge, but also can reduce temperature of reaction, thereby further reduce the running cost of the method according to this invention.
Claims (21)
1. one kind is reduced the method for the oil-contg of oily sludge, the method is included in encloses container, oily sludge is contacted with hydrothermal cracking catalyst, the temperature of described contact is higher than 100 ℃ and not higher than 374 ℃, one or more in transition metal salt, organic acid transition metal salt, organometallic complex, heteropolyacid and heteropolyacid salt that described hydrothermal cracking catalyst is mineral acid.
2. method according to claim 1, wherein, the oily mass ratio in described hydrothermal cracking catalyst and described oily sludge is 0.0005～0.1:100.
3. method according to claim 2, wherein, the oily mass ratio in described hydrothermal cracking catalyst and described oily sludge is 0.001～0.05:100.
4. method according to claim 1, the organometallic complex of IIB family metal-salt that wherein, described hydrothermal cracking catalyst is mineral acid, organic acid VIIB family metal-salt, organic acid I B-group metal salt, group III A metal, the organometallic complex of group VIII metal, one or more in polyatomic heteropolyacid salt take group vib metal as polyatomic heteropolyacid salt with take group III A metal.
5. method according to claim 4, one or more in acetylacetonate, an alkali metal salt take group vib metal as polyatomic heteropolyacid and the ammonium salt take group III A metal as polyatomic heteropolyacid of the I B-group metal salt of the IIB family metal-salt that wherein, described hydrothermal cracking catalyst is sulfuric acid, the VIIB family metal-salt of oleic acid, naphthenic acid, the acetylacetonate of group VIII metal, group III A metal.
6. method according to claim 5, 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 silicoaluminate ammonium.
7. method according to claim 1, wherein, take the total mass of described oily sludge as benchmark, in described oily sludge, the massfraction of water is 20%～90%.
8. method according to claim 1, wherein, take the total amount of described oily sludge as benchmark, the massfraction of the water in described oily sludge is lower than 20%, before the method is also included in described oily sludge is contacted with hydrothermal cracking catalyst, described oily sludge is mixed with water, and the amount of described water makes total amount take described oily sludge as benchmark, in oily sludge, the massfraction of water is 20%～90%.
9. method according to claim 8, wherein, the amount of described water makes total amount take described oily sludge as benchmark, and in described oily sludge, the massfraction of water is 20%～50%.
10. according to the method described in claim 1 or 8, wherein, the temperature of described contact is 150～350 ℃.
11. methods according to claim 10, wherein, the temperature of described contact is 180～300 ℃.
12. according to the method described in claim 1 or 8, and wherein, the temperature of described contact is 120～200 ℃, and described contact is carried out under the existence of the beta-diketon shown in one or more formula IIIs,
In formula III, R
3and R
4c respectively does for oneself
1～C
6straight or branched alkyl.
13. methods according to claim 12, wherein, in the total amount of described beta-diketon and described oily sludge, the mass ratio of oil is 0.3～3:100.
14. methods according to claim 13, wherein, in the total amount of described beta-diketon and described oily sludge, the mass ratio of oil is 0.5～2:100.
15. methods according to claim 12, wherein, described beta-diketon is 2,4-diacetylmethane and/or 2,4-hexanedione.
16. according to the method described in claim 1 or 8, and wherein, the time of described contact is 12～48h.
17. according to the method described in any one in claim 1～3 and 7～9, and wherein, in described oily sludge, the content of oil is the dry mud of 100～1000g/kg.
18. 1 kinds of methods that oily sludge is processed, the method comprises:
Adopt the method described in any one in claim 1～17 that described oily sludge is contacted with hydrothermal cracking catalyst;
Isolate oil phase and water in 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 described oil phase, the oil-contg in described water is lower than 10mg/L; And
Remove the volatile matter in described solid phase so that in described solid phase the massfraction of water lower than 30%.
19. methods according to claim 18, wherein, isolate oil phase in described product of contact and the method for water and comprise: isolate the liquid phase in described product of contact, and described liquid phase separation is become to water and oil phase.
20. methods according to claim 19, wherein, the method for isolating the liquid phase in described product of contact comprises: described product of contact is carried out to gravity settling or centrifugation, to isolate the liquid phase in described product of contact.
21. methods according to claim 20, wherein, the method that described liquid phase separation is become to water and oil phase comprises: under air supporting condition, described liquid phase separation is become to water and oil phase, and separate described oil phase and water.
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