CN1243072C - Method for recovering clean oil from heavy dirty oil - Google Patents
Method for recovering clean oil from heavy dirty oil Download PDFInfo
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- CN1243072C CN1243072C CN 03134933 CN03134933A CN1243072C CN 1243072 C CN1243072 C CN 1243072C CN 03134933 CN03134933 CN 03134933 CN 03134933 A CN03134933 A CN 03134933A CN 1243072 C CN1243072 C CN 1243072C
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Abstract
The present invention provides a method for recovering clean oil from heavy dirty oil, which comprises two steps. Step one, ferric salts and aluminum salts or an inorganic polymer and a mixture of the ferric salts and the aluminum salts or any mixture of the ferric salts and the aluminum salts as a purifying agent are added into the heavy dirty oil under an alkaline condition so that metal ions and OH-root irons form a coagulation center and the coagulation center is uniformly dispersed in the heavy dirty oil and the heavy dirty oil in the form of a W/O or O/W/O type emulsified liquid is converted to an O/W type emulsified liquid form; organic sludge and mineral sludge released in the conversion process of the emulsified liquid and the coagulation center form a floccus object with large density, the floccus object is divided into three layers by means of gravity action, and the lower layer is removed. Step two, divalent/trivalent metal ions are reduced from the floccus object in the enriched oil under an acid condition so that fatty acids and naphthenic soaps are changed to free fatty acids and naphthenic acids without emulsification to reach the aim of breaking the O/W type emulsified liquid so as to realize the separation of oil, mud and water; the mud and the water are removed to obtain the clean oil.
Description
Affiliated technical field
The invention belongs to the recovery technology of heavy sump oil processing and edible vegetable oil, what relate generally to is a kind of method that reclaims edible vegetable oil from heavy sump oil.
Background technology
In the crude refining process, processes such as water, flushing ground, chemical examination blowdown are cut in crude oil electric desalting, oil product tank field can produce a large amount of oily(waste)waters, the sump oil that reclaims through oil removal, flotation, after coalescent is so-called heavy sump oil, mainly is made up of oil content, silt, organic sludge, surfactant and a large amount of water.Heavy sump oil generally exists with the form of W/O or O/W/O type emulsion at normal temperatures, is difficult to breakdown of emulsion.Existing heavy sump oil isolation technique mainly contains two kinds, Gu the first utilizes oil-water-three-phase centrifuge to separate, western developed country adopts this technology more, and advantage is that oil, water, mud three phase separation are thorough, and shortcoming is that one-time investment is big; It two is to utilize the static settling process of heating to separate, and is about to heavy sump oil and is heated to about 80 ℃, impels the emulsion breakdown of emulsion, reclaim tryphine, its shortcoming is that return period is long, and steam consumption quantity is big, contain more water and cotton-shaped organic sludge in the refiltered oil, be unfavorable for refiltered oil freshening again.Because weigh the separation of sump oil and utilize difficulty very big, present domestic most refineries lack effective processing means.
Disclosed oil sludge separation method among CN1195017A and the CN1052322A is only applicable to contain the separation of a large amount of inorganic argillous oil-water-mud three-phase system, and is very poor to the separation suitability of the heavy sump oil in refinery.
Summary of the invention
The objective of the invention is to propose a kind of method that from heavy sump oil, reclaims edible vegetable oil, improve the edible vegetable oil rate of recovery and quality, shorten recovery time and reduce cost recovery.
The method that reclaims edible vegetable oil from heavy sump oil that the present invention proposes is: this method is a two-step approach; The first step: under alkaline condition, in heavy sump oil, add scavenging agent, scavenging agent is molysite/aluminium salt or molysite/inorganic polymer/mixture of aluminium salt or any mixture between them, make metal ion and hydroxide ion form coalescent center, and coalescent center is uniformly dispersed in heavy sump oil, making the heavy sump oil phase inversion that exists with W/O or O/W/O type emulsion form is O/W type emulsion form; The organic sludge that in emulsion phase inversion process, discharges, inorganic mud and coalescent in be formed centrally the bigger floss of density, rely on action of gravity to be divided into upper, middle and lower-ranking, the upper strata is enriched oil and part floss, the middle level is a large amount of organic floc sludges, a small amount of oil and surfactant, lower floor is limpid water and black precipitate, removes sub-cloud;
Second step: under acidic conditions, restore the divalent/trivalent metal ion in the floss from enriched oil, make lipid acid and naphthenic soap class surfactant become free lipid acid and naphthenic acid, lose emulsifying effect, reach the purpose of O/W type emulsion breakdown of emulsion, free lipid acid and naphthenic acid change oil phase over to, realize the separation of oil, mud, water, remove the Ni Heshui of sub-cloud, obtain edible vegetable oil.
Alkaline condition described in the first step of recovery method of the present invention is meant in heavy sump oil and adds alkaline matter, alkaline matter can be solid, granular substance, also can be liquid, and its add-on is to control with the pH value that reacts the back water, pH value is 8-12, preferred 911.Alkaline substance can be selected from alkaline matters such as refinery alkaline residue, potassium hydroxide, sodium hydroxide, ammoniacal liquor.
Alkaline residue is the waste residue behind the refinery oil product soda finishing.
The scavenging agent that the present invention proposes is molysite/aluminium salt or the inorganic polymer/mixture of molysite/aluminium salt or their any mixture.As: Tai-Ace S 150, aluminum chloride, ferric sulfate, ferrous sulfate, iron(ic) chloride, iron protochloride, alum, bodied ferric sulfate, polyaluminium sulfate and any mixture between them etc.Its add-on 0.05%~5% of sump oil weight of attaching most importance to is preferably 0.1%~3%.
Scavenging agent mixes with the heavy sump oil of form adding of the basoid aqueous solution and with it, is about to add in the heavy sump oil after scavenging agent and alkaline matter are made into alkaline colloid aqueous solution.
Scavenging agent also can add separately in the heavy sump oil, alkaline matter is added in the heavy sump oil again.
Acidic conditions described in the present invention's second one step process is meant in the enriched oil that the first step method obtains and adds acidic substance, and its add-on is to control with the pH value that reacts the back water, and pH value is 1-6, preferred 2-5.
It is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and sour water and any mixture between them that the acidic substance that the present invention proposes can be four kinds of mineral acids commonly used.
Sour water is that refinery is handled the sour water that waste soda residue obtains.
The Heating temperature of recovery method the first step process of the present invention is 30 ℃~90 ℃, is preferably 40 ℃~70 ℃, and the effect of heating mainly is in order to reduce the viscosity of heavy sump oil, help breakdown of emulsion and sedimentation, certainly, the high more effect of its temperature is good more, then needs the more energy to provide but temperature is too high.Thus, the selection of temperature is unimportant and more or less freely.Therefore not as the characteristics of the inventive method.
Second step of the recovery method of the present invention Heating temperature of process is 30 ℃~90 ℃, is preferably 40 ℃~70 ℃, its effect and analyze the same.
In 1~5 hour reaction times in the recovery method the first step process of the present invention, preferred 2~4 hours, its reaction times, long more then reaction effect was good more, but overlong time then influences production efficiency.
1~5 hour reaction times in second step of the recovery method process of the present invention, preferred 2~4 hours, its effect and analyze the same.
The present invention reclaims edible vegetable oil from heavy sump oil method specifically can be stated as: it is two-step approach: the first step is adding scavenging agent in heavy sump oil, its add-on 0.05%~5% of sump oil weight of attaching most importance to, and preferred value is 0.1%~3% (weight); The mode that scavenging agent preferably is mixed with the basoid aqueous solution adds, and the pH value of control reaction back water is 8~12, and preferred 9~11; Mix; Usually temperature of reaction is 30 ℃~90 ℃, is preferably 40 ℃~70 ℃; 1~5 hour reaction times, preferred 2~4 hours, realize that tentatively the breakdown of emulsion of oil-water-mud and mud are coalescent, separate the water and the black floss of lower floor.Second step was to add acidic substance in the enriched oil of upper strata, made under acidic conditions and reacted, and the pH value of control reaction back water is 1~6, preferred 2~5; Mix; Usually temperature of reaction is 30 ℃~90 ℃, is preferably 40 ℃~70 ℃; 1~5 hour reaction times, preferred 2~4 hours; Breakdown of emulsion once more, the superiors are boiled oil layer, are followed successively by organic sludge, water and inorganic mud, recovery upper strata edible vegetable oil downwards.In the mud that the first step and second step produce, the water and after send waste disposal plant.
The method that from heavy sump oil, reclaims edible vegetable oil that the present invention proposes, operating procedure is simple, and starting material are cheap and easy to get, and separating effect is better and energy consumption is low, disengaging time short, simultaneously can utilize reluctant alkaline residue of refinery and sour water, have good economic and social benefit.
Description of drawings
Accompanying drawing 1 is the process flow sheet of recovery method of the present invention.
Accompanying drawing 2 by the property analysis table of recovery edible vegetable oil.
Among the figure, 1, interchanger, 2, the scavenging agent jar, 3,6, mixing tank, 4, the primary settling jar, 5, the acidic substance jar, 7, the secondary slurry tank.
Embodiment
The technical process of 1 pair of recovery method of the present invention is illustrated in conjunction with the accompanying drawings:
Heavy sump oil is after interchanger 1 is heated to design temperature, after passing through mixing tank 3 in proportion with scavenging agent in the scavenging agent jar 2, enter primary settling jar 4 from the middle part, enriched oil is derived from primary settling jar 4 tops, and together enter mixing tank 6 with acidic substance in the acidic substance jar 5, mix the back and enter secondary slurry tank 7 from the middle part, derive from secondary slurry tank 7 tops and reclaim edible vegetable oil.After primary settling jar 4 and isolated alkaline sewage in secondary slurry tank 7 bottoms and sour water (containing mud) neutralization, deliver to waste disposal plant.
The present invention both can adopt single container batch operation, can carry out the continous way operation again.
Further specify the concrete operation method and the condition of the inventive method below by example.
The character of used heavy sump oil is among the embodiment: moisture: 76% (weight), salts contg: 490mgNaCll
-1, ash content: 1.18%, oil-containing: 22% (weight), other is an organic sludge.
To contain concentration sodium hydroxide (weight) be 7.4% to used refinery alkaline residue among the embodiment.
A the first step working method and condition are given an example:
Embodiment A 1:
In the heavy sump oil of 1Kg, add 0.5g Tai-Ace S 150 (counterweight sump oil 0.05%), 0.492g potassium hydroxide, the pH value of control reaction back water is 8, and temperature of reaction is 50 ℃, and the reaction times is 2 hours.
Embodiment A 2:
In the heavy sump oil of 1Kg, add by 8g ferric sulfate (counterweight sump oil 0.8%), the basoid aqueous solution of 4.81g sodium hydroxide and the preparation of 100ml water, the pH value of control reaction back water is 10, and temperature of reaction is 40 ℃, and the reaction times is 3 hours.
Embodiment A 3:
In the heavy sump oil of 1Kg, add by 2g aluminum chloride (counterweight sump oil 0.2%), the basoid aqueous solution of 24.3ml refinery alkaline residue and the preparation of 50ml water, the pH value of control reaction back water is 9, and temperature of reaction is 35 ℃, and the reaction times is 4 hours.
Embodiment A 4:
In the heavy sump oil of 1Kg, add 25g iron(ic) chloride (counterweight sump oil 2.5%), 18.5g sodium hydroxide, the pH value of control reaction back water is 11, and temperature of reaction is 55 ℃, and the reaction times is 3 hours.
Embodiment A 5:
In the heavy sump oil of 1Kg, add by 15g iron protochloride (counterweight sump oil 1.5%), the basoid aqueous solution of 13.23g potassium hydroxide and the preparation of 100ml water, the pH value of control reaction back water is 10, and temperature of reaction is 65 ℃, and the reaction times is 1 hour.
Embodiment A 6:
Add the basoid aqueous solution that is mixed with by 35g ferrous sulfate (counterweight sump oil 3.5%) and 249ml refinery alkaline residue in the heavy sump oil of 1Kg, the pH value of control reaction back water is 10, and temperature of reaction is 80 ℃, and the reaction times is 5 hours.
Embodiment A 7:
Add the basoid aqueous solution that is mixed with by 40g alum (counterweight sump oil 4%) and 119.2ml 10% ammoniacal liquor in the heavy sump oil of 1Kg, the pH value of control reaction back water is 9, and temperature of reaction is 90 ℃, and the reaction times is 2 hours.
Embodiment A 8:
Add the basoid aqueous solution that is mixed with by 20g bodied ferric sulfate (counterweight sump oil 2%) and 162.2ml refinery alkaline residue in the heavy sump oil of 1Kg, the pH value of control reaction back water is 9, and temperature of reaction is 60 ℃, and the reaction times is 3 hours.
Embodiment A 9:
Add the basoid aqueous solution that is mixed with by 45g polyaluminium sulfate (counterweight sump oil 4.5%) 269.9ml 10% ammoniacal liquor in the heavy sump oil of 1Kg, the pH value of control reaction back water is 8, and temperature of reaction is 40 ℃, and the reaction times is 4 hours.
Embodiment A 10:
In the heavy sump oil of 1Kg, add 10g polyaluminium sulfate and iron protochloride mixture (counterweight sump oil 1%, both mixed by weight 1: 1), 6.66g sodium hydroxide, the pH value of control reaction back water is 10, and temperature of reaction is 75 ℃, and the reaction times is 2 hours.
B second step working method and condition are given an example:
Embodiment B 1:
Add dilute hydrochloric acid in the first step gained enriched oil, the pH value of control reaction back water is 2, and temperature of reaction is 35 ℃, and the reaction times is 2 hours.
Embodiment B 2:
Add phosphoric acid in the first step gained enriched oil, the pH value of control reaction back water is 5, and temperature of reaction is 50 ℃, and the reaction times is 1 hour.
Embodiment B 3:
Add rare nitric acid in the first step gained enriched oil, the pH value of control reaction back water is 3, and temperature is 70 ℃, and the reaction times is 3 hours.
Embodiment B 4:
Add refinery sour water in the first step gained enriched oil, the pH value of control reaction back water is 5, and temperature of reaction is 60 ℃, and the reaction times is 4 hours.
Embodiment B 5:
Add dilute sulphuric acid in the first step gained enriched oil, the pH value of control reaction back water is 1.5, and temperature of reaction is 90 ℃, and the reaction times is 5 hours.
Embodiment B 6:
The mixture that in the first step gained enriched oil, adds dilute sulphuric acid and dilute hydrochloric acid, the pH value of control reaction back water is 6, and temperature of reaction is 55 ℃, and the reaction times is 3.5 hours.
C comprehensively gives an example:
Embodiment C 1:
Add by 5g ferrous sulfate (counterweight sump oil 0.5%) in the heavy sump oil of 1Kg, the basoid aqueous solution that 35.7ml refinery alkaline residue and 200ml water are mixed with mixes, and the pH value of control reaction back water is 10; Temperature of reaction is 60 ℃, and the reaction times is 2 hours.Remove the water and the black floss of sub-cloud.
In the enriched oil that the first step obtains, add refinery sour water, the pH value of control reaction back water is 2, and temperature of reaction is 60 ℃, and the reaction times is 3 hours.Remove the Ni Heshui of sub-cloud, obtain edible vegetable oil.The edible vegetable oil rate of recovery is 95.45%.
Embodiment C 2:
Add the basoid aqueous solution that is mixed with by 20g ferrous sulfate (counterweight sump oil 2%), 147.4ml refinery alkaline residue and 50ml water in the heavy sump oil of 1Kg, mix, the pH value of control reaction back water is 12; Temperature of reaction is 30 ℃, and the reaction times is 4 hours.Remove the water and the black floss of sub-cloud.
In the enriched oil that the first step obtains, add refinery sour water, the pH value of control reaction back water is 3, and temperature of reaction is 50 ℃, and the reaction times is 2 hours.Remove the Ni Heshui of sub-cloud, obtain edible vegetable oil.The edible vegetable oil rate of recovery is 78.56%.
Embodiment C 3:
Add the basoid aqueous solution that is mixed with by 10g iron protochloride (counterweight sump oil 1%), 85.2ml refinery alkaline residue and 100ml water in the heavy sump oil of 1Kg, mix, the pH value of control reaction back water is 9; Temperature of reaction is 40 ℃, and the reaction times is 3 hours.Remove the water and the black floss of sub-cloud.
In the enriched oil that the first step obtains, add refinery sour water, the pH value of control reaction back water is 4, and temperature of reaction is 60 ℃, and the reaction times is 4 hours.The rate of recovery is 89.26%.
Consisting of of the used heavy sump oil of present embodiment, moisture: 60% (weight), salts contg: 481mgNaCll
-1, ash content: 1.02%, oil-containing: 36% (weight), other is an active sludge.
Embodiment C 4:
Add the basoid aqueous solution that is mixed with by 15g iron protochloride (counterweight sump oil 1.5%), 127.7ml refinery alkaline residue and 200ml water in the heavy sump oil of 1Kg, mix, the pH value of control reaction back water is 8; Temperature of reaction is 50 ℃, and the reaction times is 1 hour.Remove the water and the black floss of sub-cloud.
In the enriched oil that the first step obtains, add refinery sour water, the pH value of control reaction back water is 3, and temperature of reaction is 40 ℃, and the reaction times is 2 hours.Remove the Ni Heshui of sub-cloud, obtain edible vegetable oil.The edible vegetable oil rate of recovery is 82.32%.
Consisting of of the used heavy sump oil of present embodiment, moisture: 60% (weight), salts contg: 481mgNaCll
-1, ash content: 1.02%, oil-containing: 36% (weight), other is an organic sludge.
Claims (11)
1, a kind of method that from heavy sump oil, reclaims edible vegetable oil, it is characterized in that: the inventive method is a two-step approach; The first step: under alkaline condition, in heavy sump oil, add scavenging agent, scavenging agent is molysite/aluminium salt or molysite/inorganic polymer/mixture of aluminium salt or any mixture between them, make metal ion and hydroxide ion form coalescent center, and coalescent center is uniformly dispersed in heavy sump oil, making the heavy sump oil phase inversion that exists with W/O or O/W/O type emulsion form is O/W type emulsion form; The organic sludge that in emulsion phase inversion process, discharges, inorganic mud and coalescent in be formed centrally the bigger floss of density, rely on action of gravity to be divided into upper, middle and lower-ranking, the upper strata is enriched oil and part floss, the middle level is a large amount of organic floc sludges, a small amount of oil and surfactant, lower floor is limpid water and black precipitate, removes sub-cloud;
Second step: under acidic conditions, restore the divalent/trivalent metal ion in the floss from enriched oil, make lipid acid and naphthenic soap class surfactant become free lipid acid and naphthenic acid, lose emulsifying effect, reach the purpose of O/W type emulsion breakdown of emulsion, free lipid acid and naphthenic acid change oil phase over to, realize the separation of oil, mud, water, remove the Ni Heshui of sub-cloud, obtain edible vegetable oil.
2, the method that reclaims edible vegetable oil from heavy sump oil according to claim 1 is characterized in that: described alkaline condition is to add alkaline matter in heavy sump oil, and the pH value of control reaction back water is 8-12.
3, the method that reclaims edible vegetable oil from heavy sump oil according to claim 1 is characterized in that: described alkaline condition is to add alkaline matter in heavy sump oil, and the pH value of control reaction back water is 9-11.
4, the method that from heavy sump oil, reclaims edible vegetable oil according to claim 1, it is characterized in that: described acidic conditions is to add acidic substance in the enriched oil that the first step method obtains, the pH value of control reaction back water is 1-6.
5, the method that from heavy sump oil, reclaims edible vegetable oil according to claim 1, it is characterized in that: described acidic conditions is to add acidic substance in the enriched oil that the first step method obtains, the pH value of control reaction back water is 2-5.
6, according to claim 4 or the 5 described methods that reclaim edible vegetable oil from heavy sump oil, it is characterized in that: described acidic substance are hydrochloric acid/sulfuric acid/nitric acid/phosphoric acid.
7, according to claim 4 or the 5 described methods that reclaim edible vegetable oil from heavy sump oil, it is characterized in that: described acidic substance are sour water.
8, the method that from heavy sump oil, reclaims edible vegetable oil according to claim 1, it is characterized in that: scavenging agent adds heavy sump oil in the mode of the basoid aqueous solution and mixes with it, is about to add in the weight sump oil after scavenging agent is made into alkaline colloid aqueous solution with alkaline matter.
9, the method that reclaims edible vegetable oil from heavy sump oil according to claim 1 is characterized in that: scavenging agent adds separately in the heavy sump oil, alkaline matter is added in the heavy sump oil again.
10, the method that reclaims edible vegetable oil from heavy sump oil according to claim 1 is characterized in that: the attach most importance to 0.05%-5% of sump oil weight of the add-on of described scavenging agent (weight).
11, the method that reclaims edible vegetable oil from heavy sump oil according to claim 1 is characterized in that: the attach most importance to 0.1%-3% of sump oil weight of the add-on of described scavenging agent (weight).
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CN 03134933 CN1243072C (en) | 2003-09-30 | 2003-09-30 | Method for recovering clean oil from heavy dirty oil |
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CN101735851B (en) * | 2009-12-23 | 2013-01-02 | 大庆油田有限责任公司 | Recovery and treatment technology of dirty oil produced in sewage setting tank in produced liquid treatment |
CN103626367B (en) * | 2013-12-19 | 2015-12-30 | 中国石油大学(华东) | A kind of method of floating the recycling of oil sludge resource utilization containing gather qi together |
CN105419856B (en) * | 2016-01-12 | 2018-04-27 | 扬州大学 | A kind for the treatment of process of the aqueous sump oil of high slag inclusion |
CN106430909A (en) * | 2016-12-08 | 2017-02-22 | 马军平 | Harmless oil sludge recycling device and using method thereof |
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