CN102585889A - Acid-alkali-free refining agent for diesel oil regenerated from waste oil by catalytic cracking method and preparation method for refining agent - Google Patents
Acid-alkali-free refining agent for diesel oil regenerated from waste oil by catalytic cracking method and preparation method for refining agent Download PDFInfo
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- CN102585889A CN102585889A CN2012100647309A CN201210064730A CN102585889A CN 102585889 A CN102585889 A CN 102585889A CN 2012100647309 A CN2012100647309 A CN 2012100647309A CN 201210064730 A CN201210064730 A CN 201210064730A CN 102585889 A CN102585889 A CN 102585889A
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Abstract
The invention discloses an acid-alkali-free refining agent for diesel oil regenerated from waste oil by a catalytic cracking method and a preparation method for the refining agent. The refining agent is a compound refining agent and comprises the following components in percentage by weight: 10 to 80 percent of adsorption precipitation agent, 5 to 10 percent of auxiliary active ingredient, 0 to 10 percent of cationic surfactant, 0 to 10 percent of nonionic surfactant, 0 to 5 percent of cosurfactant and the balance of diesel oil. The acid-alkali-free refining agent has a good effect of decolorizing and deodorizing diesel oil subjected to oxidative discoloration and deterioration and biomass diesel oil, crude oil can be truly refined without acid or alkali, decolorizing and deodorizing can be finished in one process, the refining agent is easy and convenient to operate and can be used twice, the removed waste residues can be treated to form an agricultural chemical fertilizer, and environmental pollution is avoided.
Description
Technical field
The present invention relates to waste oil comprehensive utilization and oil fuel processing technique field, particularly a kind of urge split method waste oil regeneration diesel oil exempt from acid-alkali refining agent and preparation method.
Background technology
Waste and old oils mainly comprises MO (petroleum-type) and vegetable and animals oils (oils), and they are very different on composition.The comprehensive utilization of present waste and old oils mainly can be divided into three types, and one type is that waste and old oil product (mineral oils) is carried out being used as low side fuel after the roughing, causes resource utilization to can not get performance, causes the wasting of resources.Another kind of is the oil refining process of continuing to use the big factory of petrochemical industry; Waste oil removal of impurities → the go into still → intensification → waste oil steam that dewaters gets into the thick diamicton of Catalytic Layer → remove → remove thin diamicton → absorption → condensation → s.t. → alkali diesel oil that neutralizes → be deployed into, complex process, and equipment is many; Investment is big, and general producer is difficult to bear.Also have one type to be that waste cooking oil or acidifying oil (oils) are produced biodiesel processes, the someone claims that without soda acid with methyl alcohol and simple distillation has just become qualified biofuel product once, this is to disguise replacement of concept.This method is basic just to be reduced greasy molecular weight, does not also change the carbon-chain structure of molecule, and refining depth and anti-oxidant degree do not reach requirement, and such oil still is original grease still, can't reach the physical and chemical index of diesel oil.The state-of-the-art technology of the comprehensive utilization of present waste and old oils it is said it is short-path distillation or molecular distillation; Both solved color problem, and removed soda acid again and washed problem such as cause pH to exceed standard, resistance to emulsion is defective, but investment had been big; Technical requirements is high, and practicality is not strong.We can say also there is not truly the diesel regenerated continuous production type industrialized unit of waste oil cracking of a cover in the market, so regenerated diesel oil viscosity, density, colourity, flash-point, oxidation-resistance etc. are not up to standard.
The diesel oil of waste oil catalytic pyrolysis, as without the refining oxidation blackout that is prone to, do not reach the new national standard requirement less than 3.5 colourity requirement, have only through just introducing to the market after the decolouring.In addition, in process of production because problems such as the unreasonable and raw material of technology make colourity, the smell of product not reach requirement; The monosodium glutamate system of must decolouring could be removed peculiar smell, oxide compound, colloid, makes pitch black, muddy oil product become limpid bright; Increase stability, reach the use standard.
Traditional oil fuel process for purification is an acid-alkali refining; Utilize bronsted lowry acids and bases bronsted lowry to some the unfavorable components in the oil fuel exactly; Like dissolving and reactions such as sulfide, nitride and organic acid, phenol, colloid and alkene, diolefine; These objectionable impuritiess are removed from oil fuel to some extent, to improve oil quality.The technical process of acid-alkali refining generally has: caustic prescrub → pickling → washing → alkali cleaning → steps such as washing, and sometimes with electric field action.This method technology is simple, facility investment and process cost are lower; But treatment losses is big; Product yield is low, and the refining oil product that obtains again can blackening in very short time, and the stink and the peculiar smell of oil the inside are difficult to remove; Also exist the soda acid waste residue to be difficult for problems such as processing and discharge of wastewater, can cause serious secondary pollution environment.
Summary of the invention
The technical problem that the present invention will solve is; Provide that a kind of technology is simple, energy-conserving and environment-protective, cost is low, efficient is high urge split method waste oil regeneration diesel oil exempt from acid-alkali refining agent and preparation method; Mainly be to split the refining of crude oil in the method waste oil regeneration diesel production technology to urging; Through the refining weight diesel oil that obtains or oil fuel modest viscosity, limpid bright, color and luster good, free from extraneous odour, reaches the corresponding label diesel oil standard of GB.
Another technical problem that the present invention will solve provides this and urges the preparation method who exempts from the acid-alkali refining agent of splitting method waste oil regeneration diesel oil.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, said finishing agent is compound finishing agent; Comprise following component: absorption-sinking agent 10～80%, help active ingredient 5～10%, cats product 0～10%; Nonionogenic tenside 0～10%; Cosurfactant 0～5%, surplus are diesel oil, and above per-cent all is weight percentage.Said diesel oil is used to regulate the viscosity of exempting from the acid-alkali refining agent as solvent.
As preferably; Said absorption-sinking agent is to have the adsorption bridging effect to catch the active substance of effect with the deposition net, is selected from one or more the combination in quadrol, triethylamine, N-alkyl diethylolamine, hexahydroaniline, diethylenetriamine, triethylene diamine, triethylene tetramine, the TEPA.
As preferably, the said one or more kinds of combinations that help in the carbonic ether that active ingredient is selected from thanomin, trolamine, isopropylamine, N-phenyldiethanol-amine, sulfuric acid vinyl ester, guanidine class.
As preferably, said cats product is the one or more kinds of combinations in the soap, alkyl quaternary ammonium salt, Poly Dimethyl Diallyl Ammonium Chloride, polymethyl acyl-oxygen ethyl-trimethyl salmiac of cationic polymers.
As preferably, said nonionogenic tenside is the one or more kinds of combinations in the tensio-active agent, polyoxyethylene 20 sorbitan monooleate, polyoxyethylene 20 sorbitan trioleate, polyoxyethylene-type nonionogenic tenside, polyoxyethylene nonylphenol nonionogenic tenside of polyoxyethylene sorbitan oleic acid ester class.
As preferably, said cosurfactant is XU 61518.10, to the one or more kinds of combinations in NP, n-Heptyl alcohol, n-Octanol, the sec-n-octyl alcohol.
A kind of preparation method who exempts from the acid-alkali refining agent of splitting method waste oil regeneration diesel oil that urges; May further comprise the steps: in reaction kettle, add a certain amount of diesel oil earlier; Add the absorption-sinking agent measure again successively, help active ingredient, cats product, nonionogenic tenside and cosurfactant; At the uniform velocity stirred 30 minutes, and promptly got the said acid-alkali refining agent of exempting from.
As preferably; Said absorption-sinking agent is to have the adsorption bridging effect to catch the active substance of effect with the deposition net, is selected from one or more the combination in quadrol, triethylamine, N-alkyl diethylolamine, hexahydroaniline, diethylenetriamine, triethylene diamine, triethylene tetramine, the TEPA;
The said one or more kinds of combinations that help in the carbonic ether that active ingredient is selected from thanomin, trolamine, isopropylamine, N-phenyldiethanol-amine, sulfuric acid vinyl ester, guanidine class;
Said cats product is the one or more kinds of combinations in the soap, alkyl quaternary ammonium salt, Poly Dimethyl Diallyl Ammonium Chloride, polymethyl acyl-oxygen ethyl-trimethyl salmiac of cationic polymers;
Said nonionogenic tenside is the one or more kinds of combinations in the tensio-active agent, polyoxyethylene 20 sorbitan monooleate, polyoxyethylene 20 sorbitan trioleate, polyoxyethylene-type nonionogenic tenside, polyoxyethylene nonylphenol nonionogenic tenside of polyoxyethylene sorbitan oleic acid ester class;
Said cosurfactant is XU 61518.10, to the one or more kinds of combinations in NP, n-Heptyl alcohol, n-Octanol, the sec-n-octyl alcohol.
The present invention provide a kind of urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, its beneficial effect is: can remove colloid, bituminous matter, sulfide, oxide compound and unsaturated hydrocarbons etc. well, make processed oil limpid bright, smell is pure, puts for a long time and never degenerates.Of the present inventionly exempt from the acid-alkali refining agent to oxidation stain, rotten diesel oil, biodiesel; Have very superior decolouring to go the effect of distinguishing the flavor of, can really realize need not acid, alkali makes with extra care thick oil product, and the decolouring and deodorizing one procedure can be accomplished; Operate very simple and convenient; Reusable twice, the waste residue that takes off can not cause any pollution to environment through being treated as agrochemical.
Provided by the invention a kind of urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, have following characteristics:
(1) broken the complicated technology of classical acid, alkali, carclazyte decolouring and deodorizing, need not heat, directly added finishing agent through stirring, deposition, separating and get final product;
(2) broken many bodies in the past and separated impurity removal process, integrated removal of impurities, decolour, go to distinguish the flavor of;
(3) technology is simple, cost is low, efficient is high;
(4) flexibility is strong, can make with extra care to urge to split the various crude oils of producing in the method waste oil regeneration diesel production technology;
(5) diesel oil modest viscosity, free from extraneous odour after refining, acid number, colourity meet country or industry standard, good stability, the long-term storage nondiscoloration is never degenerated.
Urge the making method of splitting method waste oil regeneration diesel oil crude oil, may further comprise the steps:
1) preparation gas phase catalyst
To cross 120 mesh sieves, mechanical stirring with 26 kilograms in the former powder of rare earth ion metathetical Y zeolite REY, 10 kilograms of high silica ZSM-5 molecular screen primary powders, 12 kilograms of activated aluminas, 55 kilograms of attapulgites; Mix; Mixed powder and the sial complex sol sticker for preparing are mediated for 15 kilograms, and control pigment mass ratio is 0.6: 1, fully mediates after the extrusion moulding of screw rod banded extruder, pelletizing; Dry under the room temperature; 120 ° of C are down after dry 3 hours, roasting 5 hours under 600 ° of C under oxygen atmosphere, and making diameter is the cylindric gas phase catalyst particle of 4mm.
2) preparation liquid-phase catalyst
30 kilograms of Aluminum chloride anhydrouss, 25 kilograms in active silicic acid aluminium and zeyssatite are pulverized for 45 kilograms, and mechanical stirring mixes, and crosses 200 mesh sieves, and oven dry is 1 hour under 100 ° of C, makes liquid-phase catalyst.
3) reaction
The gas phase catalyst of in the gas phase catalysis tower, packing into.With waste oil; After pre-treatment such as dehydration, decon, the mud that deoils, the matter of removing photoresist, deoxidation thing, pump in the scission reaction still, in the ratio of charging capacity 0.15% liquid-phase catalyst for preparing is directly added scission reaction still and waste oil and mix and carry out catalytic pyrolysis; Respectively under the effect of liquid, gas phase special-purpose catalyst; At 350～550 ° of C,, approach the molecular structure of diesel oil with formation with the waste oil catalytic pyrolysis.The cracked oil steam that comes out from the gas phase catalysis tower is collected with scoop after condenser condenses, and after water-and-oil separator separated lower floor's moisture, the upper strata was crude oil, was faint yellow, and clarification is almost tasteless.Waste oil in the above-mentioned technology comprises: used oil, waste lubricating oil, useless gear oil, useless machinery oil, waste hydraulic oil, useless transformer oil, damaged tire are slightly refined oil, slightly oil refining of plastic waste, heavy oil, wax oil, residual oil, coal tar, washing oil, waste cooking oil (being commonly called as sewer oil, hogwash fat, swill oil), acidifying oil, oil-fat plant tankage, the useless all kinds of waste oil of plant-animal wet goods of deceiving; Can be wherein a kind of, or their mixture.
Provided by the invention urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, be to urge with above-mentioned that to split the crude oil of producing in the method waste oil regeneration diesel production technology refining and become the finished diesel fuel that reaches the corresponding label diesel oil standard of GB.
This finishing agent does not contain soda acid, has not only thoroughly changed shortcomings such as the waste discharge that the classical acid sodafining brings, environmental pollution, complex procedures, production cost are high, consuming time, power consumption, and can improve the quality of products greatly; And really accomplish pollution-free; Zero release, the protection environment is benefited the nation and the people.
In sum, provided by the invention urge split method waste oil regeneration diesel oil exempt from that acid-alkali refining agent and preparation method have that technology is simple, cost is low, efficient is high, the beneficial effect of safety, environmental protection.
Embodiment
Embodiment 1:
In reaction kettle, add 35 kilograms of diesel oil; Add 240 kilograms of N-alkyl diethylolamine, 28 kilograms of isopropylamine, 24 kilograms of Poly Dimethyl Diallyl Ammonium Chlorides, 20 kilograms of polyoxyethylene nonylphenols more successively and to 4 kilograms of NPs; At the uniform velocity stirred 30 minutes, and made and exempt from the acid-alkali refining agent.
With the crude oil of coal tar through urging the method catalytic pyrolysis of splitting to obtain; After oily water separation, import refining stirred pot, what add oil product amount 1.4% exempts from the acid-alkali refining agent, fully stirs 3～10 minutes; Staticly settled 5～10 minutes; Tell lower floor's residue, the upper strata oil product that obtains obtains refining finished product after filter filters.It is faint yellow that product is, clarification, and free from extraneous odour can be used as oil fuel.Through measuring density 860kg/m
3, kinematic viscosity 6.5mm
2/ s, condensation point-15 ° C, 55 ° of C of close flash point, acidity 5mgKOH/100mL, 1 grade of copper corrosion, No. 2.5, colourity, calorific value>=10200 kcal/kg.
Embodiment 2:
In reaction kettle, add 40 kilograms of diesel oil; Add 3 kilograms of 210 kilograms of diethylenetriamines, 32 kilograms of sulfuric acid vinyl esters, 29 kilograms of polymethyl acyl-oxygen ethyl-trimethyl salmiacs, 25 kilograms of polyoxyethylene 20 sorbitan monooleates and XU 61518.10s more successively; At the uniform velocity stirred 30 minutes, and made and exempt from the acid-alkali refining agent.
With the mixture of useless gear oil and sewer oil, both ratios are 90: 10, through the crude oil of urging the method catalytic pyrolysis of splitting to obtain; After oily water separation, import refining stirred pot, what add oil product amount 1.1% exempts from the acid-alkali refining agent, fully stirs 3～10 minutes; Staticly settled 5～10 minutes; Tell lower floor's residue, the upper strata oil product that obtains obtains refining finished product after filter filters.It is faint yellow that product is, clarification, and free from extraneous odour can be used as oil fuel.Through measuring density 873kg/m
3, kinematic viscosity 7.0mm
2/ s, condensation point-10 ° C, 60 ° of C of close flash point, acidity 6mgKOH/100mL, 1 grade of copper corrosion, No. 3.0, colourity, calorific value>=10600 kcal/kg.
Embodiment 3:
In reaction kettle, add 33 kilograms of diesel oil; Add 5 kilograms of 280 kilograms of hexahydroaniline, 20 kilograms of N-phenyldiethanol-amines, 22 kilograms of the soaps of cationic polymers, 28 kilograms of polyoxyethylene-type nonionogenic tensides and sec-n-octyl alcohols more successively; At the uniform velocity stirred 30 minutes, and made and exempt from the acid-alkali refining agent.
With the crude oil of waste hydraulic oil through urging the method catalytic pyrolysis of splitting to obtain; After oily water separation, import refining stirred pot, what add oil product amount 1.8% exempts from the acid-alkali refining agent, fully stirs 3～10 minutes; Staticly settled 5～10 minutes; Tell lower floor's residue, the upper strata oil product that obtains obtains refining finished product after filter filters.Product is water white, and clarification is almost tasteless, can be used as oil fuel.Through measuring density 865kg/m
3, kinematic viscosity 7.0mm
2/ s, condensation point-11 ° C, 60 ° of C of close flash point, acidity 5mgKOH/100mL, 1 grade of copper corrosion, No. 2.0, colourity, calorific value>=10800 kcal/kg.
Embodiment 4:
In reaction kettle, add 36 kilograms of diesel oil; Add 7 kilograms of 200 kilograms of triethylene tetramines, 34 kilograms of trolamines, 25 kilograms of Poly Dimethyl Diallyl Ammonium Chlorides, 30 kilograms of polyoxyethylene 20 sorbitan trioleates and n-Heptyl alcohols more successively; At the uniform velocity stirred 30 minutes, and made and exempt from the acid-alkali refining agent.
With the crude oil of used oil through urging the method catalytic pyrolysis of splitting to obtain; After oily water separation, import refining stirred pot, what add oil product amount 1.2% exempts from the acid-alkali refining agent, fully stirs 3～10 minutes; Staticly settled 5～10 minutes; Tell lower floor's residue, the upper strata oil product that obtains obtains refining finished product after filter filters.It is faint yellow that product is, and clarification is almost tasteless, can be used as oil fuel.Through measuring density 853kg/m
3, kinematic viscosity 7.0mm
2/ s, condensation point-10 ° C, 55 ° of C of close flash point, acidity 6mgKOH/100mL, 1 grade of copper corrosion, No. 2.5, colourity, calorific value>=10500 kcal/kg.
Embodiment 5:
In reaction kettle, add 40 kilograms of diesel oil; Add 3 kilograms of 210 kilograms of diethylenetriamines, 32 kilograms of sulfuric acid vinyl esters, 29 kilograms of polymethyl acyl-oxygen ethyl-trimethyl salmiacs, 25 kilograms of polyoxyethylene 20 sorbitan monooleates and XU 61518.10s more successively; At the uniform velocity stirred 30 minutes, and made and exempt from the acid-alkali refining agent.
With the crude oil of waste cooking oil through urging the method catalytic pyrolysis of splitting to obtain; After oily water separation, import refining stirred pot, what add oil product amount 2% exempts from the acid-alkali refining agent, fully stirs 3～10 minutes; Staticly settled 5～10 minutes; Tell lower floor's residue, the upper strata oil product that obtains obtains refining finished product after filter filters.It is faint yellow that product is, and clarification is almost tasteless, can be used as oil fuel.Through measuring density 873kg/m
3, kinematic viscosity 7.5mm
2/ s, 0 ° of C of condensation point, 60 ° of C of close flash point, acidity 6mgKOH/100mL, 1 grade of copper corrosion, No. 3.0, colourity, calorific value>=10400 kcal/kg.
Although with reference to embodiment to disclosed relate to a kind of urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent and the preparation method has carried out special description; But the embodiment of above description is illustrative rather than restrictive; Promptly the invention is not restricted to above-mentioned specific embodiment; Under the situation that does not break away from the spirit and scope of the present invention, all variations and modification are all within scope of the present invention.
Claims (8)
- One kind urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, it is characterized in that: said finishing agent is compound finishing agent, comprises following component: absorption-sinking agent 10～80%; Help active ingredient 5～10%; Cats product 0～10%, nonionogenic tenside 0～10%, cosurfactant 0～5%; Surplus is a diesel oil, and above per-cent all is weight percentage.
- 2. according to claim 1 urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent; It is characterized in that: said absorption-sinking agent is to have the adsorption bridging effect to catch the active substance of effect with the deposition net, is selected from one or more the combination in quadrol, triethylamine, N-alkyl diethylolamine, hexahydroaniline, diethylenetriamine, triethylene diamine, triethylene tetramine, the TEPA.
- 3. according to claim 2 urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, it is characterized in that: the said one or more kinds of combinations that help in the carbonic ether that active ingredient is selected from thanomin, trolamine, isopropylamine, N-phenyldiethanol-amine, sulfuric acid vinyl ester, guanidine class.
- 4. according to claim 3 urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, it is characterized in that: said cats product is the one or more kinds of combinations in the soap, alkyl quaternary ammonium salt, Poly Dimethyl Diallyl Ammonium Chloride, polymethyl acyl-oxygen ethyl-trimethyl salmiac of cationic polymers.
- 5. according to claim 4 urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, it is characterized in that: said nonionogenic tenside is the one or more kinds of combinations in the tensio-active agent, polyoxyethylene 20 sorbitan monooleate, polyoxyethylene 20 sorbitan trioleate, polyoxyethylene-type nonionogenic tenside, polyoxyethylene nonylphenol nonionogenic tenside of polyoxyethylene sorbitan oleic acid ester class.
- 6. according to claim 5 urge split method waste oil regeneration diesel oil exempt from the acid-alkali refining agent, it is characterized in that: said cosurfactant is XU 61518.10, to the one or more kinds of combinations in NP, n-Heptyl alcohol, n-Octanol, the sec-n-octyl alcohol.
- 7. the described preparation method who exempts from the acid-alkali refining agent of splitting method waste oil regeneration diesel oil that urges of claim 1-6; It is characterized in that: may further comprise the steps: in reaction kettle, add diesel oil earlier; Add absorption-sinking agent more successively, help active ingredient, cats product, nonionogenic tenside and cosurfactant; At the uniform velocity stirred 30 minutes, and promptly got the said acid-alkali refining agent of exempting from.
- 8. the preparation method who exempts from the acid-alkali refining agent of splitting method waste oil regeneration diesel oil that urges according to claim 7; It is characterized in that: said absorption-sinking agent is to have the adsorption bridging effect to catch the active substance of effect with the deposition net, is selected from one or more the combination in quadrol, triethylamine, N-alkyl diethylolamine, hexahydroaniline, diethylenetriamine, triethylene diamine, triethylene tetramine, the TEPA;The said one or more kinds of combinations that help in the carbonic ether that active ingredient is selected from thanomin, trolamine, isopropylamine, N-phenyldiethanol-amine, sulfuric acid vinyl ester, guanidine class;Said cats product is the one or more kinds of combinations in the soap, alkyl quaternary ammonium salt, Poly Dimethyl Diallyl Ammonium Chloride, polymethyl acyl-oxygen ethyl-trimethyl salmiac of cationic polymers;Said nonionogenic tenside is the one or more kinds of combinations in the tensio-active agent, polyoxyethylene 20 sorbitan monooleate, polyoxyethylene 20 sorbitan trioleate, polyoxyethylene-type nonionogenic tenside, polyoxyethylene nonylphenol nonionogenic tenside of polyoxyethylene sorbitan oleic acid ester class;Said cosurfactant is XU 61518.10, to the one or more kinds of combinations in NP, n-Heptyl alcohol, n-Octanol, the sec-n-octyl alcohol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11220468B2 (en) | 2017-09-11 | 2022-01-11 | Arr-Maz Products. L.P. | Fertilizer coating for dust control and/or anti-caking |
| CN115353928A (en) * | 2022-08-19 | 2022-11-18 | 唐亮 | Regenerated lubricating oil based on chemical method treatment |
-
2012
- 2012-03-13 CN CN2012100647309A patent/CN102585889A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11220468B2 (en) | 2017-09-11 | 2022-01-11 | Arr-Maz Products. L.P. | Fertilizer coating for dust control and/or anti-caking |
| CN115353928A (en) * | 2022-08-19 | 2022-11-18 | 唐亮 | Regenerated lubricating oil based on chemical method treatment |
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Application publication date: 20120718 |