CN109536202A - A kind of preprocess method of cold-rolling oil Preparation of Biodiesel from Waste Oils raw material - Google Patents
A kind of preprocess method of cold-rolling oil Preparation of Biodiesel from Waste Oils raw material Download PDFInfo
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- CN109536202A CN109536202A CN201710868718.6A CN201710868718A CN109536202A CN 109536202 A CN109536202 A CN 109536202A CN 201710868718 A CN201710868718 A CN 201710868718A CN 109536202 A CN109536202 A CN 109536202A
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- waste
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- rolling oil
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- 239000003921 oil Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 239000010731 rolling oil Substances 0.000 title claims abstract description 47
- 239000002994 raw material Substances 0.000 title claims abstract description 38
- 239000003225 biodiesel Substances 0.000 title claims abstract description 31
- 238000005097 cold rolling Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005189 flocculation Methods 0.000 claims abstract description 10
- 230000016615 flocculation Effects 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000002910 solid waste Substances 0.000 claims abstract description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- 239000001110 calcium chloride Substances 0.000 claims description 14
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 14
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000004530 micro-emulsion Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- -1 fuel-displaced Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/10—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for with the aid of centrifugal force
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0058—Working-up used lubricants to recover useful products ; Cleaning by filtration and centrifugation processes; apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
- C10G2300/1007—Used oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention relates to a kind of preprocess method of cold-rolling oil Preparation of Biodiesel from Waste Oils raw material, include the following steps: to filter after heating cold-rolling oil, removes solid waste, oil strain is obtained;Demulsifier is added to described cross in oil strain, stirring is allowed to demulsification reaction;Flocculant is added into the waste rolling oil after demulsification, implements flocculation;By the waste rolling oil centrifuge separation after flocculation, oil, waste water, residue are respectively obtained;The oil is collected, biodiesel raw material is obtained.Moreover, it relates to a kind of recycling and reusing method of biodiesel raw material and waste rolling oil.It is the method for the present invention mild condition, pollution-free, high-efficient;It is good to recycle oil quality, quality can satisfy production of biodiesel requirement;Harmless to human body, waste of resource, does not reduce the harm to environment.
Description
Technical field
The invention belongs to field of renewable energy;Be related to a kind of preprocess method of biodiesel raw material, it is especially a kind of by
The preprocess method for the ROLLING OIL Preparation of Biodiesel from Waste Oils raw material that metallurgical cold rolling product generates.
Background technique
In metallurgy industry, ROLLING OIL used in cold rolling mill cold-rolled products is frequently with oil emulsion or animal and plant fat as lubrication
Agent and coolant.Using after a certain period of time, cooling and lubricating effect declines, material oxidation deterioration.When the impurities accumulation of generation is to one
After determining degree, it is necessary to use the ROLLING OIL before new ROLLING OIL replacement.Replaced waste rolling oil be substantially include yin-
Nonionic surfactant, grease, solid greasy filth (main component is ferric oxide particles) and water micro emulsion.This microemulsion
Liquid has higher stability, and the waste rolling oil appearance of this micro emulsion is reddish brown, or is dark thick shape, volume compared with
Greatly, moisture content is 20% or more, and specific gravity is close to 1.In a heated condition, organic matter contained by waste rolling oil is readily volatilized, generates
Strong smog and pungent odour belongs to the hazardous waste that country forbids discharge to pollute the environment.Total comes
It sees, waste rolling oil has the double characteristic of pollution and resource, implement appropriate recycling, regeneration treatment and recycling to it,
It is the inexorable trend for the sustainable development for realizing that resource maximizes and environmental pollution minimizes.
Before, most domestic waste oil regeneration factory regenerates waste rolling oil using sulfuric acid backward in technique-carclazyte method
Processing.This technique decolorizing effect is obvious, stable product quality.However, due to using a large amount of concentrated sulfuric acid to connect with aqueous waste oil
Touching occurs very exothermic reaction, is easy to appear bumping tank boil-overs accident, while it is serious to corrode equipment, generates a large amount of acid sludge, acid
Water, it is difficult to processing and utilization.In addition, carclazyte is at high price, it is difficult to be recycled, be easy to cause environment great secondary calamity
Evil.
In view of the above technical defects, people gradually adopt anacidity waste oil regeneration technology to be recycled waste oil.
Chinese patent application CN200710163473.3 discloses a kind of aluminum strip foil roll mill regeneration process of rolling oil.The work
Contaminated ROLLING OIL is stored in sump oil case first by skill, after filter filtering and heat exchanger processing, is re-fed into vacuum item
Circulating-heating is carried out in the rectifying column of part, is evaporated under reduced pressure, then condensing recovery.The circulation that ROLLING OIL may be implemented in this technique makes
With, and save the cost.
Chinese patent application CN200810141346.8 discloses a kind of process lubrication coolant oil regeneration method.This method is adopted
It is different using each component boiling range in miscella with rotating scraped film evaporator, it is condensed after being distilled by heating under reduced pressure, by technological lubrication
Cooling purifies out from miscella to be utilized again.
Chinese patent application CN201510663599.1 discloses a kind of recovery processing process of the oil of useless rolling, including with
Lower step: filtering waste rolling oil;Extractant and flocculant and isolated first supernatant is added;Adsorbent is added simultaneously thereto
Separation, obtains the second supernatant;The component between 80~100 DEG C and 240~360 DEG C is collected in vacuum distillation respectively.
The pollution of above-mentioned anacidity waste oil regeneration technology is small, and yield is high, good product quality, achieve certain economic benefit but
Above-mentioned technology still remains following shortcoming:
(1) way of distillation equipment investment is big, and cost is high;Distillation process needs high temperature, and temperature is difficult to control, and it is high to consume energy.
(2) extractant and flocculant belong to chemical reagent, and investment ratio is big, increase production cost, and bring at waste water
The difficulty of reason.
Therefore, it needs to replace existing work using small, the high-efficient anacidity technology of waste oil regenerating of a kind of mild condition, pollution
Skill realizes the recycling and reusing of waste rolling oil;Wish that obtained combination of reclaimed grease can satisfy the requirement of biodiesel again simultaneously.
Summary of the invention
The first technical problem to be solved by the present invention is to provide a kind of mild condition, pollution-free, high-efficient cold rolling
The preprocess method of oily Preparation of Biodiesel from Waste Oils raw material.
The second technical problem to be solved by the present invention is to provide a kind of density and acid value can satisfy production of biodiesel
It is required that biodiesel raw material.
The third technical problem to be solved by the present invention is to provide a kind of recycling and reusing method of waste rolling oil.
To solve the above-mentioned problems, on the one hand, it is former that the present invention provides a kind of cold-rolling oil Preparation of Biodiesel from Waste Oils
The preprocess method of material, includes the following steps:
It is filtered after cold-rolling oil is heated, removes solid waste, oil strain is obtained;
Demulsifier is added to described cross in oil strain, stirring is allowed to demulsification reaction;
Flocculant is added into the waste rolling oil after demulsification, implements flocculation;
By the waste rolling oil centrifuge separation after flocculation, oil, waste water, residue are respectively obtained;
The oil is collected, biodiesel raw material is obtained.
Preprocess method according to the present invention, wherein the heating temperature is 60-95 DEG C.Preferably, the heating
Temperature is 65-90 DEG C;It is highly preferred that the heating temperature is 70-85 DEG C;And most preferably, the heating temperature is 75-
85℃.In a specific embodiment, the heating temperature is 80 DEG C.
Preprocess method according to the present invention, wherein the filter for being filtered through 100-400 mesh screen into
Row.Preferably, the filter for being filtered through 100-300 mesh screen carries out;It is highly preferred that described be filtered through 150-300
The filter of mesh screen carries out;And most preferably, the filter for being filtered through 150-200 mesh screen carries out.At one
In specific embodiment, the filter for being filtered through 150 mesh screens is carried out.
Preprocess method according to the present invention, wherein the demulsifier is composite cation demulsifier.
Preprocess method according to the present invention, wherein the demulsifier is by sodium chloride, calcium chloride, magnesium chloride and sulphur
Sour aluminium and the water of surplus composition.
Preprocess method according to the present invention, wherein sodium chloride, calcium chloride, the content of magnesium chloride and aluminum sulfate are each
From independently being 8-12wt%.Preferably, the content of sodium chloride, calcium chloride, magnesium chloride and aluminum sulfate is each independently 8.5-
11.5wt%;It is highly preferred that sodium chloride, calcium chloride, magnesium chloride and aluminum sulfate content be each independently 9-11wt%;With
And most preferably, the content of sodium chloride, calcium chloride, magnesium chloride and aluminum sulfate is each independently 9.5-10.5wt%.At one
In specific embodiment, sodium chloride, calcium chloride, magnesium chloride and aluminum sulfate content be each independently 10wt%.
Preprocess method according to the present invention, wherein the weight ratio for crossing oil strain and composite cation demulsifier
For 1:0.05-0.30.Preferably, the oil strain and the weight ratio of composite cation demulsifier crossed is 1:0.06-0.25;More preferably
Ground, the oil strain and the weight ratio of composite cation demulsifier crossed is 1:0.08-0.20;And most preferably, described to cross oil strain
Weight ratio with composite cation demulsifier is 1:0.10-0.15.In a specific embodiment, it is described cross oil strain with it is compound
The weight ratio of cationic demulsifier is 1:0.12.
Preprocess method according to the present invention, wherein the mixing time after demulsifier is added can be by art technology
Personnel flexibly grasp, as long as can make solution uniformly and react sufficiently completely.In a specific embodiment, described to stir
Mixing the time is 30-40min.
Preprocess method according to the present invention, wherein the flocculant is viscosity average molecular weigh 2,000,000-2,000 ten thousand
Cationic polyacrylamide.Preferably, the flocculant is the cationic polyacrylamide of viscosity average molecular weigh 4,000,000-1,600 ten thousand;
It is highly preferred that the flocculant is the cationic polyacrylamide of viscosity average molecular weigh 6,000,000-1,200 ten thousand;And most preferably,
The flocculant is the cationic polyacrylamide of viscosity average molecular weigh 8,000,000-1,000 ten thousand.In a specific embodiment, institute
State the cationic polyacrylamide that flocculant is viscosity average molecular weigh 9,500,000.
Preprocess method according to the present invention, wherein the flocculant usage is the 0.1- for crossing oil strain
0.6wt%.Preferably, the flocculant usage is the 0.1-0.5wt% for crossing oil strain;It is highly preferred that the flocculant is used
Amount is the 0.1-0.4wt% for crossing oil strain;And most preferably, the flocculant usage is the 0.1- for crossing oil strain
0.3wt%.In a specific embodiment, the flocculant usage is the 0.2wt% for crossing oil strain.
Preprocess method according to the present invention, wherein the mixing time after flocculant is added can be by art technology
Personnel flexibly grasp, as long as can make solution uniformly and react sufficiently completely.In a specific embodiment, described to stir
Mixing the time is 20-30min.
Preprocess method according to the present invention, wherein the centrifuge passes through disk centrifugal 100-400 mesh screen
Filter carries out.As known to those skilled in the art, certain revolving speed and time are controlled, the solids such as fuel-displaced, water and slag can be separated
Waste.
On the other hand, the present invention provides the biodiesel raw materials that above-mentioned preprocess method obtains.The biodiesel raw material
Density be 0.828-0.864g/cm3, acid value≤0.6mgKOH/g.
Another aspect, the present invention provides a kind of recycling and reusing method of waste rolling oil, this method includes above-mentioned cold rolling
The preprocess method of liquefaction Preparation of Biodiesel from Waste Oils raw material, which is characterized in that further comprise entering waste water at sewage
The step of managing pond processing, and/or, the step for carrying out catalytic cleanerr refining is mixed with the solid waste being obtained by filtration including residue
Suddenly.
To sum up, invention broadly provides a kind of pretreatment sides of cold-rolling oil Preparation of Biodiesel from Waste Oils raw material
Method can effectively remove the impurity in particulate matter, metal salt, moisture and the various compounds of waste rolling oil.Through the invention
Waste rolling oil is effectively treated, and can obtain can satisfy the feedstock oil that the esterification, catalysis, pyrogenic process of preparation biodiesel require,
And the residue generated in production process is that the processing of lower step creates conditions, and truly realizes waste oil regeneration skilled industry
The application of change can successfully convert hazardous waste to the clean energy resource utilized again.
It is not intended to limited to any theory, it has been recognised by the inventors that being added in demulsifier by monovalence, divalent and Tricationic
Charge effect occurs for the micro emulsion that the composite cation demulsifier of salt composition can be formed with cold-rolling oil waste oil, thus
Destroy micro emulsion double electrical layers.In addition, composite cation demulsifier can also hydrolyze to form gel in water, generate
Absorption and cohesion facilitate the solid residue in greasy filth to form larger particles sedimentation.Above-mentioned a variety of compound actions are largely
On cause preprocess method of the present invention to obtain biodiesel raw material density and acid value can satisfy the production of biodiesel and want
It asks.
Compared with prior art, the present invention has following advantageous effects:
1, waste rolling oil regeneration enterprise is said, exempting sulfuric acid and distillation carclazyte method has investment small, and equipment is simple, is convenient for
Operation, processing cost is low, the high-quality feature of oil recovery.
2, composite demulsifying agent of the invention is Inorganic water-soluble metal salt, is common industrial chemicals, is not belonging to chemical danger
Dangerous product, cheap and easy to get, use is safe, does not have corrosivity to equipment, while avoiding the volatilization of organic pollutant.
3, simple for process, equipment less energy-consuming can be such that oil, waste water and residue is quickly completely separated, production efficiency
Height generates, no pollution to the environment without peculiar smell.
4, the grease recycled, can reach the raw material for preparing Biodiesel Standards requirement, waste water is as clear as crystal, by simply locating
Reason can reach discharge standard, the solid wastes such as oil-containing mixture can urge after micro alkali neutralization and chemical reagent processing
Change, the raw material of coking refining, three-waste free discharge has good social benefit, environmental benefit and economic benefit.
Specific embodiment
Below by embodiment, the present invention is further described in detail.
Embodiment 1:
Waste rolling oil ester is now used to vapor or 80 DEG C of heat-conducting oil heating in oil storage tank, by 200 mesh stainless steel filtering nets
The filter of basket-hanging is filtered to remove the wastes such as impurity, and oil strain is obtained.
Raw material sodium chloride, calcium chloride, magnesium chloride and each 10wt% of aluminum sulfate are taken, above-mentioned raw materials are ground into carefully with pulverizer
Powder, then be uniformly mixed with 60wt% water, it is dissolved into composite cation demulsifier.
Oil strain 1000kg was taken, is input into the reaction kettle with blender and insulation jacket with pump, is added under stiring
Concentration is 40wt% composite cation demulsifier 100kg, is stirred to react 30~40 minutes, completes the demulsification of waste rolling oil.
Then water-soluble to the cationic polyacrylamide that the waste rolling oil lotion addition concentration after being demulsified is 0.1wt% is completed
Liquid 110kg continues stirring 20~30 minutes, further implements De-emulsification flocculent, promotes water-oil separating.
Mixture after flocculation is input into disk centrifugal separator, precipitation and separation is carried out, obtains oil-water residue, be collected respectively,
The oil separated enters finished product storage tank, as makees the feedstock oil that preparation biodiesel requires.
The waste water separated is as clear as crystal can qualified discharge by simple process into treatment tank.It isolates
The raw material that the residue come is refined as catalytic cleanerr.
Embodiment 2
Waste rolling oil ester is now used to vapor or 85 DEG C of heat-conducting oil heating in oil storage tank, by 150 mesh stainless steel filtering nets
The filter of basket-hanging is filtered to remove the wastes such as impurity, and oil strain is obtained.
Raw material sodium chloride, calcium chloride, magnesium chloride and each 10.5wt% of aluminum sulfate are taken, above-mentioned raw materials are ground into pulverizer
Fine powder, then be uniformly mixed with 58wt% water, it is dissolved into composite cation demulsifier.
Oil strain 3000kg was taken, is input into the reaction kettle with blender and insulation jacket, is added under stiring dense with pump
Degree is stirred to react 40~50 minutes for 42% composite cation demulsifier 375kg, completes the demulsification to ROLLING OIL.
The cationic-type polyacrylamide 25.3kg that concentration is 0.2wt% viscosity average molecular weigh 9,500,000 is subsequently added into continue to stir
It mixes, further implements De-emulsification flocculent, promote water-oil separating.
Mixture after flocculation is input into disc centrifugal separator, precipitation and separation obtains oil-water residue and collects respectively, and oil enters
Finished product oil storage tank is the feedstock oil making preparation biodiesel and requiring.
The waste water separated enters treatment tank processing, can qualified discharge by simple process.The residue of discharge
Raw material as catalytic cleanerr refining.
Embodiment 3
Waste rolling oil ester is now used to vapor or 75 DEG C of heat-conducting oil heating in oil storage tank, by 200 mesh stainless steel filtering nets
The filter of basket-hanging is filtered to remove the wastes such as impurity, and oil strain is obtained.
Raw material sodium chloride, calcium chloride, magnesium chloride and each 9.5wt% of aluminum sulfate are taken, above-mentioned raw materials are ground into pulverizer
Fine powder, then be uniformly mixed with 62wt% water, it is dissolved into composite cation demulsifier.
The ROLLING OIL 5000kg for taking filtering is input into the reaction kettle with blender and insulation jacket with pump, is being stirred
The lower water-soluble demulsifier 750kg that concentration is added and is 38%, is stirred to react 50~60 minutes, completes the demulsification to ROLLING OIL.
Being subsequently added into concentration is that 0.3wt% cationic-type polyacrylamide 38.3kg continues to stir, and further implements demulsification
Flocculation promotes water-oil separating.
Mixture after flocculation is input into disc centrifugal separator, precipitation and separation obtains oil-water residue and collects respectively, and oil enters
Finished product oil storage tank is the feedstock oil making preparation biodiesel and requiring.
The waste water separated enters treatment tank processing, can qualified discharge by simple process.The residue of discharge
Raw material as catalytic cleanerr refining.
Comparative example 1:
Raw material calcium chloride, magnesium chloride and aluminum sulfate each 10wt%, 10wt% and 20wt% are taken respectively, by above-mentioned raw materials powder
Broken machine is ground into fine powder, then is uniformly mixed with 60wt% water, is dissolved into composite cation demulsifier, remaining is the same as embodiment 1.
Comparative example 2:
Raw material sodium chloride, calcium chloride and magnesium chloride each 20wt%, 10wt% and 10wt% are taken respectively, by above-mentioned raw materials powder
Broken machine is ground into fine powder, then is uniformly mixed with 60wt% water, is dissolved into composite cation demulsifier, remaining is the same as embodiment 1.
Comparative example 3:
Raw material calcium chloride and magnesium chloride each 20wt% and 20wt% are taken respectively, and above-mentioned raw materials are ground into fine powder with pulverizer
End, then be uniformly mixed with 60wt% water, it is dissolved into composite cation demulsifier, remaining is the same as embodiment 1.
Table 1 gives the density and acid value and waste water appearance of biodiesel raw material obtained by embodiment 1-3 and comparative example 1-3
Situation.Relevant test method and condition are referring to professional standard.
Table 1
As can be seen from Table 1, the density of biodiesel raw material obtained by the embodiment of the present application 1-3 and acid value are significantly better than and compare
Example 1-3;In addition, waste water appearance clear, no suspended substance.The application is added by monovalence, divalent and trivalent sun in demulsifier
A variety of compound works that the micro emulsion that the composite cation demulsifier and cold-rolling oil waste oil of ion salt composition are formed occurs
With the result for largely leading to this significant difference.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., is all included in the scope of protection of the present invention.
Claims (10)
1. a kind of preprocess method of cold-rolling oil Preparation of Biodiesel from Waste Oils raw material, includes the following steps:
It is filtered after cold-rolling oil is heated, removes solid waste, oil strain is obtained;
Demulsifier is added to described cross in oil strain, stirring is allowed to demulsification reaction;
Flocculant is added into the waste rolling oil after demulsification, implements flocculation;
By the waste rolling oil centrifuge separation after flocculation, oil, waste water, residue are respectively obtained;
The oil is collected, biodiesel raw material is obtained.
2. preprocess method according to claim 1, wherein the heating temperature is 60-95 DEG C.
3. preprocess method according to claim 1, wherein the demulsifier is composite cation demulsifier.
4. preprocess method according to claim 3, wherein the demulsifier is by sodium chloride, calcium chloride, magnesium chloride and sulphur
Sour aluminium and the water of surplus composition.
5. preprocess method according to claim 4, wherein sodium chloride, calcium chloride, the content of magnesium chloride and aluminum sulfate are each
From independently being 8-12wt%.
6. according to the described in any item preprocess methods of claim 3-5, wherein described to cross oil strain and composite cation demulsifier
Weight ratio be 1:0.05-0.30.
7. preprocess method according to claim 1, wherein the flocculant is viscosity average molecular weigh 2,000,000-2,000 ten thousand
Cationic polyacrylamide;The flocculant usage is the 0.1-0.6wt% for crossing oil strain.
8. preprocess method according to claim 1, wherein the centrifuge passes through disk centrifugal 100-400 mesh screen
Filter carry out.
9. a kind of biodiesel raw material, which is characterized in that obtained by the described in any item preprocess methods of claim 1-8.
10. a kind of recycling and reusing method of waste rolling oil, this method includes the described in any item cold-rolling oils of claim 1-8
The preprocess method of Preparation of Biodiesel from Waste Oils raw material, which is characterized in that further comprise that waste water is made to enter treatment tank
The step of processing, and/or, include the steps that residue is mixed with the solid waste being obtained by filtration and carries out catalytic cleanerr refining.
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