CN102952570B - Method for preparing environmentally-friendly rubber oil through two-segment countercurrent solvent extraction - Google Patents
Method for preparing environmentally-friendly rubber oil through two-segment countercurrent solvent extraction Download PDFInfo
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Abstract
The invention relates to a method for preparing environmentally-friendly rubber oil through two-segment countercurrent solvent extraction. The method treats vacuum-distillated aromatic hydrocarbon extract oil as a raw material, and adopts a polyhydroxy alcohol or a polyhydroxy alcohol ester as a first extraction segment solvent and a ternary composite solvent which comprises 60-83% by volume of furfural, 15-35% by volume of the polyhydroxy alcohol or the polyhydroxy alcohol ester, and the balance an aqueous NaCl solution as a second extraction segment solvent to carry out two-segment solvent extraction, and the environmentally-friendly rubber oil is obtained under operation conditions that the top temperature of an extraction tower is 50-100DEG C and the solvent-oil volume ratio is 0.5-3.0:1. By using the method to refine the aromatic hydrocarbon extract oil, the contents of fused ring compounds in the prepared refined oil are reduced to below 3%, the sum of eight PAHs is less than 10mg/kg, and the total yield of the refined oil is higher than 60wt%.
Description
Technical field
The present invention relates to the method for solvent treatment hydrocarbon ils, particularly relate to the environment-friendly rubber oil utilizing double solvents extracting naphthenic lube oil component to come for the preparation of rubber for tire and goods thereof.
Background technology
As everyone knows, the rubber oil of aromatic hydrocarbons type and the consistency of the alkadiene such as styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber rubber and effect fine, particularly extensive in the utilization of tyre industry.Along with European Union completely forbids the poisonous aromatic hydrocarbon oil DAE (disitillate aromatic extraction) of use to Tire production and import, no matter be rubber for tire manufacturers, or Tire production enterprise, is all actively tackling, finding the product substituting aromatic hydrocarbon oil DAE.
Because this standard/regulation is initiated from European Union, the substitute products scheme therefore about aromatic hydrocarbon oil DAE is roughly divided into three classes: TDAE, MES, NAP.Wherein TDAE (process aromatic hydrocarbon oil treated disitillate aromatic extraction) re-refines after the poisonous polycyclic aromatic hydrocarbons of removing to former aromatic hydrocarbon oil to produce, there is relatively high aromaticity content (tlc aromaticity content is greater than 60% usually), with rubber for tire, there is good consistency, tire rubber article more original DAE formula in anti-slippery, wear-resisting etc. declines remarkable, is therefore also the focal point of numerous enterprises client.
TDAE take DAE as product prepared by raw material, the rubber oil method for preparing ingredients thereof of relevant patent a kind of low polycyclic aromatic hydrocarbons PCA as international patent application No.505524/1994 discloses, and raw material is from deasphalted oil, and its viscosity is very large, but is of limited application; EP417980A1 discloses the method adopting two-section extraction technique to prepare the rubber process oil of the low polycyclic aromatic hydrocarbons PCA of high aromatic hydrocarbons, its defect is the Extract from first paragraph extraction process, simultaneously as the raw material of second segment, the difference of the polar solvent that its density and second segment use is very little, cause the second extracting section oil difficult with the phase-splitting of solvent, yield is very low simultaneously, is usually less than 51wt%; EP0839891A2 provides a kind of technical oil preparation method preparing polycyclic aromatic hydrocarbons PCA and be less than 3%, and it is characterized in that 100 DEG C of kinematic viscosity are between 2 ~ 70cst, polar compound content is less than 10wt%, and aromatic hydrocarbons and polar compound sum are not less than 40wt%; International patent application No.501346/1995 provides and carries out from the bright stock raw material of the non-carcinogenic of long residue feed and/or deasphalted oil the method that Aromatics Extractive Project prepares rubber oil; International patent application No.505524/1994 and WO92/14479 discloses the rubber process oil utilizing 350 ~ 600 of middle-eastern crude DEG C of vacuum distillates to prepare low polycyclic aromatic hydrocarbons PCA; International patent application No.503215/1996 discloses a kind of method adopting alkylated reaction to reduce the teratogenic effect of condensed-nuclei aromatics; US2002/0188054A1, US6399697B1, US6605695B2 disclose the mixture utilizing polar solvent process residual oil 20 ~ 90v% and lubricant base 10-80%, and its extraction solvent is than 0.5 ~ 2.5: 1, extraction tower tower top temperature 60 ~ 115 DEG C, extraction tower column bottom temperature 45 ~ 80 DEG C; FR 2685705A1 utilizes distillation-Aromatics Extractive Project-dewaxing combination process to prepare the product of the low polycyclic aromatic hydrocarbons PCA content of aromaticity content 40 ~ 50%; WO9844075mobil oil company discloses and adopts the second polar solvent to process extract oil of lubricating oil from first paragraph Aromatics Extractive Project, prepares the rubber oil of low polycyclic aromatic hydrocarbons PCA; EP 0417980A1 discloses the preparation method of BP company rubber oil, adopt polar solvent reextraction from the extraction oil of the first Aromatics Extractive Project section, second segment solvent ratio 1 ~ 1.8: 1, second extraction tower (counter-current extraction tower) thermograde: tower top 50 ~ 90 DEG C, at the bottom of tower 20 ~ 60 DEG C, prepared product aromaticity content is greater than 50%, and polycyclic aromatic hydrocarbons PCA content is less than 3%; The Extract of Aromatics Extractive Project section cools by EP 839891, and obtain the rubber oil component of cold analysis oil as low polycyclic aromatic hydrocarbons PCA, the solvent of its Aromatics Extractive Project section can be phenol, furfural and NMP.
The technique that preparation TDAE is more special has: EP0489371B and DE4038458C2 discloses the preparation technology utilizing carbon dioxide upercritical fluid extraction polycyclic aromatic hydrocarbons PCA; US2003/0168382A1 carries out the technique of hydrotreatment after disclosing and extracting distillate and aromatic hydrocarbons out oil mixing, its catalyzer is Ni-Mo, Ni-Mo-Co series catalysts, treatment temp top condition is 265 ~ 324 DEG C, and reaction pressure is 6.0 ~ 8.0MPa, air speed 0.5 ~ 1.5.Preparation TDAE compares has the US6146520 of feature to be the technique of the mixed solvent secondary extracting utilizing sulfone class, propylene carbonate etc., may be used for the MI index or the polycyclic aromatic hydrocarbons PCA content that reduce DAE.Extraction process described by this patent is roughly as follows: from the material (containing DAE) of the first extracting section at the extraction temperature of the second extracting section at 20 ~ 65 DEG C, be enough to duration of contact remove polycyclic aromatic hydrocarbons PCA and form the two-phase be separated, the solvent of the second extracting section can be dimethyl sulfoxide (DMSO), the mixed solvent of tetramethylene sulfone and propylene carbonate etc., its specific inductivity is usually above the specific inductivity (25 DEG C of specific inductivity are at least more than 44) of the first extracting section.Be separated extraction phase and the extracting phase of the second extracting section, can obtain yield at least 70%, polycyclic aromatic hydrocarbons PCA is less than 3% or the MI rubber processing oil being rich in aromatic hydrocarbons that is less than 1.0.In fact, the object of employing mixed solvent is exactly the solubleness in order to reduce conventional aromatic hydrocarbon extraction solvent, the solvent combination disclosed in the text of this contrast patent: NMP/water, furfural/propylene carbonate, furfural/sulfolane, furfural/water, NMP/ethylene glycol, furfural/ethylene glycol, DMSO/cyclohexane.The mixed solvent applied in embodiment be combined as DMSO/cyclohexane.
Independent application tri compound solvent (1) furfural 50v% ~ 89v%; 2) polyhydroxy-alcohol or polyhydroxy alkyl ester 10v% ~ 30v%; 3) the NaCl aqueous solution of surplus) process DAE, similar with US6146520, namely salt solution (the NaCl aqueous solution) is utilized to destroy the dissolving power of furfural to aromatic hydrocarbons, improve PCA or PAHs selectivity, its defect is that the product P CA after processing is greater than 3%, discontented toe ring guaranteed request.
And apply merely polyhydroxy-alcohol or polyhydroxy alkyl ester, because it is to the dissolving power extreme difference of hydro carbons in DAE, although good to the selectivity of condensed-nuclei aromatics PCA or PAHs, essential oil yield is usually more than 70%, but the PCA content of treated oil is greater than 6% usually, even if adopt the means of twice extracting, be also only the reduction causing yield, the PCA content of treated oil is still more than 6%, and therefore the effect of application is not good separately.
Summary of the invention
The object of the invention is the method providing two sections of solvent extraction aromatic hydrocarbon oil DAE.Wherein the solvent of first paragraph application is that (its density is more than or equal to 1.2 × 10 to polyhydroxy-alcohol (ester)
3kg/m
3, the specific inductivity of 20 DEG C is greater than 40), can be any one in glycerine, monoacetin, glyceryl diacetate, ethylene carbonate, propylene carbonate; Second segment solvent is tri compound solvent: 1) furfural 50v% ~ 89v%; 2) polyhydroxy-alcohol or polyhydroxy alkyl ester 10v% ~ 30v%; 3) the NaCl aqueous solution of surplus.Apply combination solvent provided by the invention in the refining plant with two extraction tower series systems, under felicity condition, carry out two sections of countercurrent extraction to aromatic hydrocarbon oil DAE, namely solvent from top to bottom, and aromatic hydrocarbon oil raw material carries out extractive distillation from bottom to top.
The method of environment-friendly rubber oil is prepared in two sections of counter current solvent extractings of the present invention: extract oil out for raw material with the aromatic hydrocarbons of reduced pressure distillate, adopt polyhydroxy-alcohol or polyhydroxy alkyl ester as the first extracting section solvent, adopt tri compound solvent by volume percentages: 1) furfural 60 ~ 83%; 2) polyhydroxy-alcohol or polyhydroxy alkyl ester 15 ~ 35%; 3) the NaCl aqueous solution of surplus is as the second extracting section solvent, carries out two sections of solvent extractions, and at extraction tower head temperature scope 50-100 DEG C, solvent and oil volume obtain environment-friendly rubber oil than under the operational condition of 0.5-3.0: 1.
Described polyhydroxy-alcohol or polyhydroxy alkyl ester are glycerine, the one in monoacetin, propylene carbonate, ethylene carbonate.
The tower top temperature scope of the first extracting section 85 DEG C-100 DEG C, column bottom temperature scope 65 DEG C-80 DEG C, solvent ratio 1.5-2.5: 1; The tower top temperature scope of the second extracting section 75 DEG C-90 DEG C, column bottom temperature scope 55 DEG C-70 DEG C, solvent ratio 1.0-2.0: 1.
The technical process of applying two sections of solvent extractions provided by the invention is: first with solvent pump, first extraction tower polyhydroxy-alcohol (ester) solvent is made first paragraph counter-current extraction tower or extractor, then by heat exchange or ancillary heating equipment, the liquid phase in container is warmed up within the scope of extraction temperature, with feedstock pump, aromatic hydrocarbon oil oil is introduced from the bottom of the first counter-current extraction tower again, first time counter current contact is from bottom to top carried out with polyhydroxy-alcohol (ester) solvent entering tower or enter tank, then raffinate on the top of extraction tower epimere after the sedimentation of for some time, enter into the bottom of second segment counter-current extraction tower by drawing pipeline from the top of container, counter current contact is from bottom to top carried out with the tri compound solvent entering tower in the second counter-current extraction tower, then device is gone out from the extraction pipeline of the second counter-current extraction column overhead, obtain raffinate.Raffinate obtains required environmental tire rubber oil product after solvent recuperation and water vapour stripping/nitrogen air lift desolventizing.
The filler of counter-current extraction tower normally stainless steel filler, the stainless steel Dixon ring that stainless steel structured packing or layering huddle can be selected.
Process raw material of the present invention is that the aromatic hydrocarbons of reduced pressure distillate extracts oil (DAE) out, and its normal pressure boiling range scope is between 350 DEG C ~ 550 DEG C, and usual density range is 940 ~ 1050kg/m
3, polycyclic aromatic hydrocarbons PCA content is generally 15-40%, and refractive index (20 DEG C) is usually between 1.54 ~ 1.60.
Described aromatic hydrocarbons extracts oily raw material out, and CA% is between 30-40 for its aromatic carbon percentage composition (calculating of ASTM D2140 method), and 100 DEG C of kinematic viscosity are between 35-60mm
2/ s, 20 DEG C of density are 940-1050kg/m
3.
Apply two-stage extraction technique of the present invention and tri compound solvent to process aromatic hydrocarbon oil DAE, fused ring compound (comprising PAHs or the PNA) content of prepared treated oil (raffinating oil of two-stage extraction) is reduced to less than 3%, and the summation of 8 kinds of PAHs (EPA8270C method) is less than 10mg/kg.Apply two-stage extraction technique of the present invention and tri compound solvent, the total recovery of treated oil (raffinating oil of two-stage extraction) is higher than 60wt%.Under good condition, yield is 65-75wt%, and under best conditions, yield reaches 70-75wt%.
Embodiment
The cycloalkyl aromatic hydrocarbon oil DAE of process of the present invention, be Kelamayi cycloalkyl cut furfural extract oil, its property representation is:
100 DEG C of kinematic viscosity 35-60mm that ASTM D445 method measures
2/ s, the acid number that GB/T264 method measures is 2.5-4.0mgKOH/g, boiling range scope (the initial boiling point IBP 370-385 DEG C that ASTM D1160 method measures, 5% recovered temperature 410-425 DEG C, 99% recovered temperature 535-555 DEG C), 20 DEG C of density that SH/T0604 method measures are 990-1005kg/m
3(CA% is 32-37 in the carbon type distribution that ASTM D2140 method measures, CP% is 40-45, CN% is 20-25), the polycyclic aromatic hydrocarbon content that IP346 method measures is 16-23wt%, EPA8270C method measures 8 kinds of PAHs (BaP benzo (a) pyrenes, BeP benzo (e) pyrene, BaA benzo (a) anthracene, CHR bends, BbFA benzo (b) fluoranthene, BjFA benzo (j) fluoranthene, BkFA benzo (k) fluoranthene, DBAhA dibenzo (a, h) anthracene) total content be 400-550mg/kg.
Embodiment 1
The small-sized furfural extraction test and solvent recuperation testing apparatus of 1kg/h feed throughput have been carried out the test of tri compound solvent two-stage extraction, and stock oil is above-mentioned Kelamayi cycloalkyl cut furfural extract oil.The solvent of two-stage extraction is respectively: the first extracting section solvent is the industry glycerol of 100%, the second extracting section tri compound solvent, and tri compound solvent composition is: the 1. NaCl solution 2v% of furfural 83v% 2. glycerine 15v% 3. massfraction 13wt%.
By purity be 99.0% industry glycerol solvent be injected into the first counter-current extraction tower through pumping from the top of the first counter-current extraction tower and the upper limb of filler extraction section, namely stock oil with 90 DEG C ± 10 DEG C the upper limb of settling section to pump into the first counter-current extraction tower through oil pump from the bottom of the first counter-current extraction tower to carry out counter-current extraction, extraction temperature is 70 ~ 90 DEG C, tower top settling section temperature is 85 DEG C ± 1 DEG C, settling section temperature at the bottom of tower is 65 DEG C ± 1 DEG C, and solvent volume ratio is 2.4: 1, tri compound solvent is injected the upper limb of the second counter-current extraction tower filler extraction section, countercurrent extraction is carried out with the raffinate from the first extraction tower of the lower settling section upper limb from the second counter-current extraction tower, control extraction temperature 60 DEG C ~ 80 DEG C, tower top temperature is 75 DEG C ± 1 DEG C, and column bottom temperature is 55 DEG C ± 1 DEG C, solvent volume ratio is 1.2: 1, by the raffinate of the second extracting section through one section or multistage underpressure distillation, (underpressure distillation condition: residual voltage 30-50mmHg, heat up in a steamer temperature out 50-70 DEG C) and through nitrogen air lift or water vapor air lift, stripping conditions: condition (vapor-liquid ratio, 15wt%-30wt%, stripping temperature 240-300 DEG C), maximum boiling point solvent in tri compound solvent composition is reclaimed completely (being converted into atmospheric boiling point higher than 300 DEG C), raffinating oil of obtaining is environmental tire rubber oil, environmental tire rubber oil yield is 66.7wt%, aromaticity content (ASTM D2140 method) is 16.6%, PCA content 2.88wt%, eight kinds of total contents limiting condensed-nuclei aromatics are 6.98mg/kg, wherein the content of benzo (a) pyrene is 0.48mg/kg.
Embodiment 2
Identical small-sized furfural extraction test and solvent recuperation testing apparatus have been carried out the test of tri compound solvent two-stage extraction, and stock oil is all above-mentioned Kelamayi cycloalkyl cut furfural extract oil.The solvent of two-stage extraction is respectively: the solvent of the first extracting section is 100% industry glycerol (purity 99.0%), and its composition of the tri compound solvent of the second extracting section is changed to: the 1. NaCl solution 5v% of furfural 65v% 2. glycerine 35v% 3. massfraction 14wt%.
By purity be 99.0% industry glycerol solvent be injected into the first counter-current extraction tower through pumping from the top of the first counter-current extraction tower and the upper limb of filler extraction section, namely stock oil with 80 DEG C ± 10 DEG C the upper limb of settling section to pump into the first counter-current extraction tower through oil pump from the bottom of the first counter-current extraction tower to carry out counter-current extraction, extracting section thermograde is 80 ~ 100 DEG C, tower top settling section temperature is 95 DEG C ± 1 DEG C, settling section temperature at the bottom of tower is 75 DEG C ± 1 DEG C, and solvent volume ratio is 2.0: 1, tri compound solvent is injected the upper limb of the second counter-current extraction tower filler extraction section, countercurrent extraction is carried out with the raffinate from the first extraction tower of the lower settling section upper limb from the second counter-current extraction tower, extracting section thermograde 60 DEG C ~ 80 DEG C, tower top settling section temperature is 75 DEG C ± 1 DEG C, and settling section temperature at the bottom of tower is 55 DEG C ± 1 DEG C, solvent volume ratio is 1.3: 1, by the raffinate of the second extracting section through one section or multistage underpressure distillation, (underpressure distillation condition: residual voltage 30-50mmHg, heat up in a steamer temperature out 50-70 DEG C) and through nitrogen air lift or water vapor air lift, stripping conditions: condition (vapor-liquid ratio, 15wt%-30wt%, stripping temperature 240-300 DEG C), maximum boiling point solvent in tri compound solvent composition is reclaimed completely (being converted into atmospheric boiling point higher than 300 DEG C), raffinating oil of obtaining is environment-friendly rubber oil, environment-friendly rubber oil yield is 61.4wt%, aromaticity content (ASTM D2140 method) is 16.7%, PCA content 2.78wt%, eight kinds of total contents limiting condensed-nuclei aromatics are 6.24mg/kg, wherein the content of benzo (a) pyrene is 0.45mg/kg.
Embodiment 3
Identical small-sized furfural extraction test and solvent recuperation testing apparatus have been carried out the test of tri compound solvent two-stage extraction, and stock oil is all above-mentioned Kelamayi cycloalkyl cut furfural extract oil.The solvent of two-stage extraction is respectively: the solvent of the first extracting section is 100% monoacetin (purity 99.0%), and its composition of the tri compound solvent of the second extracting section is changed to: the 1. NaCl solution 10v% of furfural 60v% 2. glycerine 30v% 3. massfraction 15wt%.
By purity be 99.0% monoacetin solvent be injected into the first counter-current extraction tower through pumping from the top of the first counter-current extraction tower and the upper limb of filler extraction section, namely stock oil with 60 DEG C ± 10 DEG C the upper limb of settling section to pump into the first counter-current extraction tower through oil pump from the bottom of the first counter-current extraction tower to carry out counter-current extraction, extracting section thermograde is 65 ~ 85 DEG C, tower top settling section temperature is 80 DEG C ± 1 DEG C, settling section temperature at the bottom of tower is 70 DEG C ± 1 DEG C, and solvent volume ratio is 1.8: 1, tri compound solvent is injected the upper limb of the second counter-current extraction tower filler extraction section, countercurrent extraction is carried out with the raffinate from the first extraction tower of the lower settling section upper limb from the second counter-current extraction tower, extracting section thermograde 60 DEG C ~ 80 DEG C, tower top settling section temperature is 75 DEG C ± 1 DEG C, and settling section temperature at the bottom of tower is 55 DEG C ± 1 DEG C, solvent volume ratio is 1.9: 1, by the raffinate of the second extracting section through one section or multistage underpressure distillation, (underpressure distillation condition: residual voltage 30-50mmHg, heat up in a steamer temperature out 50-70 DEG C) and through nitrogen air lift or water vapor air lift, stripping conditions: condition (vapor-liquid ratio, 15wt%-30wt%, stripping temperature 240-300 DEG C), maximum boiling point solvent in tri compound solvent composition is reclaimed completely (being converted into atmospheric boiling point higher than 300 DEG C), raffinating oil of obtaining is environmental tire rubber oil, environmental tire rubber oil yield is 66.2wt%, aromaticity content (ASTM D2140 method) is 17.0%, PCA content 2.93wt%, eight kinds of total contents limiting condensed-nuclei aromatics are 7.33mg/kg, wherein the content of benzo (a) pyrene is 0.33mg/kg.
Embodiment 4
Identical small-sized furfural extraction test and solvent recuperation testing apparatus have been carried out the test of tri compound solvent two-stage extraction, and stock oil is all above-mentioned Kelamayi cycloalkyl cut furfural extract oil.The solvent of two-stage extraction is respectively: the solvent of the first extracting section is 100% propylene carbonate (purity 99.0%), and its composition of the tri compound solvent of the second extracting section is changed to: the 1. NaCl solution 10v% of furfural 60v% 2. glycerine 30v% 3. massfraction 15wt%.
By purity be 99.0% propylene carbonate solvent be injected into the first counter-current extraction tower through pumping from the top of the first counter-current extraction tower and the upper limb of filler extraction section, namely stock oil with 90 DEG C ± 10 DEG C the upper limb of settling section to pump into the first counter-current extraction tower through oil pump from the bottom of the first counter-current extraction tower to carry out counter-current extraction, extracting section thermograde is 80 ~ 100 DEG C, tower top settling section temperature is 95 DEG C ± 1 DEG C, settling section temperature at the bottom of tower is 75 DEG C ± 1 DEG C, and solvent volume ratio is 2.3: 1, tri compound solvent is injected the upper limb of the second counter-current extraction tower filler extraction section, countercurrent extraction is carried out with the raffinate from the first extraction tower of the lower settling section upper limb from the second counter-current extraction tower, extracting section thermograde 65 DEG C ~ 85 DEG C, tower top settling section temperature is 80 DEG C ± 1 DEG C, and settling section temperature at the bottom of tower is 60 DEG C ± 1 DEG C, solvent volume ratio is 1.7: 1, by the raffinate of the second extracting section through one section or multistage underpressure distillation, (underpressure distillation condition: residual voltage 30-50mmHg, heat up in a steamer temperature out 50-70 DEG C) and through nitrogen air lift or water vapor air lift, stripping conditions: condition (vapor-liquid ratio, 15wt%-30wt%, stripping temperature 220-260 DEG C), maximum boiling point solvent in tri compound solvent composition is reclaimed completely, raffinating oil of obtaining is environment-friendly rubber oil, environment-friendly rubber oil yield is 70.1wt%, aromaticity content (ASTM D2140 method) is 17.2%, PCA content 2.93wt%, eight kinds of total contents limiting condensed-nuclei aromatics are 7.05mg/kg, wherein the content of benzo (a) pyrene is 0.39mg/kg.
Embodiment 5
Identical small-sized furfural extraction test and solvent recuperation testing apparatus have been carried out the test of tri compound solvent two-stage extraction, and stock oil is all above-mentioned Kelamayi cycloalkyl cut furfural extract oil.The solvent of two-stage extraction is respectively: the solvent of the first extracting section is 100% ethylene carbonate (purity 99.0%), and its composition of the tri compound solvent of the second extracting section is changed to: the 1. NaCl solution 10v% of furfural 60v% 2. glycerine 30v% 3. massfraction 15wt%.
By purity be 99.0% diglycol carbonate ester solvent be injected into the first counter-current extraction tower through pumping from the top of the first counter-current extraction tower and the upper limb of filler extraction section, namely stock oil with 70 DEG C ± 10 DEG C the upper limb of settling section to pump into the first counter-current extraction tower through oil pump from the bottom of the first counter-current extraction tower to carry out counter-current extraction, extracting section thermograde is 70 ~ 90 DEG C, tower top settling section temperature is 85 DEG C ± 1 DEG C, settling section temperature at the bottom of tower is 65 DEG C ± 1 DEG C, and solvent volume ratio is 1.5: 1, tri compound solvent is injected the upper limb of the second counter-current extraction tower filler extraction section, countercurrent extraction is carried out with the raffinate from the first extraction tower of the lower settling section upper limb from the second counter-current extraction tower, extracting section thermograde 65 DEG C ~ 85 DEG C, tower top settling section temperature is 80 DEG C ± 1 DEG C, and settling section temperature at the bottom of tower is 60 DEG C ± 1 DEG C, solvent volume ratio is 1.6: 1, by the raffinate of the second extracting section through one section or multistage underpressure distillation, (underpressure distillation condition: residual voltage 30-50mmHg, heat up in a steamer temperature out 50-70 DEG C) and through nitrogen air lift or water vapor air lift, stripping conditions: condition (vapor-liquid ratio, 15wt%-30wt%, stripping temperature 220-260 DEG C), maximum boiling point solvent in tri compound solvent composition is reclaimed completely, raffinating oil of obtaining is environment-friendly rubber oil, environment-friendly rubber oil yield is 74.3wt%, aromaticity content (ASTM D2140 method) is 17.4%, PCA content 2.96wt%, eight kinds of total contents limiting condensed-nuclei aromatics are 7.05mg/kg, wherein the content of benzo (a) pyrene is 0.39mg/kg.
Embodiment 6
The present embodiment is the simultaneous test using furfural as first paragraph extraction solvent.
Identical small-sized furfural extraction test and solvent recuperation testing apparatus have been carried out the test of tri compound solvent two-stage extraction, and stock oil is all above-mentioned Kelamayi cycloalkyl cut furfural extract oil.
The solvent of two-stage extraction is respectively: the first extracting section solvent 100% Technical furfural is (through dehydration cycle, water ratio is less than 0.5wt%), the solvent of the second extracting section is tri compound solvent (furfural 70v%, ethylene carbonate 25v%, the NaCl solution 5v% of massfraction 15wt%).
Technical furfural solvent water ratio being less than 0.5wt% is injected into the first counter-current extraction tower through pumping from the top of the first counter-current extraction tower and the upper limb of filler extraction section, namely stock oil with 60 DEG C ± 10 DEG C the upper limb of settling section to pump into the first counter-current extraction tower through oil pump from the bottom of the first counter-current extraction tower to carry out counter-current extraction, extracting section thermograde is 50 ~ 70 DEG C, tower top settling section temperature is 65 DEG C ± 1 DEG C, settling section temperature at the bottom of tower is 45 DEG C ± 1 DEG C, and solvent volume ratio is 1.5: 1, tri compound solvent is injected the upper limb of the second counter-current extraction tower filler extraction section, countercurrent extraction is carried out with the raffinate from the first extraction tower of the lower settling section upper limb from the second counter-current extraction tower, extracting section thermograde 65 DEG C ~ 85 DEG C, tower top settling section temperature is 80 DEG C ± 1 DEG C, and settling section temperature at the bottom of tower is 60 DEG C ± 1 DEG C, solvent volume ratio is 1.5: 1, by the raffinate of the second extracting section through one section or multistage underpressure distillation, (underpressure distillation condition: residual voltage 30-50mmHg, heat up in a steamer temperature out 50-70 DEG C) and through nitrogen air lift or water vapor air lift, stripping conditions: condition (vapor-liquid ratio, 15wt%-30wt%, stripping temperature 220-260 DEG C), maximum boiling point solvent in tri compound solvent composition is reclaimed completely, raffinating oil of obtaining is environment-friendly rubber oil, environment-friendly rubber oil yield is 49.6wt%, aromaticity content (ASTM D2140 method) is 16.2%, PCA content 2.96wt%, eight kinds of total contents limiting condensed-nuclei aromatics are 5.05mg/kg, wherein the content of benzo (a) pyrene is 0.27mg/kg.
From the implementation result of embodiment 1 to embodiment 5, the polycyclic aromatic hydrocarbons PCA raffinated oil all is less than 3%, the total amount of 8 kinds of restriction condensed-nuclei aromatics PAHs all reaches the requirement of European Union 2005/69/EC annex 1*, be nontoxic environment-friendly rubber oil, and the yield of environment-friendly rubber oil is all more than 60wt%.
From the implementation result of comparative example 6, application furfural is as the first extraction solvent, tri compound solvent as the second extraction solvent, and the yield of raffinating oil of embodiment is only 49.6wt%, comparatively embodiment 1 to embodiment 5, decline all in various degree, at least decline about 11 percentage points.
* note: European Union 2005/69/EC instruction annex 1: benzopyrene (BaP) content adopting GC-MS method to measure should lower than 1mg/kg, 8 kinds of PAHs (BaP benzo (a) pyrenes simultaneously, BeP benzo (e) pyrene, BaA benzo (a) anthracene, CHR bends, BbFA benzo (b) fluoranthene, BjFA benzo (j) fluoranthene, BkFA benzo (k) fluoranthene, DBAhA dibenzo (a, h) anthracene) total content should lower than 10mg/kg.
Claims (1)
1. the method for environment-friendly rubber oil is prepared in two sections of counter current solvent extractings, it is characterized in that: in the small-sized furfural extraction test and solvent recuperation testing apparatus of 1kg/h feed throughput, carry out the test of tri compound solvent two-stage extraction, stock oil is Kelamayi cycloalkyl cut furfural extract oil; The solvent of two-stage extraction is respectively: the first extracting section solvent is the industry glycerol of 100%, and the second extracting section is tri compound solvent, and tri compound solvent composition is: the NaCl solution 2v% of furfural 83v%, glycerine 15v%, massfraction 13wt%;
By purity be 99.0% industry glycerol solvent be injected into the first counter-current extraction tower through pumping from the top of the first counter-current extraction tower and the upper limb of filler extraction section, namely stock oil with 90 DEG C ± 10 DEG C the upper limb of settling section to pump into the first counter-current extraction tower through oil pump from the bottom of the first counter-current extraction tower to carry out counter-current extraction, extraction temperature is 70 ~ 90 DEG C, tower top settling section temperature is 85 DEG C ± 1 DEG C, settling section temperature at the bottom of tower is 65 DEG C ± 1 DEG C, and solvent volume is than being 2.4:1; Tri compound solvent is injected the upper limb of the second counter-current extraction tower filler extraction section, countercurrent extraction is carried out with the raffinate from the first extraction tower of the lower settling section upper limb from the second counter-current extraction tower, control extraction temperature 60 DEG C ~ 80 DEG C, tower top temperature is 75 DEG C ± 1 DEG C, and column bottom temperature is 55 DEG C ± 1 DEG C; Solvent volume is than being 1.2:1; By the raffinate of the second extracting section through one section or multistage underpressure distillation, underpressure distillation condition: residual voltage 30-50mmHg, heat up in a steamer temperature out 50-70 DEG C, and through nitrogen air lift or water vapor air lift, stripping conditions: vapor-liquid ratio, 15wt%-30wt%, stripping temperature 240-300 DEG C, reclaimed completely by maximum boiling point solvent in tri compound solvent composition, be converted into atmospheric boiling point higher than 300 DEG C, raffinating oil of obtaining is environmental tire rubber oil.
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| EP0417980A1 (en) * | 1989-09-12 | 1991-03-20 | BP Oil Deutschland GmbH | Process for the production of process oils with a low content of polycyclic aromatic compounds |
| US6146520A (en) * | 1997-04-02 | 2000-11-14 | Mobil Oil Corporation | Selective re-extraction of lube extracts to reduce mutagenicity index |
| CN1361813A (en) * | 1999-07-23 | 2002-07-31 | 埃克森美孚研究工程公司 | Selective extraction using mixed solvent system |
| CN101870886A (en) * | 2010-06-07 | 2010-10-27 | 中国石油大学(华东) | Production method of environment-friendly rubber oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0417980A1 (en) * | 1989-09-12 | 1991-03-20 | BP Oil Deutschland GmbH | Process for the production of process oils with a low content of polycyclic aromatic compounds |
| US6146520A (en) * | 1997-04-02 | 2000-11-14 | Mobil Oil Corporation | Selective re-extraction of lube extracts to reduce mutagenicity index |
| CN1361813A (en) * | 1999-07-23 | 2002-07-31 | 埃克森美孚研究工程公司 | Selective extraction using mixed solvent system |
| CN101870886A (en) * | 2010-06-07 | 2010-10-27 | 中国石油大学(华东) | Production method of environment-friendly rubber oil |
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