CN105647634B - A kind of preparation method of waste lubricating oil production clear gusoline technique and its catalyst - Google Patents
A kind of preparation method of waste lubricating oil production clear gusoline technique and its catalyst Download PDFInfo
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- 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
- C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a kind of waste lubricating oil production clear gusoline technique and its preparation methods of catalyst, it produces clear gusoline technique and includes visbreaking and filtering and impurity removing of the waste lubricating oil in the presence of emulsion containing catalyst with absorption except the preprocessing process of poisonous substance, hydro-upgrading and the fraction cutting of full distillate oil by pretreatment, and provide the oil-soluble catalyst of above-mentioned regeneration technology（Visbreaking）And hydrogenation catalyst.By being catalyzed visbreaking and filtering absorption pretreatment, using subsequent hydro-upgrading, deep desulfuration, denitrogenation can remove the various undesirable components in waste lubricating oil, improve oil quality.It is cut using the hydro-upgrading and fraction of full fraction, on the one hand improves the resource recovery of waste lubricating oil, on the other hand obtain flexible products scheme, regenerate the high income of oil product, the diesel oil and base oil quality index of production entirely reach standard requirement.
Description
Technical field
It is specifically a kind of using waste oil pretreatment-hydro-upgrading the invention belongs to waste lubricant oil regeneration technical field
Production cleaning diesel oil and the technique of lube base oil and its preparation of catalyst and application method.
Background technology
As China's industrialization and Development of China's Urbanization are accelerated, the constraint degree of resource and environment increasingly sharpens, valuable source
Self-supporting capability is insufficient, and the external dependence degree of especially oil rises year by year.Change the unidirectional line style of " resource-product-use is abandoned "
Utilizing Resource Pattern comprehensively utilizes mode for the circular form of " resource-product-use recycling-regenerated resources ", comprehensive to improve resource
Utilization ratio is closed, and reduces waste discharge with important strategic importance.Waste lubricant oil regeneration has the section saved and substitute oil
Energy economic characteristics and the environmental protection industry characteristic for avoiding waste oil pollution environment are the important components of strategic emerging industries, have
There is vast potential for future development, be conducive to accelerate to build resource-effective, the environmental-friendly mode of production and consumption mode, enhancing can be held
Continuous developing ability.The technological difficulties of useless lubricating oil Reclaimed Base Oil have：Reclaimed Base Oil must be sloughed effectively including metal
Impurity and ensure higher yield and reach the basic oil quality of natural oil processing；Production process green and efficiently do not generate or
It is few to generate " secondary pollution ".It is mature on the whole at present using the technology of " distillation+hydrofinishing ", produces base oil and reach completely
To I International class or II class base oil standard, Reclaimed Base Oil yield is higher, substantially without " three wastes " emission problem.
Internal lube oil regeneration technology is still based on sulfuric acid-carclazyte technique at present, and not only waste oil regeneration rate is low for this technique,
About 60%, and a large amount of acid sludge, waste soda residue and sewage are generated in the process, therefore cause serious secondary pollution.It is mutually secondary
The waste lubricant oil regeneration rate of the solvent extraction technology of exhibition is about 70%, if the nitrogen phosphorus organic wastewater of high-content is discharged by the process
In water, body eutrophication can be caused, cause water pollution.Therefore environmental protection, the exploitation of economic waste lubricant oil regeneration new process
The task of top priority is had become with research.At present, western developed country is all using distillation-hydrogenation technique as most environmentally friendly in waste oil regeneration, most
Tool operability and the technique of scale are researched and developed, but since hydrogenation method regeneration technology is relative complex there are process, behaviour
Make the shortcomings of condition is harsher, and the preparation of hydrogenation catalyst is also the subject for needing to further investigate always.Additionally, due to
The centralized collection relative difficulty of waste oil, raw material sources are unstable, distillation-device blocking and corrosion etc. existing for hydrogen addition technology route
Problem affects the long-term operation of process units.Therefore there is still a need for constantly visit for distillation-plus the used oil regenerated technology of hydrogen route
Rope.
Chinese patent, publication number CN 102786985 provide a kind of method of waste lubricating oil recycling, the method
Waste lubricating oil is distilled, obtains being less than 500 DEG C of fractions and more than 500 DEG C fractions, less than 500 DEG C fractions are on sulfide catalyst
Hydrofining reaction, then obtain gasoline, diesel oil and base oil fractions oil through distillation.And more than 500 DEG C fractions will pass through reaction and steam
Rear repeated hydrogenation is evaporated to refine.Its hydrogenation catalyst is support type NiMo, NiW, CoMo sulfides catalyst.
Chinese patent, publication number CN 102504933 provides a kind of method for regenerating waste lubricating oil, pre- including waste lubricating oil
Processing, short-path distillation and the several steps of hydrofinishing, hydrogenation catalyst is iron molybdenum, cobaltmolybdate catalyst.
Chinese patent, publication number CN 100445355 provide a kind of waste lubricating oil hydrogenation reproducing method, and this method is main
It is by after waste lubricating oil adsorption treatment, pre- hydrofinishing is carried out in equipped with protectant reactor, enters back into and add hydrogen main reaction
Device, the hydrofinishing under the action of hydrogenation catalyst, product carry out fractionation cutting, and the waste oil rate of recovery is 83.5%.Its hydrogenation catalyst
Agent is so that alumina support supports active component W, Ni and adjuvant component P and is made.
Chinese patent, publication number CN 101797509 provide a kind of used lubricating oil complete hydrogenation regenerated catalyst and its system
Preparation Method and application, catalyst are made of catalyst carrier alumina and active component, active component WO3, NiO and auxiliary agent
Si。
Chinese patent, publication number CN 103013644 provide a kind of method from waste lubricating oil production base oil, packet
Separative element and hydrotreating unit are included, waste lubricating oil obtains distillate I and II, distillate I and II after separative element distillation
It alternately in hydrotreating unit and hydrotreating catalyst haptoreaction, then strips respectively, obtains lube base oil I and II.
Its hydrotreating catalyst is using aluminium oxide or aluminium oxide-silicon oxide as carrier, using Ni, Co, Mo, W as hydrogenation active metal component,
Auxiliary agent for fluorine, boron and phosphorus one or more or be free of.
Chinese patent, 103421594 B of publication number CN provide a kind of process for regeneration of waste lubricating oil, and step includes useless
Lubricating oil visbreaking pretreatment, atmospheric and vacuum distillation, pre-add hydrogen and hydrofinishing, and provide a kind of for above-mentioned regeneration technology
Hydrogenation catalyst；By the waste lubricating oil visbreaking of early period and adsorption treatment and atmospheric and vacuum distillation, then add by subsequent
Hydrogen refines, deep desulfuration, denitrogenation, can remove the various undesirable components in waste lubricating oil, increases substantially the matter of reclaimed oil
Amount；Product yield after regeneration is high, and the lube base oil quality index of production entirely reaches the mark of lubricating oil general basic oil
Alignment request.
More than patent content shows that can regenerate waste lubricating oil using distillation-plus hydrogen route obtains standard compliant lubricating oil
Base oil product.But since the source of waste oil is different, the impurity of waste oil and constituent are complicated, especially tenor is high
Deng the stationarity of continuity and long-term operation to production process proposes higher requirement；In addition, for some higher chlorine
For the waste oil raw material of hydrocarbon content, it is desirable that catalyst has higher dechlorinating ability.Distillation-hydrogenation process generation accounts for raw material composition
10-20% distills Residual oil（Decompression residuum）, the metallization decomposed containing a large amount of gum asphalt and additive in this part Residual oil
Object, especially heavy metal compound are closed, natural environment is returned to often through the blend component as pitch, causes secondary pollution.
In addition, due to distillation process by the residual lubricating oil component discharge in waste oil in decompression residuum（Residual oil）, simple distillation fraction
The hydrofinishing of oil is difficult the multigrade lubricating oil base oil for obtaining high viscosity-temperature index and meeting high temperature viscosity.Reclaimed Base Oil process
In distillation Residual oil（Decompression residuum）Residual lubricating oil base oil component in base oil is preferable residue lubrication
The raw material of oil base oil, makes good use of this part Residual oil, can not only obtain higher waste oil regeneration yield but also and high quality
The raw material of Reclaimed Base Oil ensures.
Invention content
Insufficient for the top of the prior art, the present invention provides a kind of waste lubricating oil production clear gusoline technique and its catalysis
The preparation method of agent with reference to proprietary catalyst and its grading technology and adjusts technological parameter, can produce and meet cleansing oil
The diesel oil and lube base oil of product standard.
Technical solution proposed by the present invention includes catalytic hydroprocessing visbreaking（Demetalization and inhibition green coke）Pretreating process, knot
Wide boiling range hydro-upgrading technology is closed, is employed including load hydrogenation catalyst with high performance and its grading technology so that
Not only quality is high for the diesel oil and lube base oil product that can be obtained by the technique and its mating catalyst technology, Er Qiesheng
Production process has the characteristics that stability.
First, a kind of waste lubricating oil production clear gusoline technique is provided, step includes pretreatment plus hydrogen and fraction is cut
It cuts, it is specific as follows：
（1）, pre-treatment step：
Waste lubricating oil enters catalysis Visbreaking reactor, operating condition after being mixed with oil-soluble dispersed catalyst：Temperature 280-
340 DEG C, volume space velocity 0.5-1.5h-1, pressure 0.1MPa-2MPa, hydrogen to oil volume ratio 500-1000V/V；It is catalyzed visbreaking
Treated, and waste lubricating oil enters the reactor equipped with adsorbent after filtering；The oil-soluble dispersed catalyst dosage is useless
The 0.5-1% of weight of oil is lubricated, the oil-soluble dispersed catalyst is by one kind and cetyl in urea, acetic acid and EDTA
Trimethylammonium hydroxide mixing composition；By this pretreatment, can remove moisture in waste lubricating oil, mechanical admixture, additive,
Colloid, coke for being generated in colloid, asphalitine and reaction process etc. obtain satisfactory hydrogenation of total effluent raw material.
（2）Hydrogenation step：
A. hydrotreating：Enter hydrotreating reactor by the waste lubricating oil of pretreatment, which is
Catalyst for hydro-upgrading is loaded with Hydrodewaxing catalyst, and operating condition is：300-400 DEG C of reaction temperature, volume space velocity are
0.3-1.5h-1, pressure 8-16MPa, hydrogen to oil volume ratio 200-800V/V；By this process it is possible to it removes in waste lubricating oil
The hetero atoms such as S, N, O, while aromatic hydrocarbons and wax content in distillate can be reduced, improve stability to reach and reduce pour point
Purpose.
B. hydrofinishing：Oil plant through hydrogenated processing enters hydrofining reactor, which is non-negative
Load type Hydrobon catalyst, operating condition are：250-340 DEG C of temperature, volume space velocity 0.5-1.5h-1, pressure 8-
16MPa, hydrogen to oil volume ratio 200-600V/V；By this process it is possible to further remove the undesirable components in distillate, system
The diesel oil and lube base oil of clear gusoline standard must be met.
By the waste lubricating oil of pretreatment, by hydrotreating and hydrofinishing, it can produce and meet clear gusoline mark
Accurate diesel oil and lube base oil.
(3) fraction cutting step：
Oil plant by hydrofinishing is sent into destilling tower and is fractionated, and obtains a variety of clear gusolines.A variety of clear gusoline packets
Include naphtha, diesel oil and lube cut etc..
Above-mentioned technique is more preferably：
Preferably, the step（1）Oil-soluble dispersed catalyst is by one kind and 16 in urea, acetic acid and EDTA
Alkyltrimethylammonium hydroxide is according to mass ratio 1:10 mixing compositions.
Preferably, the step（2）Middle catalyst for hydro-upgrading and Hydrodewaxing catalyst by volume 1:1 filling.
Preferably, the adsorbent is made of ceramic ring, active macroporous aluminium oxide and diatomite mixed packing, wherein activity is big
Hole aluminium hydroxide presses 7 with diatomite first：Again with ceramic ring according to 3 after 3 mass ratio molding:1 volume ratio filling, the ceramic ring
It is filled in top.
In order to preferably realize above-mentioned production clear gusoline technique, then provide and urged with the hydro-upgrading of above-mentioned process matching
The preparation method of agent, Hydrodewaxing catalyst and Hydrobon catalyst：
First, the catalyst for hydro-upgrading is prepared by the following method：
A, the preparation of carrier
The main component of carrier is aluminum hydroxide solid elastomer, and auxiliary element selection diatomite, HY, USY or Beta molecular sieve will
Aluminum hydroxide solid elastomer, auxiliary element, sesbania powder and mass fraction 65% nitric acid in mass ratio 100：（5-25）:3：（1-5）With it is suitable
Amount distilled water is sufficiently mixed uniform, kneading；Then kneading, extruded moulding；It is dry in 80-120 DEG C of baking oven after room temperature is dried
Carrier after roasting then in 400-600 DEG C of Muffle kiln roasting 4-8h, is pinched item and catalyst carrier is made by 4-12h；
B, the preparation of maceration extract
After distilled water and concentrated phosphoric acid stirring are boiled, load weighted MoO is poured into3And basic nickel carbonate, Ni/Ni+Mo
Molar ratio is 0.2 ~ 0.3, continues to be heated to reflux, until being completely dissolved into clear solution, clear solution is transferred in volumetric flask
It is spare；
C, the preparation of catalyst
Catalyst uses equi-volume impregnating load active component, and detailed process is：The water absorption rate of above-mentioned carrier is measured, is pressed
According to weighing carrier and prepared maceration extract is needed, will be added dropwise on carrier after the maceration extract constant volume being configured, stirring makes
Must impregnate uniformly, be dried in air after sealing and standing 8-12h, the dry 4-8h in 80-120 DEG C of baking oven, after be transferred to 400-600
DEG C Muffle furnace roasting 4-8h, it is final be made needed for catalyst.
Second, the Hydrodewaxing catalyst is prepared by the following method：
A, the preparation of carrier
The main component of carrier is aluminum hydroxide solid elastomer, auxiliary element selection SAPO-11 molecular sieves, ZSM-5 molecular sieve or
ZSM-22 molecular sieves, by aluminum hydroxide solid elastomer, auxiliary element, sesbania powder and 65% nitric acid in mass ratio 100：（15-70）:3：（2-
5）Uniform, kneading is sufficiently mixed with appropriate distilled water；Then kneading, extruded moulding；After room temperature is dried, in 80-120 DEG C of baking oven
Carrier after roasting then in 400-600 DEG C of Muffle kiln roasting 4-8h, is pinched item and catalyst load is made by middle dry 4-12 h
Body；
B, the preparation of maceration extract
In appropriate containers, one or more metallic compounds in load weighted molybdenum, tungsten, cobalt, nickel are added in, add suitable quantity of water
Stirring until being completely dissolved into clear solution, clear solution is transferred to spare in volumetric flask；
C, the preparation of catalyst
Catalyst uses equi-volume impregnating load active component, and detailed process is：The water absorption rate of above-mentioned carrier is measured, is pressed
According to weighing carrier and prepared maceration extract is needed, will be added dropwise on carrier after the maceration extract constant volume being configured, stirring makes
Must impregnate uniformly, be dried in air after sealing and standing 8-12h, the dry 4-8h in 80-120 DEG C of baking oven, after be transferred to 300-600
DEG C Muffle kiln roasting 4-8h, it is final be made needed for catalyst.
Third, the Hydrobon catalyst is prepared by the following method：
A, the preparation of presoma
It is Ni by metal molar ratio:Mo:W=2:1:1 basic nickel carbonate or nickel nitrate, ammonium heptamolybdate and metatungstic acid
Ammonium powder is added in beaker, then adds in EDTA, and EDTA accounts for the 2%-10% of several substance total weights in front, adds suitable
Deionized water stirs to obtain solution, and the above-mentioned solution prepared is added in autoclave, 5-15h is reacted under conditions of 90-170 DEG C
After turn off heating and make its natural cooling, filtered after reaction, obtained filter cake first in infrared lamp dried, is then existed again
It is dried in 120 DEG C of baking ovens to get to Ni-Mo-W presomas.
B, the preparation of catalyst
By aluminum hydroxide solid elastomer, Ni-Mo-W presomas, sesbania powder and 65% nitric acid in mass ratio 100：（15-50）:3：（2-
5）Uniform, kneading is sufficiently mixed with appropriate distilled water；Then kneading, extruded moulding；It is dried in air, in 80-120 DEG C of baking oven
300-600 DEG C of roasting 4-8h of Muffle furnace, final obtained required catalyst are transferred to after dry 4-8h
The present invention proposes that technical solution includes the visbreaking and filtering waste lubricating oil in the presence of emulsion containing catalyst
With absorption except the preprocessing process of poisonous substance, the hydro-upgrading and fraction of the full distillate oil by pretreatment are cut, and carry for removal of impurities
The oil-soluble catalyst of above-mentioned regeneration technology is supplied（Visbreaking）And hydrogenation catalyst.It is inhaled by being catalyzed visbreaking and filtering
Attached pretreatment, using subsequent hydro-upgrading, deep desulfuration, denitrogenation can remove various non-ideal groups in waste lubricating oil
Point, improve oil quality.It is cut using the hydro-upgrading and fraction of full fraction, on the one hand improves the resource reclaim of waste lubricating oil
On the other hand rate obtains flexible products scheme, regenerate the high income of oil product, and the diesel oil and base oil quality index of production are complete
Portion reaches standard requirement.And production process has the characteristics that stability.
Specific embodiment
Technical scheme of the present invention is further described below in conjunction with specific embodiment, wherein embodiment 1 is useless profit
Lubricating oil produces the overall craft flow of clear gusoline technique, and embodiment 2-6 is directed to the waste lubricating oil of a certain composition, further refines
Illustrate the preparation method of each processing step and each catalyst.
Embodiment 1
A kind of waste lubricating oil produces clear gusoline technique, includes the following steps：
1. pretreating process
Waste lubricating oil and cetyltrimethylammonium hydroxide and urea（Mass ratio 10:1）The disperse type catalyzer of composition
Enter catalysis Visbreaking reactor after mixing, disperse type catalyzer dosage is the 0.5-1% of waste lubricating oil weight；Visbreaking process operates
Condition：280-340 DEG C of temperature, volume space velocity 0.5-1.5h-1, pressure 0.1MPa-2MPa, hydrogen to oil volume ratio 100-
500V/V, the waste lubricating oil of visbreaking process enter after filtering equipped with sorbent reactions device, and above-mentioned adsorbent is by ceramic ring, activity
Macroporous aluminium oxide is formed with diatomite mixed packing；Wherein active macropore aluminium hydroxide presses 7 with diatomite first：3 mass ratio
Again with ceramic ring according to 3 after molding:1 volume ratio filling, top is filled with ceramic ring.
By this pretreatment, can remove moisture in waste lubricating oil, mechanical admixture, additive, colloid, asphalitine and
Colloid, coke for being generated in reaction process etc. obtain satisfactory hydrogenation of total effluent raw material.
2. hydrogenation technique and its catalyst
By the waste lubricating oil of pretreatment, by hydrotreating and hydrofinishing, it can produce and meet clear gusoline mark
Accurate diesel oil and lube base oil.
Hydrotreating：Waste lubricating oil by pretreatment enters hydrotreating reactor, and catalyst in reactor is adds hydrogen
Modifying catalyst loads according to a certain percentage with Hydrodewaxing catalyst, 300-400 DEG C of reaction temperature, volume space velocity 0.3-
1.5h-1, pressure 8-16MPa, hydrogen to oil volume ratio 200-800V/V.By this process it is possible to remove the S in waste lubricating oil,
N, the hetero atoms such as O, while aromatic hydrocarbons and wax content in distillate can be reduced, to reach the mesh for improving stability and reducing pour point
's.
Hydrofinishing：Oil plant through pre- hydrofinishing enters plus hydrogen main reactor, under the action of Hydrobon catalyst
It is reacted, operating condition is：250-340 DEG C of temperature, volume space velocity 0.5-1.5h-1, pressure 8-16MPa, hydrogen oil volume
Than for 200-600V/V.By this process it is possible to further remove the undesirable components in distillate, it is made and meets clear gusoline
The diesel oil and lube base oil of standard.
（1）The preparation method of catalyst for hydro-upgrading
A, the preparation of carrier
The main component of carrier is aluminum hydroxide solid elastomer, and auxiliary element selects diatomite, HY or USY or Beta molecular sieves,
By aluminum hydroxide solid elastomer, auxiliary element, sesbania powder and 65% nitric acid in mass ratio 100：（5-25）:3：（1-5）With appropriate distilled water
It is sufficiently mixed uniform, kneading；Then kneading, extruded moulding；After room temperature is dried, the dry 4-12h in 80-120 DEG C of baking oven, so
Afterwards in 400-600 DEG C of Muffle kiln roasting 4-8h, the carrier after roasting is pinched into item, catalyst carrier is made.
B, the preparation of maceration extract
In appropriate containers, distilled water and suitable concentrated phosphoric acid are added in, after stirring is boiled, by distilled water and concentrated phosphoric acid
After solution stirring is boiled, load weighted MoO is poured into3And basic nickel carbonate, Ni/Ni+Mo molar ratios are 0.2 ~ 0.3, continue to heat
Reflux until being completely dissolved into clear solution, clear solution is transferred to spare in volumetric flask.
C, the preparation of catalyst
Catalyst uses equi-volume impregnating load active component, and detailed process is：The water absorption rate of above-mentioned carrier is measured, is pressed
According to weighing carrier and prepared maceration extract is needed, will be added dropwise on carrier after the maceration extract constant volume being configured, stirring makes
Must impregnate uniformly, be dried in air after sealing and standing 8-12h, the dry 4-8h in 80-120 DEG C of baking oven, after be transferred to 400-600 DEG C
Muffle furnace roasting 4-8h, it is final be made needed for catalyst.
（2）The preparation method of pour point depression catalyst
A, the preparation of carrier
The main component of carrier is aluminum hydroxide solid elastomer, auxiliary element selection SAPO-11 molecular sieves, ZSM-5 molecular sieve or
ZSM-22 molecular sieves, by aluminum hydroxide solid elastomer, auxiliary element, sesbania powder and 65% nitric acid in mass ratio 100：（15-70）:3：（2-
5）Uniform, kneading is sufficiently mixed with appropriate distilled water；Then kneading, extruded moulding；After room temperature is dried, in 80-120 DEG C of baking oven
Carrier after roasting then in 400-600 DEG C of Muffle kiln roasting 4-8h, is pinched item and catalyst load is made by middle dry 4-12 h
Body.
B, the preparation of maceration extract
In appropriate containers, one or more metallic compounds in load weighted molybdenum, tungsten, cobalt, nickel are added in, add suitable quantity of water
Stirring until being completely dissolved into clear solution, clear solution is transferred to spare in volumetric flask.
C, the preparation of catalyst
Catalyst uses equi-volume impregnating load active component, and detailed process is：The water absorption rate of above-mentioned carrier is measured, is pressed
According to weighing carrier and prepared maceration extract is needed, will be added dropwise on carrier after the maceration extract constant volume being configured, stirring makes
It must impregnate uniformly, be dried in air after sealing and standing 8-12h, 300-600 is transferred to after dry 4-8h in 80-120 DEG C of baking oven
DEG C Muffle kiln roasting 4-8h, it is final be made needed for catalyst.
（3）The preparation method of Hydrobon catalyst
A, the preparation of presoma
It is Ni by metal molar ratio:Mo:W=2:1:1 basic nickel carbonate or nickel nitrate, ammonium heptamolybdate and metatungstic acid
Ammonium powder is added in beaker, then adds in EDTA, and EDTA accounts for the 2%-10% of several substance total weights in front, adds suitable
Deionized water stirs to obtain solution, and the above-mentioned solution prepared is added in autoclave, 5-15h is reacted under conditions of 90-170 DEG C
After turn off heating and make its natural cooling, filtered after reaction, obtained filter cake first in infrared lamp dried, is then existed again
It is dried in 120 DEG C of baking ovens to get to Ni-Mo-W presomas
B, the preparation of catalyst
By aluminum hydroxide solid elastomer, presoma, sesbania powder and 65% nitric acid in mass ratio 100：（15-50）:3：（2-5）With it is suitable
Amount distilled water is sufficiently mixed uniform, kneading；Then kneading, extruded moulding；It is dried in air, the dry 4- in 80-120 DEG C of baking oven
300-600 DEG C of roasting 4-8h of Muffle furnace, final obtained required catalyst are transferred to after 8h.
3. product rectification process
By technique 2 plus hydrogen resulting product, i.e., it is sent into destilling tower by the oil plant of hydrofinishing and is fractionated, obtain stone brain
Oil, diesel oil and lube cut.
Embodiment 2
Waste lubricating oil（Property is shown in Table one, table two）With cetyltrimethylammonium hydroxide and urea containing 0.5-1%
（Mass ratio 10:1）Disperse type catalyzer mixing after enter useless profit of the catalysis Visbreaking reactor Jing Guo catalytic hydroprocessing visbreaking process
Lubricating oil enters the reactor equipped with adsorbent after filtering, is handled under hydro condition, operating condition is：Reaction temperature
320 DEG C, volume space velocity 1.5h-1, pressure 1MPa, hydrogen to oil volume ratio 500V/V, above-mentioned adsorbent is by ceramic ring, active macropore
Aluminium oxide is formed with diatomite mixed packing；Wherein active macropore aluminium hydroxide presses 7 with diatomite first：3 mass ratio molding
Afterwards again with ceramic ring according to 3:1 volume ratio filling, top is filled with ceramic ring.By this pretreatment, can remove in waste lubricating oil
Moisture, mechanical admixture, additive, colloid, the colloid, the coke that generate in asphalitine and reaction process etc., conformed to
The long distillate hydrogenating materials asked（Property is shown in Table one, table two）.
The property of one waste lubricating oil raw material of table and its prefinished products
The constituent content of two waste lubricating oil raw material of table and its prefinished products
Embodiment 3
The preparation method of catalyst for hydro-upgrading, step are：
The preparation of catalyst carrier：According to 1：0.1：0.03：0.05 mass ratio, weighs aluminum hydroxide solid elastomer respectively
100.0 g, 10.0 g of USY molecular sieve, 3.0 g of sesbania powder, 65% 5.0 g of nitric acid will add in 75ml distillations in 65% nitric acid
Water is configured to dust technology, and dilute nitric acid solution is added in after aluminum hydroxide solid elastomer, ultra-steady Y molecular sieve, sesbania powder are sufficiently mixed uniformly
Kneading if Sample moisture not enough adds suitable distilled water kneading again, makes powder be uniformly mixed as much as possible.In F-26 (II) double spiral shells
Extruded moulding (the cylindric items of 1.6 mm of Ф) on bar banded extruder, room temperature is dried, then 6 h are dried at 120 DEG C, finally in Muffle furnace
550 DEG C of roasting 4h, obtain alumina support.5.0 g carriers are weighed with electronic balance and are put into beaker, and adding in deionized water makes it
Carrier is not crossed, the free water of carrier surface is blotted after placing 1 hour with filter paper, its water absorption rate is calculated after weighing.
The configuration of maceration extract is configured according to 100g catalyst is produced, and the phosphoric acid of 55g distilled water and 5.3g85% is added
Enter beaker, be heated to 90 DEG C, add in 7.1g basic nickel carbonates and 22.5g molybdenum trioxides, be heated to reflux, until being completely dissolved, obtain
To maceration extract.
It weighs the above-mentioned carriers of 74g to add in conical flask, above-mentioned solution is settled to 80ml, is added to taper in multiple times on a small quantity
In bottle, fully rock until maceration extract is absorbed complete, 12 h of closed standing by carrier, dried, then 6 are dried at 120 DEG C in air
H, finally 500 DEG C of roasting 4h in Muffle furnace, obtain catalyst for hydro-upgrading.
Embodiment 4
The preparation method of Hydrodewaxing catalyst, step are：
The preparation of catalyst carrier：According to 1：0.4：0.03：0.05 mass ratio, weighs aluminum hydroxide solid elastomer respectively
100.0 g, 40.0 g of ZSM-5 molecular sieve, 3.0 g of sesbania powder, 65% 5.0 g of nitric acid are steamed 60ml is added in 65% nitric acid
Distilled water is configured to dust technology, and above-mentioned dilute nitre is added in after aluminum hydroxide solid elastomer, ZSM-5 molecular sieve, sesbania powder are sufficiently mixed uniformly
Sour kneading if Sample moisture not enough adds suitable distilled water kneading again, makes reagent be uniformly mixed as much as possible.It is double in F-26 (II)
Extruded moulding (the cylindric items of 1.6 mm of Ф) on screw rod banded extruder, room temperature is dried, then 6 h are dried at 120 DEG C, finally in Muffle furnace
In 550 DEG C roasting 4h, obtain alumina support.5.0 g carriers are weighed with electronic balance and are put into beaker, and adding in deionized water makes it
Carrier is not crossed, the free water of carrier surface is blotted after placement 1h with filter paper, its water absorption rate is calculated after weighing.
The configuration of pour-point depressant maceration extract is configured according to 100g catalyst is produced, by 70g distilled water and 14.9 nitric acid
Nickel adds in beaker, stirs to being completely dissolved, obtains maceration extract.
It weighs the above-mentioned carriers of 97g to add in conical flask, above-mentioned solution is settled to 75ml, is added to taper in multiple times on a small quantity
In bottle, fully rock until maceration extract is absorbed complete, 12 h of closed standing by carrier, dried in air, in 120 DEG C of baking oven
6 h are dried, finally 500 DEG C of roasting 4h in Muffle furnace, obtain Hydrodewaxing catalyst.
Embodiment 5
The preparation method of Hydrobon catalyst, step are：
It is Ni by metal molar ratio:Mo:W=2:1:1 nickel nitrate, ammonium heptamolybdate and ammonium metawolframate powder is added to
In beaker, EDTA is then added in, EDTA accounts for the 3% of several substance total weights in front, adds suitable deionized water and stir molten
The above-mentioned solution prepared is added in autoclave by liquid, and turning off heating after reaction 6h under conditions of 90 DEG C makes its natural cooling,
It is filtered after reaction, obtained filter cake first in infrared lamp is dried, is then dried in 120 DEG C of baking ovens to get to Ni- again
Mo-W presomas.
By aluminum hydroxide solid elastomer, presoma, sesbania powder and 65% nitric acid in mass ratio 100：（15-50）：3：（2-5）With it is suitable
Amount distilled water is sufficiently mixed uniform, kneading；Then kneading, extruded moulding；It is dried in air, the dry 4- in 80-120 DEG C of baking oven
300-600 DEG C of roasting 4-8h of Muffle furnace, final obtained required catalyst are transferred to after 8h.
Embodiment 6
Using the distillate of 2 gained of embodiment as hydrogenating materials, using made from embodiment 3, embodiment 4, embodiment 5
Catalyst by hydrotreating and refines, obtains hydrogenated products.
Hydroprocessing operations condition：360-400 DEG C of temperature, volume space velocity 0.3-1.5h-1, pressure 8-16MPa, hydrogen oil
Volume ratio is 200-800V/V.
Hydrofinishing operating condition：300 DEG C of temperature, volume space velocity 0.5-1.5h-1, pressure 8-16MPa, hydrogen oil volume
Than for 200-600V/V.
Liquid is received under each reaction temperature and product distribution is shown in Table three, and hydrogenated products are cut by Atmospheric vacuum, cut out 170-350 DEG C
Diesel oil distillate（Property is shown in Table four）, the base oil fractions more than 350 DEG C（Property is shown in Table five）.The diesel oil of gained at each temperature
It disclosure satisfy that state V diesel oil requirements；Base oil pour point is higher at 340 DEG C, other product indexs can reach II classes basis oil index
The requirement it is required that base oil obtained by other operation temperatures can touch the mark.
Three liquid of table is received and product distribution
Four diesel oil property of table
The basic oil nature of table five
Above example is only the exemplary embodiments of the present invention, within the scope of the present invention, is selected other former
Material and proportioning, control parameter, can reach the identical experiment effect of above-described embodiment, just differ a citing herein.
Claims (7)
1. a kind of waste lubricating oil produces clear gusoline technique, it is characterised in that：Its step includes pretreatment plus hydrogen and fraction is cut
It cuts, it is specific as follows：
（1）, pre-treatment step：
Waste lubricating oil enters catalysis Visbreaking reactor, operating condition after being mixed with oil-soluble dispersed catalyst：Temperature 280-340
DEG C, volume space velocity 0.5-1.5h-1, pressure 0.1MPa-2MPa, hydrogen to oil volume ratio 500-1000V/V；It is catalyzed visbreaking process
Waste lubricating oil afterwards enters the reactor equipped with adsorbent after filtering；The oil-soluble dispersed catalyst dosage is useless lubrication
The 0.5-1% of weight of oil, the oil-soluble dispersed catalyst is by one kind and cetyl front three in urea, acetic acid and EDTA
Base ammonium hydroxide mixing composition；
（2）Hydrogenation step：
A. hydrotreating：Enter hydrotreating reactor by the waste lubricating oil of pretreatment, the catalyst in reactor is adds hydrogen
Modifying catalyst is loaded with Hydrodewaxing catalyst, and operating condition is：300-400 DEG C of reaction temperature, volume space velocity 0.3-
1.5h-1, pressure 8-16MPa, hydrogen to oil volume ratio 200-800V/V；
B. hydrofinishing：Oil plant through hydrogenated processing enters hydrofining reactor, which is non-loading type
Hydrobon catalyst, operating condition are：250-340 DEG C of temperature, volume space velocity 0.5-1.5h-1, pressure 8-16MPa, hydrogen
Oil volume ratio is 200-600V/V；
（3）Fraction cutting step：
Oil plant by hydrofinishing is sent into destilling tower and is fractionated, and obtains a variety of clear gusolines.
2. waste lubricating oil according to claim 1 produces clear gusoline technique, it is characterised in that：The step（1）Middle oil
Dissolubility dispersed catalyst is by one kind in urea, acetic acid and EDTA with cetyltrimethylammonium hydroxide according to mass ratio
10:1 mixing composition.
3. waste lubricating oil according to claim 1 produces clear gusoline technique, it is characterised in that：The step（2）In plus
Hydrogen modifying catalyst and Hydrodewaxing catalyst by volume 1:1 filling.
4. waste lubricating oil according to claim 1 produces clear gusoline technique, it is characterised in that：The adsorbent is by porcelain
Ring, active macroporous aluminium oxide and diatomite mixed packing form, wherein active macropore aluminium hydroxide presses 7 with diatomite first：3
Again with ceramic ring according to 3 after mass ratio molding:1 volume ratio filling, the ceramic ring are filled in top.
5. clear gusoline technique is produced according to any waste lubricating oils of claim 1-4, which is characterized in that described plus hydrogen changes
Matter catalyst is prepared by the following method：
A, the preparation of carrier
The main component of carrier is aluminum hydroxide solid elastomer, and auxiliary element selects diatomite, HY, USY or Beta molecular sieve, by hydrogen-oxygen
Change the nitric acid in mass ratio 100 of aluminium dry glue, auxiliary element, sesbania powder and mass fraction 65%：（5-25）:3：（1-5）It is steamed with appropriate
Distilled water is sufficiently mixed uniform, kneading；Then kneading, extruded moulding；After room temperature is dried, the dry 4- in 80-120 DEG C of baking oven
Carrier after roasting then in 400-600 DEG C of Muffle kiln roasting 4-8h, is pinched item and catalyst carrier is made by 12h；
B, the preparation of maceration extract
After distilled water and concentrated phosphoric acid stirring are boiled, load weighted MoO is poured into3And basic nickel carbonate, Ni/Ni+Mo molar ratios
It is 0.2 ~ 0.3, continues to be heated to reflux, until being completely dissolved into clear solution, clear solution is transferred to spare in volumetric flask；It is dense
The concentrated phosphoric acid of phosphoric acid solution selected as mass fraction 85%；
C, the preparation of catalyst
Catalyst uses equi-volume impregnating load active component, and detailed process is：The water absorption rate of above-mentioned carrier is measured, according to need
Carrier and prepared maceration extract are weighed, will be added dropwise on carrier after the maceration extract constant volume being configured, stirring is so that leaching
Stain is uniform, is dried in air after sealing and standing 8-12h, the dry 4-8h in 80-120 DEG C of baking oven, after be transferred to 400-600 DEG C
Muffle furnace roasts 4-8h, final that required catalyst is made.
6. clear gusoline technique is produced according to any waste lubricating oils of claim 1-4, it is characterised in that：It is described to face hydrogen drop
Solidifying catalyst is prepared by the following method：
A, the preparation of carrier
The main component of carrier is aluminum hydroxide solid elastomer, and auxiliary element selects SAPO-11 molecular sieves, ZSM-5 molecular sieve or ZSM-
22 molecular sieves, by the nitric acid in mass ratio 100 of aluminum hydroxide solid elastomer, auxiliary element, sesbania powder and mass fraction 65%：（15-
70）:3：（2-5）Uniform, kneading is sufficiently mixed with appropriate distilled water；Then kneading, extruded moulding；After room temperature is dried, in 80-
Carrier after roasting then in 400-600 DEG C of Muffle kiln roasting 4-8h, is pinched item by dry 4-12 h in 120 DEG C of baking oven
Catalyst carrier is made；
B, the preparation of maceration extract
In appropriate containers, one or more metallic compounds in load weighted molybdenum, tungsten, cobalt, nickel are added in, suitable quantity of water is added to stir
It mixes, until being completely dissolved into clear solution, clear solution is transferred to spare in volumetric flask；
C, the preparation of catalyst
Catalyst uses equi-volume impregnating load active component, and detailed process is：The water absorption rate of above-mentioned carrier is measured, according to need
Carrier and prepared maceration extract are weighed, will be added dropwise on carrier after the maceration extract constant volume being configured, stirring is so that leaching
Stain is uniform, is dried in air after sealing and standing 8-12h, the dry 4-8h in 80-120 DEG C of baking oven, after be transferred to 300-600 DEG C
Muffle kiln roasting 4-8h, it is final that required catalyst is made.
7. clear gusoline technique is produced according to any waste lubricating oils of claim 1-4, it is characterised in that：Described plus hydrogen essence
Catalyst processed is prepared by the following method：
A, the preparation of presoma
It is Ni by metal molar ratio:Mo:W=2:1:1 basic nickel carbonate or nickel nitrate, ammonium heptamolybdate and ammonium metatungstate powder
End is added in beaker, then adds in EDTA, and EDTA accounts for the 2%-10% of several substance total weights in front, adds appropriate deionization
Water stirs to obtain solution, and the above-mentioned solution prepared is added in autoclave, turns off after reacting 5-15h under conditions of 90-170 DEG C
Heating makes its natural cooling, is filtered after reaction, obtained filter cake is first dried in infrared lamp, then again in 120 DEG C of bakings
It is dried in case to get to Ni-Mo-W presomas；
B, the preparation of catalyst
By the nitric acid in mass ratio 100 of aluminum hydroxide solid elastomer, Ni-Mo-W presomas, sesbania powder and mass fraction 65%：（15-
50）:3：（2-5）Uniform, kneading is sufficiently mixed with appropriate distilled water；Then kneading, extruded moulding；It is dried in air, in 80-
300-600 DEG C of roasting 4-8h of Muffle furnace, final obtained required catalyst are transferred in 120 DEG C of baking ovens after dry 4-8h.
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| CN107325839A (en) * | 2017-07-12 | 2017-11-07 | 宁波中循环保科技有限公司 | Method for regenerating waste lubricating oil |
| CN107418621A (en) * | 2017-07-12 | 2017-12-01 | 宁波中循环保科技有限公司 | The method for removing metallic compound in waste lubricating oil |
| CN108558663A (en) * | 2018-06-11 | 2018-09-21 | 徐州得铸生物科技有限公司 | A kind of synthetic method of senecioic acid methyl esters |
| CN110577844A (en) * | 2019-09-26 | 2019-12-17 | 重庆工商大学 | Full-hydrogenation regeneration process for waste lubricating oil and preparation method of hydrogenation catalyst |
| CN116426314A (en) * | 2023-05-16 | 2023-07-14 | 重庆工商大学 | Method for catalytically thermally cracking industrial waste oil by microwaves |
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| CN101797509A (en) * | 2010-03-26 | 2010-08-11 | 抚顺新瑞催化剂有限公司 | Used lubricating oil complete hydrogenation type regenerated catalyst and preparation method and application thereof |
| CN103421594A (en) * | 2013-07-01 | 2013-12-04 | 中国石油大学(华东) | Waste lubricating oil regeneration technology and preparation method for hydrogenation catalyst |
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| CN103421594A (en) * | 2013-07-01 | 2013-12-04 | 中国石油大学(华东) | Waste lubricating oil regeneration technology and preparation method for hydrogenation catalyst |
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