CN112371079A - Deteriorated oil regeneration treatment adsorbent and preparation method thereof - Google Patents
Deteriorated oil regeneration treatment adsorbent and preparation method thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 109
- 230000008929 regeneration Effects 0.000 title claims abstract description 33
- 238000011069 regeneration method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 35
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 15
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
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- 239000000203 mixture Substances 0.000 claims description 17
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- 238000004519 manufacturing process Methods 0.000 claims description 11
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- 238000012216 screening Methods 0.000 claims description 5
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- UPEMFLOMQVFMCZ-UHFFFAOYSA-N [O--].[O--].[O--].[Pm+3].[Pm+3] Chemical compound [O--].[O--].[O--].[Pm+3].[Pm+3] UPEMFLOMQVFMCZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910001940 europium oxide Inorganic materials 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 2
- 229940075630 samarium oxide Drugs 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
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- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 60
- 238000001179 sorption measurement Methods 0.000 description 19
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- 239000000499 gel Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
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- 241001391944 Commicarpus scandens Species 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000003712 decolorant Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000010736 steam turbine oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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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
- C10M175/0008—Working-up used lubricants to recover useful products ; Cleaning with the use of adsorbentia
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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
- C10M175/0083—Lubricating greases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
Abstract
The invention provides a degraded oil regeneration treatment adsorbent and a preparation method thereof, wherein sodium metaaluminate, silica sol, rare earth oxide, sulfuric acid and kaolin are used as main raw materials, the sodium metaaluminate and the silica sol are stirred to form gel, then a mixed solution of the sulfuric acid and the rare earth oxide is slowly dripped, the pH value of the gel is adjusted, the gel is transferred into a stainless steel reaction kettle for dynamic crystallization, and the gel is fully washed, filtered, dried, ground and sieved by a 200-mesh sieve to obtain the porous adsorbent. Weighing kaolin with a certain mass, and carrying out acidification modification by sulfuric acid to obtain the modified kaolin. The porous adsorbent and the modified kaolin are evenly mixed and then roasted to obtain the adsorbent. The invention has the advantages of wide raw material source, low price, simple preparation method process, convenient operation and high yield. The compressive strength of the spherical adsorbent can reach 10-12N/mm, the deacidification rate of the deteriorated oil can reach 80-90%, and the oil sludge removing effect is obvious.
Description
Technical Field
The invention relates to the field of adsorbents for regeneration treatment of electric power oil, and particularly relates to an adsorbent for regeneration treatment of deteriorated oil and a preparation method thereof.
Background
The electric oil mainly comprises transformer oil, turbine lubricating oil, anti-fuel oil and the like, and is blood for ensuring the safe and stable operation of electric equipment. The oil product is aged under the combined action of various factors such as temperature, oxygen, moisture, electric field and the like in the operation process to generate oxidation products such as aldehydes, ketones, phenols, carboxylic acids, low-molecular organic acids and the like which are dissolved in the oil, so that on one hand, the physicochemical property of the oil product is reduced, the insulating property of electric equipment is further reduced, and the abrasion of the equipment is increased; on the other hand, these acids can corrode materials of the power equipment, and seriously jeopardize the service life of the equipment. When the oil product is degraded, regeneration treatment is needed, and the adsorption regeneration treatment technology has the advantages of simple operation process, good treatment effect, low equipment investment, low operation cost and the like, so that the service cycle of the oil product can be effectively prolonged, the resource can be recycled, the production cost is saved, remarkable economic and social benefits are brought, and the adsorption regeneration treatment technology is widely applied to the treatment of the electric oil. The adsorbent is the key and core of the adsorption treatment technology and is always the focus of research.
The adsorbents commonly used for the regeneration of the deteriorated oil at present comprise activated clay, 801 adsorbent, activated alumina, silica gel and the like, and the adsorbents are not special regenerated adsorbents for the deteriorated transformer oil, so that the problems of large usage amount, medium loss reduction, poor deacidification and decolorization effects and the like exist. With the continuous emergence of novel adsorption materials, the development and application of alternative adsorbents become problems which are urgently needed to be solved in the field of oil treatment and the trend of future development. The regeneration adsorbent for electric oil (CN102908989A a high-performance micropore adsorbent for regeneration treatment of electric oil and a preparation method thereof) and (CN 103432983A a micropore polarity induction adsorbent for regeneration treatment of electric oil and a preparation method thereof) which are developed by the West-an thermal research institute have good treatment effects, but have complex production process, difficult industrial production and high price. The waste transformer oil regeneration adsorbent (CN 101406824A) developed by the filial inductance power supply company has simple production process and good treatment effect, but is irregular block-shaped, has poor hardness and is easy to break into powder, so that the adsorbent can pollute an oil system. The patent No. CN101992059A discloses an adsorbent for refining and decoloring waste transformer oil, silver nitrate, copper sulfate and aluminum chloride are used as a reduction system, the use proportion of the reduction system needs to be adjusted according to the pollution condition of the waste transformer oil, and the popularization and the application are limited. Patent No. CN110465261A discloses a process for preparing an adsorbent for recycling and regenerating waste transformer oil and an application thereof, wherein natural clay is used as a raw material, and an alkaline pore-forming agent is added after slurry preparation, dispersion and impurity removal to form a nano pore channel.
In summary, the conventional adsorbents for regeneration of deteriorated oil all have the defects of large usage amount, weak adsorption performance and the like, and an adsorbent with stable structure, uniform particle size, strong adsorption capacity, obvious deacidification and decoloration effects is required, and the preparation method has the advantages of wide raw material source, low price, simple process, convenience in operation, stable structure and capability of large-scale production.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the adsorbent for the regeneration treatment of the degraded oil and the preparation method thereof, and the adsorbent can effectively remove aldehydes, ketones, phenols, carboxylic acids, low-molecular organic acids and other oxidation products dissolved in the oil, which are generated by the degradation of the oil product, reduce the acid value of the transformer oil, effectively decolor and remove oil sludge precipitates, thereby comprehensively recovering various physical and chemical indexes of the oil product. The preparation method is simple and convenient, has wide raw material sources, easy operation, low cost and high yield, and is particularly suitable for industrial production.
The invention also provides the adsorbent prepared by the preparation method, and the adsorbent has the advantages of uniform particle size, stable structure, good adsorption effect and the like.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
an adsorbent for regeneration treatment of deteriorated oil, the particle size distribution of the composition of the adsorbent is 0.7-0.9 μm, and the pore volume is 0.6-0.8 ml/g; after mixing and forming, the mixture is in a particle shape with the diameter of 1-2mm, and the compressive strength is 10-12N/mm; the deacidification rate of the adsorbent to the degraded oil reaches 80-90%, and oil sludge can be efficiently removed.
The preparation method of the deteriorated oil regeneration treatment adsorbent comprises the following steps:
step (1): preparation of porous adsorbents
Dissolving sodium metaaluminate in water to prepare a solution of 50g/L, slowly adding the solution into silica sol with the concentration of 25-30%, stirring for 2-3 hours, and precipitating slurry; then slowly dripping mixed solution of sulfuric acid and rare earth oxide to form gel; adjusting the pH value of the gel, stirring uniformly, transferring the gel into a stainless steel reaction kettle for dynamic synthesis, wherein the rotating speed is as follows: 300r/min, crystallization conditions: crystallizing for 24 hours at 50-80 ℃; fully washing, filtering, drying and grinding the discharged material, and sieving the material by a 200-mesh sieve to obtain porous adsorbent raw powder;
step (2): preparation of modified Kaolin
Weighing a certain mass of kaolin into a beaker, adding 8% sulfuric acid according to the liquid-solid mass ratio of 5: 1 for acid modification, stirring for 2 hours at room temperature, filtering, and washing to neutrality; drying the acid-modified kaolin at 105 ℃, grinding, and sieving with a 200-mesh sieve to obtain modified kaolin;
and (3): preparation of finished adsorbent
Mixing and stirring raw powder of the porous adsorbent and kaolin uniformly, placing the mixture in a ball rolling machine, spraying a silica sol solution in the operation process, screening spherical particles by using a double-layer sieve with the diameter of 1-2mm in the forming process to obtain the spherical adsorbent, and placing the spherical adsorbent in a roasting furnace for roasting at 200-400 ℃ for 3 hours to obtain the finished adsorbent.
In the step (1), the pH value of the gel is adjusted to 6-7.
The rare earth oxide in the step (1) is one or a mixture of more of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide and europium oxide.
The method for preparing 1 liter of the mixed solution of the rare earth oxide and the sulfuric acid in the step (1) comprises the following steps: 0.5g of rare earth oxide is weighed into a beaker, slowly added into 10mL of concentrated sulfuric acid, stirred until the rare earth oxide is completely dissolved, and then slowly added into 1L of water.
In the mixture of the raw powder of the porous adsorbent and the kaolin in the step (3), the mass ratio of the raw powder of the porous adsorbent to the kaolin is (7-8): (2-3).
Spraying a silica sol solution with the concentration of 10-20% in the step (3).
The diameter of the resulting spherical adsorbent was 2 mm.
Compared with the prior art, the invention has the beneficial effects that:
because a small amount of rare earth is introduced into the adsorbent, the rare earth element has large atomic radius and is easy to lose 6s electrons and 5d or 4f electrons on the outer layer, and vacancy and other defects can be generated in the substitution of non-equivalent ions, so that the surface of an inner crystal is highly polarized, the coulomb force and the electrostatic adsorption force among crystals are improved, and the stability and the adsorption performance of the adsorbent are greatly improved.
The kaolin has a layer chain structure, has strong adsorption capacity and binding power, is hydrophilic and oleophobic, can dredge micropores after acid activation modification treatment, remove impurities, improve the types and the number of active groups of the kaolin, can be well compatible with organic matters, can effectively adsorb impurities such as pigments in oil products, is not easy to break after adsorption saturation, and is an adsorbent and a decolorant with excellent performance.
The adsorbent provided by the invention has the advantages of wide raw material source, low price, simple preparation method process, convenience in operation, stable structure and capability of large-scale production. The compressive strength of the spherical adsorbent prepared by the invention can reach 10-12N/mm, the deacidification rate of the transformer oil can reach 80-90%, and the effects of decoloring and dielectric loss reduction are obvious.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an X-ray diffraction pattern of the adsorbent prepared in example 2.
FIG. 2 is an electron micrograph of the adsorbent prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The invention provides a performance comparison test of the adsorbent and 801 adsorbent, silica gel, activated alumina and 13X molecular sieve regenerated transformer oil, and the effects of deacidification, decoloration and dielectric loss reduction of the adsorbent are obviously superior to those of the 801 adsorbent, silica gel, activated alumina and 13X molecular sieve.
Example 1
Preparation of porous adsorbent:
step 1: dissolving sodium metaaluminate in water to prepare a solution of 50g/L, slowly adding the solution into silica sol with the concentration of 25-30%, and stirring for 2-3 hours to precipitate slurry.
Step 2: weighing 0.5g of rare earth oxide in a beaker, slowly adding the rare earth oxide into 10mL of concentrated sulfuric acid, stirring until the rare earth oxide is completely dissolved, then slowly adding the rare earth oxide into 1L of water to prepare a mixed solution of the rare earth oxide and sulfuric acid, and adjusting the pH of the gel prepared in the step 1 to be 6-7 by using the mixed solution.
And step 3: and (3) putting the gel prepared in the step (2) into a stainless steel reaction kettle, and crystallizing at 80 ℃ for 24 hours at the rotating speed of 300 r/min. And after discharging, fully washing, filtering, drying, grinding and sieving by a 200-mesh sieve to obtain the porous adsorbent.
Preparing modified kaolin:
weighing 20g of kaolin into a beaker, adding 200mL of 8% sulfuric acid, stirring at room temperature for 2h, filtering, washing to neutrality, drying the acid-modified kaolin at 105 ℃, grinding, and sieving with a 200-mesh sieve to obtain the modified kaolin.
Preparing a finished adsorbent product:
respectively weighing the porous adsorbent and the modified kaolin according to the weight ratio of 9:1, uniformly mixing, putting into a ball rolling machine, spraying 10-20% of silica sol solution in the operation process, screening spherical particles by using a double-layer sieve with the diameter of 1-2mm in the forming process to finally obtain the spherical adsorbent with the diameter of 2mm, and roasting in a roasting furnace at 200-400 ℃ for 3 hours to obtain a finished product, namely the spherical adsorbent.
Example 2
Preparation of porous adsorbent:
step 1: dissolving sodium metaaluminate in water to prepare a solution of 50g/L, slowly adding the solution into silica sol with the concentration of 25-30%, and stirring for 2-3 hours to precipitate slurry.
Step 2: weighing 0.5g of rare earth oxide in a beaker, slowly adding the rare earth oxide into 10mL of concentrated sulfuric acid, stirring until the rare earth oxide is completely dissolved, then slowly adding the rare earth oxide into 1L of water to prepare a mixed solution of the rare earth oxide and sulfuric acid, and adjusting the pH of the gel prepared in the step 1 to be 6-7 by using the mixed solution.
And step 3: and (3) putting the gel prepared in the step (2) into a stainless steel reaction kettle, and crystallizing at 80 ℃ for 24 hours at the rotating speed of 300 r/min. And after discharging, fully washing, filtering, drying, grinding, and sieving by a 200-mesh sieve to obtain the porous adsorbent.
Preparing modified kaolin:
weighing 20g of kaolin into a beaker, adding 200mL of 8% sulfuric acid, stirring at room temperature for 2h, filtering, washing to neutrality, drying the acid-modified kaolin at 105 ℃, grinding, and sieving with a 200-mesh sieve to obtain the modified kaolin.
Preparing a finished adsorbent product:
weighing the porous adsorbent and the modified kaolin according to the weight ratio of 8:1, uniformly mixing, putting into a ball rolling machine, spraying 10-20% of silica sol solution in the operation process, screening spherical particles by using a double-layer sieve with the diameter of 1-2mm in the forming process to finally obtain the spherical adsorbent with the diameter of 2mm, and roasting in a roasting furnace at 200-400 ℃ for 3 hours to obtain a finished product, namely the spherical adsorbent.
Example 3
Preparation of porous adsorbent:
step 1: dissolving sodium metaaluminate in water to prepare a solution of 50g/L, slowly adding the solution into silica sol with the concentration of 25-30%, and stirring for 2-3 hours to precipitate slurry.
Step 2: weighing 0.5g of rare earth oxide in a beaker, slowly adding 10mL of concentrated sulfuric acid, stirring until the rare earth oxide is completely dissolved, then slowly adding the mixture into 1L of water to prepare a mixed solution of the rare earth oxide and sulfuric acid, and adjusting the pH of the gel prepared in the step 1 to 6-7 by using the mixed solution.
And step 3: and (3) putting the gel prepared in the step (2) into a stainless steel reaction kettle, and crystallizing at 80 ℃ for 24 hours at the rotating speed of 300 r/min. And after discharging, fully washing, filtering, drying, grinding, and sieving by a 200-mesh sieve to obtain the porous adsorbent.
Preparing modified kaolin:
weighing 20g of kaolin into a beaker, adding 200mL of 8% sulfuric acid, stirring at room temperature for 2h, filtering, washing to neutrality, drying the acid-modified kaolin at 105 ℃, grinding, and sieving with a 200-mesh sieve to obtain the modified kaolin.
Preparing a finished adsorbent product:
weighing the porous adsorbent and the modified kaolin according to the weight ratio of 7:1, uniformly mixing, putting into a ball rolling machine, spraying 10-20% of silica sol solution in the operation process, screening spherical particles by using a double-layer sieve with the diameter of 1-2mm in the forming process to finally obtain the spherical adsorbent with the diameter of 2mm, and roasting in a roasting furnace at 200-400 ℃ for 3 hours to obtain a finished product, namely the spherical adsorbent.
Adsorbent regeneration oil performance detection
An 801 adsorbent, silica gel, activated alumina and a 13X molecular sieve are selected to be used for carrying out a regeneration comparison test on the deteriorated transformer oil with the adsorbent in the embodiment 2 of the invention. The oil regeneration test adopts a contact method, namely 2 g of adsorbent is respectively weighed and added into 500 g of degraded transformer oil, the mixture is stirred for 1h in a constant-temperature water bath at 55 ℃, the adsorbent is fully contacted with the oil to achieve the optimal adsorption effect, the mixture of the oil and the adsorbent is filtered and separated after the adsorption is finished, and the appearance, the water-soluble acid, the acid value, the interfacial tension, the medium loss factor and the volume resistivity of the degraded transformer oil and the regenerated oil are measured according to a detection method specified in GB/T14542 and 2017 Transformer oil maintenance and management guide rules.
TABLE 1 comparative test of regeneration performance of deteriorated transformer oil
An 801 adsorbent, silica gel, activated alumina and 13X molecular sieve are selected to be used for carrying out a deteriorated steam turbine oil regeneration comparison test with the adsorbent of the embodiment 2 of the invention. The oil regeneration test adopts a contact method, namely 2 g of adsorbent is respectively weighed and added into 500 g of degraded turbine oil, the mixture is stirred for 1h in a constant-temperature water bath at 55 ℃ so that the adsorbent is fully contacted with the oil to achieve the optimal adsorption effect, the mixture of the oil and the adsorbent is filtered and separated after the adsorption is finished, and the appearance, the acid value and the demulsification degree of the degraded turbine oil and the regenerated oil are determined according to a detection method specified in GB/T14541 and 2017 mineral turbine oil maintenance and management guide rules for power plants.
TABLE 2 deteriorated turbine oil regeneration Performance comparison test
The 801 adsorbent, silica gel, activated alumina and 13X molecular sieve are selected to be used for carrying out a degradation fire-resistant oil regeneration comparison test with the adsorbent of the embodiment 2 of the invention. The oil regeneration test adopts a contact method, namely 2 g of adsorbent is respectively weighed and added into 500 g of degraded fire-resistant oil, the mixture is stirred for 1h in a constant-temperature water bath at 55 ℃ so that the adsorbent is fully contacted with the oil to achieve the optimal adsorption effect, the mixture of the oil and the adsorbent is filtered and separated after the adsorption is finished, and the appearance, acid value and volume resistivity of the degraded fire-resistant oil and the regenerated oil are measured according to the detection method specified in DLT 571-2014 phosphate fire-resistant oil operation and maintenance guide rules for power plants.
TABLE 3 comparative test of deteriorated fuel resistance
As can be seen from tables 1-3, the adsorbent provided by the invention has excellent adsorption capacity for decoloring, deacidifying and removing oil sludge, can greatly improve the physical and chemical properties of the deteriorated oil, and has adsorption properties superior to those of 801 adsorbents, silica gel, activated alumina and 13X molecular sieves.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. An adsorbent for regeneration treatment of deteriorated oil, characterized in that: the particle size of the composition of the adsorbent is 0.7-0.9 mu m, and the pore volume is 0.6-0.8 ml/g; after mixing and forming, the mixture is in a particle shape with the diameter of 1-2mm, and the compressive strength is 10-12N/mm; the deacidification rate of the adsorbent to the degraded oil reaches 80-90%, and oil sludge can be efficiently removed.
2. The method for producing the adsorbent for regenerating treatment of deteriorated oil according to claim 1, characterized in that: the method comprises the following steps:
step (1): preparation of porous adsorbents
Dissolving sodium metaaluminate in water to prepare a solution of 50g/L, slowly adding the solution into silica sol with the concentration of 25-30%, stirring for 2-3 hours, and precipitating slurry; then slowly dripping mixed solution of sulfuric acid and rare earth oxide to form gel; adjusting the pH value of the gel, stirring uniformly, transferring the gel into a stainless steel reaction kettle for dynamic synthesis, wherein the rotating speed is as follows: 300r/min, crystallization conditions: crystallizing for 24 hours at 50-80 ℃; fully washing, filtering, drying and grinding the discharged material, and sieving the material by a 200-mesh sieve to obtain porous adsorbent raw powder;
step (2): preparation of modified Kaolin
Weighing a certain mass of kaolin into a beaker, adding 8% sulfuric acid according to the liquid-solid mass ratio of 5: 1 for acid modification, stirring for 2 hours at room temperature, filtering, and washing to neutrality; drying the acid-modified kaolin at 105 ℃, grinding, and sieving with a 200-mesh sieve to obtain modified kaolin;
and (3): preparation of finished adsorbent
Mixing and stirring raw powder of the porous adsorbent and kaolin uniformly, placing the mixture in a ball rolling machine, spraying a silica sol solution in the operation process, screening spherical particles by using a double-layer sieve with the diameter of 1-2mm in the forming process to obtain the spherical adsorbent, and placing the spherical adsorbent in a roasting furnace for roasting at 200-400 ℃ for 3 hours to obtain the finished adsorbent.
3. The method for producing the deteriorated oil regeneration treatment adsorbent according to claim 2, characterized in that: in the step (1), the pH value of the gel is adjusted to 6-7.
4. The method for producing the deteriorated oil regeneration treatment adsorbent according to claim 2, characterized in that: the rare earth oxide in the step (1) is one or a mixture of more of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide and europium oxide.
5. The method for producing the deteriorated oil regeneration treatment adsorbent according to claim 2, characterized in that: the method for preparing 1 liter of the mixed solution of the rare earth oxide and the sulfuric acid in the step (1) comprises the following steps: 0.5g of rare earth oxide is weighed into a beaker, slowly added into 10mL of concentrated sulfuric acid, stirred until the rare earth oxide is completely dissolved, and then slowly added into 1L of water.
6. The method for producing the deteriorated oil regeneration treatment adsorbent according to claim 2, characterized in that: in the mixture of the raw powder of the porous adsorbent and the kaolin in the step (3), the mass ratio of the raw powder of the porous adsorbent to the kaolin is (7-8): (2-3).
7. The method for producing the deteriorated oil regeneration treatment adsorbent according to claim 2, characterized in that: spraying a silica sol solution with the concentration of 10-20% in the step (3).
8. The method for producing the deteriorated oil regeneration treatment adsorbent according to claim 2, characterized in that: the diameter of the resulting spherical adsorbent was 2 mm.
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