CN111375391B - Method for reducing oil content of waste argil - Google Patents
Method for reducing oil content of waste argil Download PDFInfo
- Publication number
- CN111375391B CN111375391B CN201811618740.6A CN201811618740A CN111375391B CN 111375391 B CN111375391 B CN 111375391B CN 201811618740 A CN201811618740 A CN 201811618740A CN 111375391 B CN111375391 B CN 111375391B
- Authority
- CN
- China
- Prior art keywords
- waste
- mixing
- solid phase
- water
- argil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000007790 solid phase Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000004927 clay Substances 0.000 claims description 65
- 239000003921 oil Substances 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 29
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 22
- 239000010687 lubricating oil Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 238000007670 refining Methods 0.000 claims description 12
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 11
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004061 bleaching Methods 0.000 claims description 7
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- ZAJNGDIORYACQU-UHFFFAOYSA-N decan-2-one Chemical compound CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 229940094933 n-dodecane Drugs 0.000 claims description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 239000004519 grease Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000002199 base oil Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LOTCVJJDZFMQGB-UHFFFAOYSA-N [N].[O].[S] Chemical class [N].[O].[S] LOTCVJJDZFMQGB-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for reducing the oil content of waste argil, which comprises the steps of mixing the waste argil, a pretreating agent and water, then dividing the obtained materials into three layers of a solid phase, a water phase and an oil phase through standing, mixing the obtained solid phase with the treating agent, standing, removing the uppermost layer of materials, further carrying out solid-liquid separation to obtain filtrate and the waste argil, and washing and drying the waste argil to obtain regenerated argil. The method for reducing the oil content of the waste argil can separate the grease, the colloid and the asphaltene in the waste argil, does not damage the structure of the argil, facilitates the subsequent regeneration and the reutilization of the argil, does not generate other pollution in the treatment process, and has higher activity of the regenerated argil.
Description
Technical Field
The invention belongs to the field of petroleum processing, and particularly relates to a method for treating waste argil generated in the production process of refined lubricating oil.
Background
In the production of lubricating oil, the refining process of removing undesirable components or the hydrogenation treatment of chemical conversion of the undesirable components is required to improve the viscosity index of the base oil and meet the requirement of viscosity-temperature performance, and the dewaxing process or the hydrodewaxing process of cracking and isomerizing the wax hydrocarbon is required to reduce the condensation point of the base oil and meet the requirement of low-temperature fluidity. The lubricating oil white clay replenishing and refining device as the last process is to mix lubricating oil stock with certain amount of white clay at certain temperature and time, treat various solvent refining and solvent dewaxing lubricating oil stocks, and remove a small amount of polar substances such as colloid, asphaltene, naphthenic acid, sulfonic acid, oxygen-nitrogen-sulfur compounds and the like and non-ideal components such as mechanical impurities and the like in raw materials in a physical adsorption mode. And then filtering and separating the white clay and the oil to obtain high-quality lubricating oil base oil, wherein the white clay is supplemented and refined to better improve the color, the oxidation stability, the emulsification resistance, the insulativity and the carbon residue value of the oil product.
Under the condition of clay refining, the clay has good adsorption effect on the colloid and the asphalt, and the colloid and the asphalt are more easily adsorbed when the molecular weight of the colloid and the asphalt is larger; oxides and sulfates are also easily adsorbed; in hydrocarbons, the order of adsorption is aromatic > naphthenic > paraffinic.
Although clay has good adsorption performance on polar substances, the adsorption of clay has a certain limit. After the adsorption polar substance is saturated, the adsorption capacity is lost. The amount of the waste clay discharged by standing the lubricating oil every year is huge, for example, the waste clay generated by a supplement refining device for the middle petrifaction of Yanshan mountain is more than 10000t per year, the waste clay is mostly brown to gray black solid slag, and some waste clays are also bonded into blocks, and at the moment, the fresh clay needs to be replaced in time. In recent years, the yield of oil product refining spent bleaching clay is continuously increased, the traditional treatment methods such as burying, blending combustion and the like are not compliant, how to treat hazardous waste regularly and realize harmlessness and recycling are becoming the focus of attention of environmental protection departments increasingly. Therefore, finding out the efficient recovery of oil in the waste clay and the comprehensive utilization of the deoiled clay becomes a hot point of research in the aspect.
Patent CN1709595A performs regeneration process treatment on the deoiled waste clay, i.e. drying, dehydrating, calcining, pickling and activating after calcining, drying and sieving to obtain regenerated clay. Similarly, patent CN102266759A discloses a method, which comprises the steps of mixing waste clay with sulfuric acid with the mass fraction of 40-60%, kneading the obtained paste into a certain shape, firing at the temperature of 600-700 ℃, cooling and crushing to obtain regenerated clay. The clay begins to lose crystal water when being heated to above 300 ℃, the structure of the clay is changed, and in addition, the introduction of concentrated sulfuric acid can also cause the collapse of the porous structure of the clay, and the two points can influence the regeneration effect; more importantly, the oil absorbed by the clay is burnt, and the recovery of resources is not realized.
Patent CN107286973A discloses a method for recovering oil from waste clay: under the first contact condition, the waste clay to be treated is contacted with an organic solvent to desorb the lubricating oil base oil in the waste clay, under the second contact condition, the waste clay subjected to primary treatment is contacted with the organic solvent to dissolve non-ideal components in the waste clay, and under the third contact condition, the waste clay subjected to secondary treatment is contacted with water to dissolve the extraction solvent in the clay. According to different proportions of the extraction solvent, batch extraction of ideal components and non-ideal components of the lubricating oil is realized. In fact, the lubricating oil recovered in this way ideally still contains heavy components such as gums, asphaltenes and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for reducing the oil content of the waste argil, which can separate the grease, colloid and asphaltene in the waste argil, does not damage the structure of the argil, facilitates the subsequent regeneration and reutilization of the argil, does not generate other pollution in the treatment process, and has higher activity of the regenerated argil.
The invention provides a method for reducing the oil content of waste argil, which comprises the following steps:
(1) Mixing waste argil, a pretreating agent and water at 60-100 ℃, preferably 70-90 ℃, standing the uniformly mixed materials to separate the materials into a solid phase layer, a water phase layer and an oil phase layer;
(2) Mixing the solid phase obtained after separation in the step (1) with a treating agent at 70-95 ℃, preferably 80-90 ℃, and then standing for layering;
(3) Removing the colloid asphaltene on the uppermost layer of the material obtained in the step (2), further performing solid-liquid separation to obtain filtrate and waste clay, and washing and drying the waste clay to obtain the regenerated clay.
In the method, the waste clay in the step (1) is the waste clay generated by a clay refining unit of a lubricating oil production device, such as the waste clay generated in the process of preparing lubricating oil by clay refining by taking normal four-line, reduced two-line, reduced three-line and reduced four-line furfural refined oil (normal and reduced pressure distillation-ketobenzene dewaxing-furfural refining) as a raw material.
In the method of the present invention, the mass ratio of the spent bleaching earth to water in step (1) is 1.
In the method of the present invention, the mixing treatment time in step (1) is 2 to 10 hours, preferably 4 to 6 hours.
In the method, the pretreatment agent in the step (1) comprises rhamnolipid and petroleum sulfonate, and the concentration of the rhamnolipid is controlled to be 300-600 mg/L, preferably 400-500 mg/L and the concentration of the petroleum sulfonate is controlled to be 2000-4000 mg/L, preferably 2500-3000 mg/L based on the addition amount of water in the step (1).
In the method, the treating agent in the step (2) comprises hydrogen peroxide solution and alkane with 5-15 carbon atoms, wherein the alkane can be one or more of n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decanone, n-undecane, n-dodecane, n-tridecane, n-tetradecane and n-pentadecane; n-heptane is preferred. The concentration of the hydrogen peroxide solution is 20 to 40wt%, preferably 25 to 35wt%, and more preferably 30wt%. In the treating agent, the mass ratio of the added hydrogen peroxide solution to the alkane is 1:1 to 1, preferably 1 to 2 to 1.
In the method of the present invention, the liquid-solid ratio of the treating agent to the solid phase in step (2) is 1:8 (mL/g) is preferably 1:4 (mL/g), more preferably 1:2.
in the method of the present invention, when the solid phase described in step (2) is mixed with a treating agent, a mixed gas of nitrogen dioxide and sulfur dioxide may be introduced into the solid phase, wherein the volume ratio of nitrogen dioxide to sulfur dioxide in the mixed gas is 1.
In the method, the drying temperature in the step (3) is 80-115 ℃, preferably 90-105 ℃; the drying time is 4 to 9 hours, preferably 5 to 6 hours.
In the method of the present invention, the solid phase obtained after the separation in step (1) is preferably further mixed with water and a pretreating agent, the treatment is repeated according to the operating conditions described in step (1), and the solid phase obtained after the treatment twice or more is further mixed with a treating agent. The aqueous phase obtained in step (2) can be recycled.
Compared with the prior art, the method for reducing the oil content of the waste argil has the following characteristics:
1. the method realizes the purpose of recovering the grease and colloid asphaltene in the waste argil under the composite action of the mixed gas of the water, the pretreatment agent, the treatment agent, the nitrogen dioxide and the sulfur dioxide, does not destroy the structure of the argil, has higher activity of the argil after recovery treatment, and can be directly recycled.
2. The method realizes the separation of most of grease in the waste argil under proper operating conditions, and the argil treated by the method has an oil content lower than 5 percent in the inspection; the used solvent water can be recycled, and the lubricating oil can be recovered; the pretreatment agent is added, so that the recycling frequency of the solvent water is increased, the BOD/COD of the cut water component is more than 0.38 through measurement, the biochemical performance is better, and the pressure of effluent treatment is reduced.
3. The treatment method ensures that the structure of the argil is not damaged, and is beneficial to the further regeneration of the argil; the method has mild process conditions, does not use toxic solvents in the whole process, greatly reduces the production cost, does not use high-temperature and high-pressure treatment means, greatly reduces the potential safety hazard, has simple operation and good replacement effect, is suitable for large-scale industrial application, and has good economic benefit.
4. In the method, in the process of treating the treating agent and the solid phase, the mixed gas of nitrogen dioxide and sulfur dioxide is introduced simultaneously, so that the mixed gas and the treating agent can play a role in compounding, the action effect of the treating agent can be improved, and the activity of the regenerated carclazyte is further improved; and the colloid and the asphaltene can be promoted to realize the quick separation from the argil and be brought to the surface of the solution, the oil content of the argil can be further reduced through the synergistic effect of the treating agent and the gas, and the activity of the argil is improved.
Detailed Description
The method for recycling and treating spent bleaching earth according to the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
The clay used in this experiment was waste clay from a lubricating oil clay refining apparatus of a certain refining company, and had a tan appearance and a harsh organic solvent taste, and the oil content was determined to be 28%.
Example 1
(1) Mixing 500g of waste argil, 1400g of water and a pretreating agent at 75 ℃, wherein the pretreating agent consists of rhamnolipid and petroleum sulfonate, the adding amount is 0.85g and 5.25g respectively, and after uniform mixing, the obtained material is divided into three layers of a solid phase, a water phase and an oil phase after standing; wherein, the COD/BOD of the water is 0.42 by determination;
(2) Mixing the solid phase obtained after separation in the step (1) with 160mL of treating agent (the treating agent is 25wt% of hydrogen peroxide and n-tridecane, and the proportion of the hydrogen peroxide to the n-tridecane is 1);
(3) Removing the colloidal asphaltene on the uppermost layer of the material obtained in the step (2), further filtering and separating to obtain filtrate and waste clay, washing the waste clay with water, and drying at 80 ℃ to obtain regenerated clay with the oil content of 2.75%.
Example 2
(1) Mixing 500g of spent bleaching earth and 2800g of water at 65 ℃, wherein the pretreating agent consists of rhamnolipid and petroleum sulfonate, the adding amount is 1.20g and 7.5g respectively, and after the materials are uniformly mixed, the obtained materials are divided into three layers of a solid phase, a water phase and an oil phase after standing, wherein the COD/BOD of the water is 0.48 by determination;
(2) Mixing the solid phase obtained in the step (1) with water at 70 ℃, standing the uniformly mixed material, and dividing the material into a solid phase layer, a water phase layer and an oil phase layer;
(3) Mixing the solid phase obtained after the separation in the step (2) with 200mL of a treating agent (the treating agent is 35wt% of hydrogen peroxide, and the ratio of the hydrogen peroxide to n-heptane is 1;
(4) Removing the colloidal asphaltene on the uppermost layer of the material obtained in the step (3), further filtering and separating to obtain filtrate and waste clay, washing the waste clay with water, and drying at 90 ℃ to obtain regenerated clay with the oil content of 1.98%.
Example 3
(1) Mixing 500g of spent bleaching earth with 2100g of water at 100 ℃, wherein the pretreating agent consists of rhamnolipid and petroleum sulfonate, the adding amount is 0.68g and 9.0g respectively, and the materials obtained after uniform mixing are divided into three layers of a solid phase, a water phase and an oil phase after standing; wherein, the COD/BOD of the water is 0.38 by determination;
(2) Mixing the solid phase obtained after separation in the step (1) with 225mL of treating agent (the treating agent is 30wt% of hydrogen peroxide and n-sunflower alkane, and the ratio of hydrogen peroxide to n-sunflower alkane is 1) at 75 ℃, and then standing for layering;
(3) Removing the colloidal asphaltene on the uppermost layer of the material obtained in the step (2), further filtering and separating to obtain filtrate and waste clay, washing the waste clay with water, and drying at 95 ℃ to obtain regenerated clay with the oil content of 4.38%.
Example 4
(1) Mixing 500g of spent bleaching earth with 3300g of water at 80 ℃, wherein the pretreating agent consists of rhamnolipid and petroleum sulfonate in the addition amount of 2.10g and 7.0g respectively, and after uniformly mixing, the obtained material is divided into three layers of a solid phase, a water phase and an oil phase after standing; wherein, the COD/BOD of the water is 0.43 by determination;
(2) Mixing the solid phase obtained after separation in the step (1) with 310mL of treating agent (the treating agent is 25wt% of hydrogen peroxide and n-octane, the ratio of the hydrogen peroxide to the n-octane is 1:3, mixing at 95 ℃, simultaneously introducing mixed gas of sulfur dioxide and nitrogen dioxide into the mixed gas, wherein the volume ratio of the nitrogen dioxide to the sulfur dioxide is 1;
(3) Removing the colloidal asphaltene on the uppermost layer of the material obtained in the step (2), further filtering and separating to obtain filtrate and waste clay, washing the waste clay with water, and drying at 100 ℃ to obtain regenerated clay with the oil content of 2.39%.
Example 5
(1) Mixing 500g of waste argil with 2450g of water at 90 ℃, wherein the pretreating agent consists of rhamnolipid and petroleum sulfonate in the addition amount of 1.25g and 7.50g respectively, and standing the uniformly mixed materials to separate the materials into a solid phase layer, a water phase layer and an oil phase layer; wherein, the COD/BOD of the water is 0.52 by determination;
(2) Mixing the solid phase obtained after separation in the step (1) with 250mL of treating agent (the treating agent is 30wt% of hydrogen peroxide and n-heptane, the ratio of the hydrogen peroxide to the n-heptane is 1, mixing at 90 ℃, simultaneously introducing mixed gas of sulfur dioxide and nitrogen dioxide into the mixture, wherein the volume ratio of the nitrogen dioxide to the sulfur dioxide in the mixed gas is 1;
(3) Removing the colloidal asphaltene on the uppermost layer of the material obtained in the step (2), further filtering and separating to obtain filtrate and waste clay, washing the waste clay with water, and drying at 105 ℃ to obtain regenerated clay with the oil content of 0.98%.
Comparative example 1
The same as example 1, except that no pretreating agent was used, the oil content of the obtained regenerated clay was 5.21%, and the cut water was found to have a COD/BOD < 0.2 and poor biodegradability.
Comparative example 2
The same as example 1 except that only 20wt% hydrogen peroxide solution was used as the treating agent, the oil content of the obtained regenerated clay was 10.61%.
Comparative example 3
The same as example 2 except that only n-heptane was used as the treating agent, the regenerated clay had an oil content of 9.64%.
Claims (21)
1. A method for reducing the oil content of spent bleaching earth, comprising the steps of:
(1) Mixing waste argil, a pretreating agent and water, standing the materials obtained after uniform mixing, and dividing the materials into three layers, namely a solid phase, a water phase and an oil phase, wherein the pretreating agent comprises rhamnolipid and petroleum sulfonate;
(2) Mixing the solid phase obtained after the separation in the step (1) with a treating agent at 70-95 ℃, and then standing for layering; the treating agent comprises hydrogen peroxide solution and alkane with 5-15 carbon atoms; the mass ratio of the hydrogen peroxide solution to the alkane is 1:1 to 1:6; the concentration of the hydrogen peroxide solution is 20-40 wt%;
(3) Removing the colloidal asphaltene on the uppermost layer of the material obtained in the step (2), further performing solid-liquid separation to obtain filtrate and waste clay, and washing and drying the waste clay to obtain regenerated clay;
when the solid phase and the treating agent are mixed in the step (2), introducing mixed gas of nitrogen dioxide and sulfur dioxide into the solid phase; the volume ratio of nitrogen dioxide to sulfur dioxide in the mixed gas is 1:1 to 1:6.
2. the method of claim 1, wherein: in the step (2), the solid phase separated in the step (1) is mixed with a treating agent at 80-90 ℃.
3. The method of claim 1, wherein: and (2) taking the addition amount of water in the step (1) as a reference, wherein the concentration of rhamnolipid is 300-600 mg/L, and the concentration of petroleum sulfonate is 2000-4000 mg/L.
4. The method of claim 1, wherein: taking the addition amount of water in the step (1) as a reference, the concentration of rhamnolipid is 400-500 mg/L, and the concentration of petroleum sulfonate is 2500-3000 mg/L.
5. The method of claim 1, wherein: the alkane is one or more of n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decanone, n-undecane, n-dodecane, n-tridecane, n-tetradecane and n-pentadecane.
6. The method of claim 1, wherein: the alkane is n-heptane.
7. The method of claim 1, wherein: the concentration of the hydrogen peroxide solution is 25-35 wt%.
8. The method of claim 1, wherein: the mass ratio of the hydrogen peroxide solution to the alkane is 1:2 to 1:3.
9. the method of claim 1, wherein: the mass ratio of the waste argil in the step (1) to water is 1:3 to 1:7.
10. the method of claim 1, wherein: the mass ratio of the waste argil in the step (1) to water is 1:4 to 1:6.
11. the method of claim 1, wherein: the liquid-solid ratio of the treating agent to the solid phase in the step (2) is 1:1 to 1:8.
12. the method of claim 1, wherein: the liquid-solid ratio of the treating agent to the solid phase in the step (2) is 1:2 to 1:4.
13. the method of claim 1, wherein: the volume ratio of nitrogen dioxide to sulfur dioxide in the mixed gas is 1:2 to 1:3.
14. the method of claim 1, wherein: the drying temperature in the step (3) is 80-115 ℃; the drying time is 4-9 h.
15. The method of claim 1, wherein: the drying temperature in the step (3) is 90-105 ℃; the drying time is 5-6 h.
16. The method of claim 1, wherein: the mixing in the step (1) is carried out at 60-100 ℃.
17. The method of claim 1, wherein: the mixing in step (1) is carried out at 70-90 ℃.
18. The method of claim 1, wherein: the mixing treatment time in the step (1) is 2-10 h.
19. The method of claim 1, wherein: the mixing treatment time in the step (1) is 4-6 h.
20. The method of claim 1, wherein: and (2) continuously mixing the solid phase obtained after separation in the step (1) with water, repeatedly treating according to the operation conditions in the step (1), and further mixing the solid phase obtained after more than two times of treatment with a treating agent.
21. The method of claim 1, wherein: the waste clay in the step (1) is from the waste clay generated by the clay refining unit of the lubricating oil production device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811618740.6A CN111375391B (en) | 2018-12-28 | 2018-12-28 | Method for reducing oil content of waste argil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811618740.6A CN111375391B (en) | 2018-12-28 | 2018-12-28 | Method for reducing oil content of waste argil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111375391A CN111375391A (en) | 2020-07-07 |
| CN111375391B true CN111375391B (en) | 2023-02-03 |
Family
ID=71220031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811618740.6A Active CN111375391B (en) | 2018-12-28 | 2018-12-28 | Method for reducing oil content of waste argil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111375391B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115178303B (en) * | 2021-04-02 | 2024-05-24 | 绍兴绿奕化工有限公司 | Method for recovering waste porous catalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4285832A (en) * | 1980-08-11 | 1981-08-25 | Orth Jr George O | Method of recovering residual vegetable oil contained in spent bleaching clay and processing the bleaching clay for reuse |
| CN1337439A (en) * | 2000-08-09 | 2002-02-27 | 大庆油田有限责任公司勘探开发研究院 | Oil-displacing agent and its application |
| CN1962837A (en) * | 2006-11-17 | 2007-05-16 | 淄博市华联矿业有限责任公司 | Process for regeneration of waste lubricating oil |
| CN101434853A (en) * | 2008-11-25 | 2009-05-20 | 中国石油大学(华东) | Method for regenerating and recovering oil refining waste clay |
| CN104232318A (en) * | 2014-10-08 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Vegetable oil spent bleaching clay recovery process |
| CN105268419A (en) * | 2014-07-16 | 2016-01-27 | 青岛百键城环保科技有限公司 | Waste white clay recycling process |
-
2018
- 2018-12-28 CN CN201811618740.6A patent/CN111375391B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4285832A (en) * | 1980-08-11 | 1981-08-25 | Orth Jr George O | Method of recovering residual vegetable oil contained in spent bleaching clay and processing the bleaching clay for reuse |
| CN1337439A (en) * | 2000-08-09 | 2002-02-27 | 大庆油田有限责任公司勘探开发研究院 | Oil-displacing agent and its application |
| CN1962837A (en) * | 2006-11-17 | 2007-05-16 | 淄博市华联矿业有限责任公司 | Process for regeneration of waste lubricating oil |
| CN101434853A (en) * | 2008-11-25 | 2009-05-20 | 中国石油大学(华东) | Method for regenerating and recovering oil refining waste clay |
| CN105268419A (en) * | 2014-07-16 | 2016-01-27 | 青岛百键城环保科技有限公司 | Waste white clay recycling process |
| CN104232318A (en) * | 2014-10-08 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Vegetable oil spent bleaching clay recovery process |
Non-Patent Citations (2)
| Title |
|---|
| 用表面活性剂溶液回收炼油厂废白土中的蜡和油及废白土的综合利用;朱宪等;《中国环境科学》;19950630;第15卷(第3期);230-234 * |
| 鼠李糖脂在石油工业中的应用研究进展;刘雪红等;《化学工业与工程技术》;20120430;第33卷(第2期);5-8 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111375391A (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101033433A (en) | Regeneration method for waste lubricating oil | |
| CN109908881B (en) | Waste clay recycling treatment method | |
| CN101445420B (en) | Process for preparing benzene aromatic hydrocarbon by crude benzene | |
| CN105296135B (en) | A kind of regeneration method of waste lubricating oil | |
| CN110484345A (en) | A kind of method for regenerating waste lubricating oil | |
| JP2002529579A5 (en) | ||
| CN111375391B (en) | Method for reducing oil content of waste argil | |
| CN105255576B (en) | The method and its application of two-stage extraction purification producing base oil by regenerating waste lubricating oil | |
| CN105754704A (en) | Method for increasing yield of base oil by adopting extracted solution for secondary extraction | |
| CN112574783B (en) | Method for comprehensively utilizing styrene tar | |
| KR20230086707A (en) | Recovery of aliphatic hydrocarbons | |
| CN116144389B (en) | Advanced refining method of waste mineral oil tower top oil composite solvent | |
| CN103865625A (en) | Method for solvent extraction regeneration of waste engine oil | |
| CN109517615B (en) | Method for recovering oil from waste argil and method for preparing lubricating oil base oil | |
| CN109517619B (en) | Solvent removing method for extracting raffinate oil from aromatic hydrocarbon | |
| CN113698958B (en) | Method for separating aromatic hydrocarbon and saturated hydrocarbon in catalytic cracking slurry oil through composite solvent | |
| CN106221791B (en) | A kind of base oil spent bleaching clay selectivity de-oiling method and its device | |
| CN105419859A (en) | Reverse back extraction refining method for petroleum reduced pressure distillation distillate and application thereof | |
| CN111073681B (en) | Method for recovering oil from waste argil and method for preparing lubricating oil base oil | |
| CN108424786B (en) | Separation method of gasoline fraction and gasoline desulfurization method | |
| CN113105937A (en) | Waste mineral oil treatment system and treatment method | |
| CN108329946B (en) | Method for separating gasoline fraction and gasoline desulfurization method | |
| CN113372949A (en) | Method for removing asphalt in raw oil | |
| CN102268281A (en) | Recovery method of furfural solvent during lube solvent refining | |
| CN107162365B (en) | Preparation method and use method of sludge oil removal agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231120 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |