KR20020007235A - Membrane for reclamation of waste lubricating oil and fabrication method thereof - Google Patents
Membrane for reclamation of waste lubricating oil and fabrication method thereof Download PDFInfo
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- KR20020007235A KR20020007235A KR1020010063621A KR20010063621A KR20020007235A KR 20020007235 A KR20020007235 A KR 20020007235A KR 1020010063621 A KR1020010063621 A KR 1020010063621A KR 20010063621 A KR20010063621 A KR 20010063621A KR 20020007235 A KR20020007235 A KR 20020007235A
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- membrane
- ceramic
- lubricating oil
- waste lubricating
- pore size
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- 239000012528 membrane Substances 0.000 title claims abstract description 108
- 239000002699 waste material Substances 0.000 title claims abstract description 64
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 112
- 239000011148 porous material Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000001471 micro-filtration Methods 0.000 claims abstract description 25
- 238000000746 purification Methods 0.000 claims abstract description 20
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 33
- 239000003921 oil Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- 239000000314 lubricant Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009295 crossflow filtration Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000035699 permeability Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2315/00—Details relating to the membrane module operation
- B01D2315/10—Cross-flow filtration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Transplantation (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
본 발명은 폐윤활유 정제용 분리막 및 그의 제조 방법에 관한 것으로, 좀더 구체적으로는 폐윤활유 정제시의 투과율을 향상시키기 위해 금속 처리를 한 세라믹 분리막 및 그의 제조 방법에 관한 것이다.The present invention relates to a waste lubricating oil purification membrane and a method for producing the same, and more particularly, to a ceramic membrane subjected to metal treatment in order to improve the permeability during the purification of waste lubricating oil, and a manufacturing method thereof.
폐윤활유는 많은 윤활성분을 함유하고 있어 정제시 윤활유의 회수율이 높을 것으로 기대되므로, 이들 재생 및 활용에 대한 연구가 활발히 수행되고 있다.Since the waste lubricant contains many lubricating components, it is expected that the recovery rate of lubricating oil will be high.
폐윤활유 재활용에는 불순물의 제거 정도 및 처리 공정에 따라 윤활유로 활용하는 방법 또는 연료유로 활용하는 방법이 있다. 연료유로 활용하기 위한 폐윤활유의 정제 공정은 비교적 간단한 침강, 원심분리 및 여과와 같은 물리적 처리 공정에 의하여 연소시 발생되는 유해물질을 사전에 제거하는 방법을 사용하고 있다.Waste lubricants can be recycled or used as fuel oil, depending on the degree of removal of impurities and the treatment process. The purification process of waste lubricating oil to be used as fuel oil uses a method of removing harmful substances generated during combustion by physical treatment processes such as relatively simple sedimentation, centrifugation and filtration.
폐윤활유의 재활용은 경제성과 실용화 면에서 정제를 통한 윤활기유 및 연료유로의 활용이라고 할 수 있다. 폐윤활유를 정제하여 연료유로 사용할 때 가장 문제시되는 점은 정제 연료유 내에 함유되어 있는 애시 (ash) 성분이다. 윤활유의 기능 향상을 위하여 첨가된 각종 첨가제, 오염에 의한 불순물 및 마모에 의한 금속 성분들이 정제 과정에서 완전히 제거되지 않으면, 연소시 애시 성분으로 존재하게 되고, 결국 열설비의 손상이나 환경 오염과 같은 문제들이 발생하게 된다.Recycling of waste lubricating oil can be regarded as utilization of lubricating base oil and fuel oil through refining in terms of economy and practical use. The most problematic point when the waste lubricating oil is refined and used as fuel oil is the ash component contained in the refined fuel oil. If various additives added to improve the function of lubricating oil, impurities caused by contamination and metal components due to abrasion are not completely removed during the refining process, they will be present as ash components during combustion, resulting in problems such as damage to thermal facilities or environmental pollution. Will occur.
현재 일부 실용화되고 있는 폐윤활유의 정제 공정은 장치 설비비가 높고 에너지 소비량이 많기 때문에 경제성이 낮을 뿐만 아니라 공정 상에서 부산물로 생성되는 산성 슬러지의 처리와 이에 관련된 2차적인 환경오염 등이 문제시 되고 있다. 따라서, 환경 친화적인 폐윤활유 정제 기술 개발에 많은 연구가 진행되어 왔으며,그 중에서도 막분리 방법이 다른 방법들에 비해 경제적이며 효율적인 공정으로 평가받고 있다.Currently, some of the practically used waste oil refining processes have high economical equipment costs and high energy consumption, and are not only economically economical but also have problems with the treatment of acidic sludge generated as by-products and secondary environmental pollution. Therefore, much research has been conducted on the development of environmentally friendly waste lubricating oil refining technology, and among them, the membrane separation method is evaluated as an economical and efficient process compared to other methods.
특히, 세라믹막은 기계적 강도와 내마모성이 우수하고 고온 고압하에서도 안정하며, 폐윤활유의 막분리 공정에서 발생하기 쉬운 파울링 (fouling) 현상을 방지하기 위한 고압 역세척 및 다양한 세척 방법으로 재생사용이 가능하기 때문에 장시간 사용할 수 있다는 장점이 있다. 따라서, 폐윤활유를 정제하기 위한 분리막으로 세라믹막을 사용하는 공정이 주목받고 있다.In particular, the ceramic membrane has excellent mechanical strength and wear resistance, is stable under high temperature and high pressure, and can be regenerated and used by high pressure backwashing and various cleaning methods to prevent fouling, which is likely to occur in the membrane separation process of waste lubricants. It has the advantage that it can be used for a long time. Therefore, the process of using a ceramic membrane as a separator for purifying waste lubricating oil has attracted attention.
폐윤활유 정제용으로 사용하기 위한 세라믹막은 우수한 분리 특성 및 투과율을 가져야 한다. 즉, 폐윤활유 내의 불순물, 특히 애시 함량을 기준치 이하로 감소시킬 수 있어야 하며, 적절한 생산성을 보장할 수 있을 정도의 높은 투과율을가져야 한다. 종래 기술에서는, 이러한 분리 특성 및 투과율을 향상시키기 위해, 주로 기공 크기를 조절하는 방법이 제안되고 있다. 그러나, 투과율을 향상시키기 위해 기공 크기를 증가시키는 경우에는 분리 효율이 저하되고, 반면에 분리 효율을 향상시키기 위해 기공 크기를 감소시키는 경우에는 투과율이 감소하는 문제가 발생한다. 따라서, 세라믹막의 분리 효율 및 투과율을 동시에 향상시킬 수 있는 방법이 요구되고 있다.Ceramic membranes for use in waste lubricating oil refining should have good separation properties and permeability. That is, it should be possible to reduce the impurities, particularly ash content, in the waste lubricating oil below the reference value, and have a high permeability to ensure adequate productivity. In the prior art, in order to improve such separation characteristics and permeability, a method of adjusting the pore size is mainly proposed. However, when the pore size is increased to improve the permeability, the separation efficiency is lowered, whereas when the pore size is decreased to improve the separation efficiency, the permeability is reduced. Therefore, there is a demand for a method capable of simultaneously improving the separation efficiency and transmittance of the ceramic film.
본 발명은 상술한 제반 문제들을 해결하기 위해 제안된 것으로, 분리 특성 및 투과율이 우수한 폐윤활유 정제용 분리막을 제공하는 데 그 목적이 있다.The present invention has been proposed to solve the above-mentioned problems, and an object thereof is to provide a separator for purification of waste lubricating oil having excellent separation characteristics and permeability.
본 발명의 다른 목적은, 상기한 폐윤활유 정제용 분리막의 제조 방법을 제공하는 데 그 목적이 있다.Another object of the present invention is to provide a method for producing the above separation membrane for waste lubricating oil.
도 1은 본 발명에 의한 폐윤활유 정제용 분리막을 나타내는 단면도.1 is a cross-sectional view showing a membrane for purification of waste lubricating oil according to the present invention.
도 2는 역침지 인상법을 설명하기 위한 도면.2 is a view for explaining a reverse immersion pulling method.
도 3은 크로스플로우형 폐윤활유 여과장치를 나타내는 개략도.3 is a schematic view showing a crossflow type waste lubricating oil filtration device.
*도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1 : 세라믹 지지체 2 : 정밀여과막1: ceramic support 2: microfiltration membrane
3 : 한외여과막 5 : 표면개질된 층3: ultrafiltration membrane 5: surface modified layer
10 : 원료 탱크 12 : 가열기10: raw material tank 12: heater
13 : 교반기 16 : 막 모듈13: stirrer 16: membrane module
17 : 분리막 18 : 배출구17: separator 18: outlet
20 : 가압 순환 펌프 21 : 밸브20 pressurized circulation pump 21 valve
22 : 압력 게이지 23 : 유량계22: pressure gauge 23: flow meter
25 : 바이패스관25: bypass tube
상술한 목적을 달성하기 위하여, 본 발명에 의한 폐윤활유 정제용 분리막은 기공 크기가 1 내지 20 ㎛ 인 다공성 세라믹 지지체와 세라믹 지지체보다 기공 크기가 작은 여과용 세라믹막이 적층된 세라믹 복층막을 금속으로 표면개질시킨 것을 특징으로 한다. 이때, 여과용 세라믹막은 기공 크기가 0.1 내지 2 ㎛ 인 정밀여과용 세라믹막이거나 또는 기공 크기가 0.1 내지 2 ㎛ 인 정밀여과용 세라믹막 및 기공 크기가 5 내지 40 nm 인 한외여과용 세라믹막이 적층된 막일 수 있다.In order to achieve the above object, the waste lubricating oil purification membrane according to the present invention is a surface-modified ceramic multilayer membrane in which a porous ceramic support having a pore size of 1 to 20 μm and a ceramic membrane for filtration having a smaller pore size than a ceramic support are laminated with metal. It is characterized in that. At this time, the filtration ceramic membrane is a microfiltration ceramic membrane having a pore size of 0.1 to 2 μm or a microfiltration ceramic membrane having a pore size of 0.1 to 2 μm and an ultrafiltration ceramic membrane having a pore size of 5 to 40 nm. It can be.
본 발명의 다른 목적을 달성하기 위하여, 폐윤활유 정제용 분리막의 제조 방법은 기공 크기가 1 내지 10 ㎛ 인 세라믹 지지체 상에 기공 크기가 0.1 내지 1 ㎛ 인 정밀여과용 세라믹막을 형성한 후 금속으로 표면개질하는 방법을 포함한다. 세라믹 복층막을 금속으로 표면개질함으로써 폐윤활유의 투과율을 향상시킬 수 있다.In order to achieve the other object of the present invention, the method for producing a separation membrane for waste lubricating oil has a surface formed of a fine filtration ceramic membrane having a pore size of 0.1 to 1 ㎛ on a ceramic support having a pore size of 1 to 10 ㎛ It includes a method of reforming. By surface-modifying the ceramic multilayer film with a metal, the transmittance of waste lubricant oil can be improved.
또한, 폐윤활유의 분리 효율을 향상시키기 위해 정밀여과막 상에 기공 크기가 5 내지 40 nm 인 한외여과용 세라믹막을 더 형성할 수도 있다. 한외여과막은 티타니아, 알루미나 및 지르코니아 중 어느 하나를 사용하는 졸-겔 공정에 의해 형성하는 것이 바람직하다.In addition, an ultrafiltration ceramic membrane having a pore size of 5 to 40 nm may be further formed on the microfiltration membrane to improve the separation efficiency of the waste lubricant. The ultrafiltration membrane is preferably formed by a sol-gel process using any one of titania, alumina and zirconia.
본 발명의 다른 측면에 의한 폐윤활유 정제용 분리막의 제조 방법은, 용매 내에 세라믹 파우더를 균일하게 분산시켜 슬러리를 제조하고, 슬러리를 다공성 세라믹 지지체 상에 코팅하고, 코팅층을 열처리하여 정밀여과용 세라믹막을 형성하고, 세라믹 지지체 및 정밀여과막을 금속으로 표면개질하는 방법으로 진행된다.According to another aspect of the present invention, there is provided a method for preparing a separation membrane for waste lubricating oil, in which a ceramic powder is uniformly dispersed in a solvent to prepare a slurry, the slurry is coated on a porous ceramic support, and the coating layer is heat treated to form a ceramic membrane for microfiltration. And the surface of the ceramic support and the microfiltration film are modified with a metal.
이때, 세라믹 지지체 상에 슬러리를 코팅하는 공정은 역침지 인상법으로 실시하는 것이 바람직하다. 또한, 금속염 용액 내에 세라믹 지지체 및 세라믹막을 소정시간 동안 침지시킨 후 열처리함으로써 세라믹 지지체 및 정밀여과막을 표면개질하는 것이 바람직하다.At this time, the step of coating the slurry on the ceramic support is preferably carried out by a reverse immersion pulling method. In addition, it is preferable to immerse the ceramic support and the ceramic film in the metal salt solution for a predetermined time and then heat-treat the surface of the ceramic support and the microfiltration film.
이하, 도면을 참조하여 본 발명의 실시예를 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
본 발명에 의한 세라믹 분리막은 폐윤활유 정제를 위한 크로스플로우 (crossflow) 형 여과 장치에서 사용하기 위한 것이다. 이러한 여과 장치에 의한 폐윤활유 정제 공정은 상승된 압력 및 온도에서 진행되므로, 분리막은 분리 특성 뿐만 아니라 기계적 강도면에서 우수해야 한다. 따라서, 도 1에 도시된 바와 같이, 기공이 큰 세라믹 지지체 상에 미세 기공을 갖는 세라믹막, 즉 여과용 세라믹막을 코팅한 세라믹 복층막을 분리막으로 사용하는 것이 바람직하다.The ceramic separator according to the present invention is for use in a crossflow type filtration apparatus for purification of waste lubricant oil. Since the waste lubricating oil purification process by such a filtration device proceeds at an elevated pressure and temperature, the membrane should be excellent in terms of separation properties as well as mechanical strength. Therefore, as shown in FIG. 1, it is preferable to use a ceramic membrane having fine pores on the ceramic support having large pores, that is, a ceramic multilayer membrane coated with a filtration ceramic membrane as a separator.
구체적으로, 도 1을 참조하면, 본발명의 일실시예에 의한 분리막은, 기공이 큰 세라믹 지지체 (1), 여과용 세라믹막 (4) 및 금속으로 표면개질된 층 (5) 을 구비한다. 여기서, 여과용 세라믹막 (4) 은 정밀여과용 세라믹막 (2) 및 한외여과용 세라믹막 (3) 으로 구성된다.Specifically, referring to FIG. 1, the separator according to an embodiment of the present invention includes a ceramic support 1 having large pores, a ceramic membrane for filtration 4, and a layer 5 surface-modified with a metal. Here, the filtration ceramic membrane 4 consists of the microfiltration ceramic membrane 2 and the ultrafiltration ceramic membrane 3.
세라믹 지지체 (1) 는 분리 기능을 갖는 정밀여과막 (2) 및 한외여과막 (3) 을 지지하는 역할을 하는 것으로, 기공 크기가 1 내지 20 ㎛ 인 것이 바람직하다. 또한, 세라믹 지지체 (1) 의 형태는 여과 장치의 막 모듈의 형태에 따라 달라질 수 있으며, 예를 들어, 튜브형이다.The ceramic support 1 serves to support the microfiltration membrane 2 and the ultrafiltration membrane 3 having a separation function, and preferably has a pore size of 1 to 20 µm. Further, the shape of the ceramic support 1 may vary depending on the shape of the membrane module of the filtration device, for example, tubular.
여과용 세라믹막 (4) 의 구성은 정제유의 용도에 따라 달라질 수 있다. 예를 들어, 정제유를 재생 연료유로 활용하고자 하는 경우 여과용 세라믹막 (4) 은 정밀여과용 세라믹막 (2) 만으로 구성되고, 윤활유로 활용하고자 하는 경우 여과용 세라믹막 (4) 은 정밀여과용 세라믹막 (2) 및 한외여과용 세라믹막 (3) 이 적층된 막으로 구성된다.The configuration of the filtration ceramic membrane 4 may vary depending on the use of refined oil. For example, when the refined oil is to be used as a regeneration fuel oil, the filtration ceramic membrane 4 is composed of only the fine filtration ceramic membrane 2, and when the filtration oil is to be used as lubricating oil, the filtration ceramic membrane 4 is used for the fine filtration. It consists of a film | membrane in which the ceramic film 2 and the ultrafiltration ceramic film 3 were laminated | stacked.
정밀여과용 세라믹막 (2) 은 예를 들어, 알루미나, 지르코니아, 티타니아, 마그네시아, 실리카 및 그들의 조합 중 어느 하나로 된 세라믹막으로, 기공 크기는 0.1 내지 1 ㎛ 인 것이 바람직하다. 한외여과용 세라믹막 (3) 은 예를 들어, 티타니아, 알루미나, 지르코니아 및 그들의 조합 중 어느 하나로 된 세라믹막으로, 기공 크기는 5 내지 40 nm 인 것이 바람직하다.The microfiltration ceramic film 2 is, for example, a ceramic film made of any one of alumina, zirconia, titania, magnesia, silica and combinations thereof, and the pore size is preferably 0.1 to 1 m. The ultrafiltration ceramic film 3 is, for example, a ceramic film made of any one of titania, alumina, zirconia and combinations thereof, and the pore size is preferably 5 to 40 nm.
여과용 세라믹막 (4) 의 표면에 금속으로 표면개질된 층 (5) 이 형성되어 있다. 표면개질된 층 (5) 은 여과막 (4) 의 표면 상에 형성된 금속층일 수도 있고, 여과막 (4) 의 상부로 금속 입자들이 침투하여 형성된 층일 수도 있다. 이러한 층 (5) 은 폐윤활유에 대한 젖음성을 향상시켜 분리막의 투과율을 증진시키게 된다. 금속은, 예를 들어, 코발트, 니켈, 은, 마그네슘, 철 및 그들의 조합 중 어느 하나일 수 있다.On the surface of the filtration ceramic film 4, a layer 5 surface-modified with a metal is formed. The surface-modified layer 5 may be a metal layer formed on the surface of the filtration membrane 4 or may be a layer formed by penetration of metal particles onto the filtration membrane 4. This layer (5) improves the wettability to the waste lubricant to enhance the permeability of the separator. The metal can be, for example, any one of cobalt, nickel, silver, magnesium, iron and combinations thereof.
다음, 이와 같은 폐윤활유 정제용 분리막의 제조 방법을 설명한다.Next, the manufacturing method of such a separation membrane for waste lubricating oil will be described.
우선, 기공이 큰 다공성 세라믹 지지체 (1) 를 제조한다. 세라믹 지지체 (1) 의 기공 크기는 폐윤활유의 투과율과 지지체 상에 형성될 코팅층의 물성을 고려하여 조절될 수 있으며, 1 내지 20 ㎛ 인 것이 바람직하다. 또한, 세라믹 지지체 (1) 의 형태는 폐윤활유 여과 장치의 막 모듈의 형태에 따라 달라질 수 있다. 세라믹 지지체 (1) 는, 예를 들어, 압출 성형법 또는 슬립 캐스팅법으로 제조하며, 통상 그 재료로 알루미나를 사용한다. 본 실시예에서, 세라믹 지지체 (1) 는 튜브형의 알루미나 지지체이다.First, a porous ceramic support 1 having large pores is produced. The pore size of the ceramic support 1 can be adjusted in consideration of the transmittance of the waste lubricating oil and the physical properties of the coating layer to be formed on the support, preferably 1 to 20 μm. In addition, the shape of the ceramic support 1 may vary depending on the shape of the membrane module of the waste lubricating oil filtration device. The ceramic support 1 is produced by an extrusion molding method or a slip casting method, for example, and alumina is usually used as the material. In this embodiment, the ceramic support 1 is a tubular alumina support.
이어서, 세라믹 지지체 (1) 상에 지지체보다 작은 크기의 기공을 갖는 여과용 세라믹막 (4) 을 형성한다. 상술한 바와 같이, 여과용 세라믹막 (4) 은 정제유의 용도에 따라 정밀여과용 세라믹막 (2) 만으로 형성할 수도 있고, 정밀여과용 세라믹막 (2) 및 한외여과용 세라믹막 (3) 을 적층시켜 형성할 수도 있다.Subsequently, a ceramic membrane for filtration 4 having pores of a smaller size than the support is formed on the ceramic support 1. As described above, the filtration ceramic membrane 4 may be formed only of the microfiltration ceramic membrane 2 according to the use of refined oil, and the microfiltration ceramic membrane 2 and the ultrafiltration ceramic membrane 3 are formed. It may be formed by laminating.
정밀여과막 (2) 은 슬러리 코팅법으로 형성하는 것이 바람직하다. 슬러리 코팅법은 용매 내에 세라믹 파우더를 균일하게 분산시킨 세라믹 슬러리를 제조하여 코팅하는 방법이다. 용매로는 물 또는 알콜을 사용하며, 세라믹 파우더로는 예를 들어, 알루미나, 지르코니아, 티타니아, 마그네시아, 실리카 및 그들의 조합 중 어느 하나를 사용할 수 있다. 또한, 세라믹 파우더를 용매 내에 균일하게 분산시키기 위해 결합제 및 분산제의 역할을 하는 첨가제를 소정량 첨가한다.The microfiltration membrane 2 is preferably formed by a slurry coating method. The slurry coating method is a method of preparing and coating a ceramic slurry in which ceramic powder is uniformly dispersed in a solvent. Water or alcohol may be used as the solvent, and any one of alumina, zirconia, titania, magnesia, silica and combinations thereof may be used as the ceramic powder. In addition, a predetermined amount of an additive which serves as a binder and a dispersant is added to uniformly disperse the ceramic powder in the solvent.
알콜을 용매로 사용하여 슬러리를 제조하는 경우에는, 첨가제로 에틸셀룰로스를 사용하는 것이 바람직하다. 슬러리의 점도 및 안정성을 유지하기 위해 용매를 끓는점까지 가열한 후 용매에 대해 약 0.1 내지 5 wt% 의 에틸셀룰로스를 첨가하고 상온으로 냉각시킨다. 그 후, 약 3 내지 30 wt% 의 세라믹 파우더를 첨가하고 약 4 내지 24 시간 동안 볼밀링하여 안정한 분산상의 슬러리를 제조한다. 용매인 알콜로는, 예를 들어, 이소프로판올을 사용한다.When preparing a slurry using alcohol as a solvent, it is preferable to use ethyl cellulose as an additive. The solvent is heated to boiling point to maintain the viscosity and stability of the slurry, then about 0.1-5 wt% of ethylcellulose is added to the solvent and cooled to room temperature. Thereafter, about 3 to 30 wt% of ceramic powder is added and ball milled for about 4 to 24 hours to prepare a stable dispersed slurry. As an alcohol which is a solvent, isopropanol is used, for example.
물을 용매로 사용하여 슬러리를 제조하는 경우에는, 첨가제로 메틸셀룰로스를 사용하는 것이 바람직하다. 용매에 메틸셀룰로스를 첨가한 후 용매에 대해 10 내지 70 wt% 의 세라믹 파우더를 첨가하고 약 4 내지 24 시간 동안 볼밀링하여 안정한 분산상의 슬러리를 제조한다.When water is used as a solvent to prepare a slurry, it is preferable to use methylcellulose as an additive. Methylcellulose is added to the solvent followed by the addition of 10 to 70 wt% of the ceramic powder to the solvent and ball milling for about 4 to 24 hours to form a stable dispersed slurry.
이와 같이 제조된 세라믹 슬러리의 입자 크기는 세라믹 지지체 (1) 의 기공 크기의 약 1/4 내지 1 배 정도인 것이 바람직하다. 그러면, 세라믹 지지체 (1) 의 기공 크기에 비해 더 작은 기공을 갖는 세라믹 막을 형성할 수 있다.The particle size of the ceramic slurry thus prepared is preferably about 1/4 to 1 times the pore size of the ceramic support 1. Then, a ceramic film having pores smaller than the pore size of the ceramic support 1 can be formed.
슬러리를 제조한 후 세라믹 지지체의 일측 표면, 즉 튜브형 알루미나 지지체의 내부 표면에 세라믹 슬러리를 코팅한다. 슬러리의 코팅은, 예를 들어, 침지법, 가압법, 침지 인상법 및 역침지 인상법 중 어느 하나를 사용할 수 있으며, 특히 역침지 인상법을 사용하는 것이 바람직하다. 역침지 인상법은 역인상 속도, 즉 슬러리가 하방으로 빠져나가는 속도를 조절함으로써 지지체의 내부 표면을 균일하게 코팅하는 방법이다.After preparing the slurry, the ceramic slurry is coated on one surface of the ceramic support, that is, the inner surface of the tubular alumina support. For coating of the slurry, any one of, for example, an immersion method, a pressing method, an immersion pulling method, and a reverse immersion pulling method can be used, and it is particularly preferable to use a reverse immersion pulling method. The reverse immersion pulling method is a method of uniformly coating the inner surface of the support by controlling the reverse impression speed, that is, the rate at which the slurry exits downward.
도 2는 역침지 인상법을 사용하여 튜브형 알루미나 지지체의 내부 표면을 슬러리로 코팅하는 방법을 나타내는 도면이다. 도 2에 도시된 바와 같이, 알루미나 지지체의 내부를 슬러리로 완전히 채운 후 밸브를 열어 슬러리가 일정 속도로 빠져나가도록 한다. 이때, 알루미나 지지체의 모세관력을 최소화시켜 코팅층의 두께를 얇게 하기 위해, 담체를 용매에 충분히 적신 다음에 코팅을 실시하는 것이 바람직하다. 역인상 속도는 담체의 길이 및 슬러리의 농도와 점도에 따라 달라질 수 있으며, 예를 들어, 10 내지 100 mm/min 의 범위 내에서 조절한다.FIG. 2 shows a method of coating the inner surface of a tubular alumina support with a slurry using a reverse immersion pulling method. As shown in Figure 2, after filling the inside of the alumina support with the slurry completely, the valve is opened to allow the slurry to exit at a constant speed. At this time, in order to minimize the capillary force of the alumina support to reduce the thickness of the coating layer, it is preferable that the carrier is sufficiently wetted with a solvent and then coated. The reverse impression speed may vary depending on the length of the carrier and the concentration and viscosity of the slurry, for example, controlled within the range of 10 to 100 mm / min.
세라믹 코팅층이 형성되면, 코팅층을 포함하는 세라믹 지지체 (1) 를 상온에서 약 1 내지 3 일 동안 건조시킨 후 약 950 내지 1300 ℃ 의 온도로 열처리한다. 그 결과, 세라믹 지지체 (1) 및 정밀여과막 (2) 으로 구성된 세라믹 복층막이 형성된다. 이때, 코팅층의 건조 시간 및 열처리 온도는 세라믹 파우더의 종류 및 입자 크기에 따라 조절된다. 정밀여과막 (2) 의 기공 크기는 세라믹 파우더의 입자 크기 및 형상에 따라 달라지는데, 폐윤활유의 투과율 및 불순물의 분리 효율을 고려하여 약 0.1 ㎛ 내지 1 ㎛ 범위인 것이 바람직하다.When the ceramic coating layer is formed, the ceramic support 1 including the coating layer is dried at room temperature for about 1 to 3 days and then heat treated at a temperature of about 950 to 1300 ° C. As a result, a ceramic multilayer film composed of the ceramic support 1 and the microfiltration film 2 is formed. At this time, the drying time and the heat treatment temperature of the coating layer is adjusted according to the type and particle size of the ceramic powder. The pore size of the microfiltration membrane 2 depends on the particle size and shape of the ceramic powder, preferably in the range of about 0.1 μm to 1 μm in consideration of the permeability of the waste lubricant and separation efficiency of impurities.
한외여과막 (3) 은 졸-겔 공정으로 형성하는 것이 바람직하다. 우선, 통상의 방법으로 입자 크기가 1 내지 100 nm 인 코팅용 졸을 제조한다. 코팅용 졸은, 예를 들어, 티타니아, 알루미나, 지르코니아 및 그들의 조합 중 어느 하나로 된 졸이다. 이러한 코팅용 졸은, 예를 들어, 침지 코팅법 또는 가압 코팅법으로 정밀여과막 (2) 상에 코팅한다. 코팅층이 형성된 세라믹 지지체 (1) 를 상온에서 1 내지 3 일간 건조한 후에 350 ℃ 내지 800 ℃ 정도의 온도에서 약 1 내지 3 시간 동안 열처리하여 한외여과막 (3) 을 형성한다. 이에 따라 형성된 한외여과막 (3) 의 기공 크기는 5 내지 40 nm 인 것이 바람직하다. 정밀여과막 (2) 상에 한외여과막 (3) 을 더 형성하면, 폐윤활유 내의 불순물들의 분리 효율이 향상되어 정제유 내의 애시 함량을 0.1 wt% 이하로 감소시킬 수 있다.The ultrafiltration membrane 3 is preferably formed by a sol-gel process. First, a coating sol having a particle size of 1 to 100 nm is prepared by a conventional method. Coating sols are, for example, sols made of any one of titania, alumina, zirconia and combinations thereof. This coating sol is coated on the microfiltration membrane 2 by, for example, an immersion coating method or a pressure coating method. The ceramic support 1 on which the coating layer is formed is dried at room temperature for 1 to 3 days and then heat treated at a temperature of about 350 ° C to 800 ° C for about 1 to 3 hours to form an ultrafiltration film 3. The pore size of the ultrafiltration membrane 3 thus formed is preferably 5 to 40 nm. If the ultrafiltration membrane 3 is further formed on the microfiltration membrane 2, the separation efficiency of the impurities in the waste lubricating oil can be improved to reduce the ash content in the refined oil to 0.1 wt% or less.
이후, 본 발명의 특징으로 여과용 세라믹막 (4) 의 투과율을 증진시키기 위한 표면개질 공정을 실시한다. 표면개질 공정은 폐윤활유의 투과율을 증진시키기 위한 것으로, 세라믹에 비해 오일에 대한 젖음성이 우수한 금속으로 여과용 세라믹막 (4) 을 처리하여 표면 특성을 변화시키게 된다.Thereafter, as a feature of the present invention, a surface modification process for enhancing the transmittance of the filtration ceramic membrane 4 is carried out. The surface modification process is to improve the permeability of the waste lubricating oil, and the surface characteristics are changed by treating the filtration ceramic membrane 4 with a metal having better wettability to oil than the ceramic.
구체적으로, 표면개질 공정은 소정 농도의 금속염 용액에 세라믹 복층막 (1, 4) 을 소정 시간 동안 침지시켜 금속을 침투시킨 후 건조하고 열처리하는 방법으로 행해질 수 있다. 그러면, 여과용 세라믹막 (4) 의 표면 및 상부에 금속으로 표면개질된 층 (5) 이 형성된다. 표면 개질을 위한 금속으로는 예를 들어, 코발트, 니켈, 은, 마그네슘, 철 및 그들의 조합 중 어느 하나를 사용할 수 있으며, 금속염 용액의 농도는 0.05 내지 0.2 몰/ℓ인 것이 바람하다. 또한, 열처리 시간 및 온도는 금속염의 종류에 따라 조절한다.Specifically, the surface modification process may be performed by immersing the ceramic multilayer films 1 and 4 in a metal salt solution of a predetermined concentration for a predetermined time to infiltrate the metal, followed by drying and heat treatment. Then, a layer 5 surface-modified with metal is formed on the surface and the top of the filtration ceramic film 4. As the metal for surface modification, for example, cobalt, nickel, silver, magnesium, iron or any combination thereof can be used, and the concentration of the metal salt solution is preferably 0.05 to 0.2 mol / l. In addition, heat processing time and temperature are adjusted according to the kind of metal salt.
이와 같은 제조 방법에 의하면, 세라믹 지지체 상에 정밀여과막 및 한외여과막을 형성한 후 금속으로 표면개질함으로써, 분리 특성이 우수할 뿐만 아니라 투과율이 높은 폐윤활유 정제용 분리막을 제조할 수 있게 된다.According to such a manufacturing method, by forming a microfiltration membrane and an ultrafiltration membrane on a ceramic support and then surface modification with a metal, it is possible to produce a separation membrane for waste lubricating oil refining as well as excellent separation characteristics and high transmittance.
다음, 본 발명에 의한 분리막을 사용하는 여과 장치에 의한 폐윤활유 정제 공정에 대해 설명한다.Next, the waste lubricating oil purification process by the filtration apparatus using the separation membrane by this invention is demonstrated.
도 3은 폐윤활유 정제용 크로스플로우형 여과 장치를 나타내는 개략도이다. 크로스플로우형 여과 장치는 원료 탱크로부터 일정 압력 및 온도로 공급된 폐윤활유가 분리막이 장착된 모듈을 통과하면서 분리막을 통하여 투과되고, 투과되지 않은 폐윤활유는 원료 탱크로 되돌아가는 순환식 여과 장치를 말하는 것이다.3 is a schematic view showing a crossflow filtration device for refining waste lubricant oil. The crossflow filtration device refers to a circulating filtration device in which waste lubricating oil supplied from a raw material tank at a constant pressure and temperature passes through a separation membrane while passing through a module equipped with a separation membrane, and non-permeable waste lubricating oil returns to the raw material tank. will be.
도 3을 참조하면, 여과 장치는 분리막 (17) 이 장착되어 폐윤활유를 정제하는 막 모듈 (16) 및 폐윤활유를 공급하는 원료 탱크 (10) 를 구비한다. 막 모듈 (16) 의 내부에 본 발명에 의한 분리막 (17) 이 장착되어 분리막 (17) 을 통해폐윤활유가 정제되고, 정제된 오일은 배출구 (18) 를 통해 수집된다. 막 모듈 (16) 은, 예를 들어, 스테인레스 스틸 재질로 형성된다. 원료 탱크 (10) 에는 가열 장치 (12) 및 교반기 (13) 가 장착되어 저장된 폐윤활유의 온도를 조절하고 여과 후 잔여 오일의 순환시 탱크 (10) 내의 온도와 농도 구배를 최소화시킨다.Referring to FIG. 3, the filtration apparatus is equipped with a membrane module 16 to which the separator 17 is mounted to purify the waste lubricant oil and a raw material tank 10 for supplying the waste lubricant oil. The membrane 17 according to the present invention is mounted inside the membrane module 16 to purify the waste lubricating oil through the separator 17, and the purified oil is collected through the outlet 18. The membrane module 16 is formed of, for example, stainless steel material. The raw material tank 10 is equipped with a heating device 12 and an agitator 13 to adjust the temperature of the stored waste lubricant oil and to minimize the temperature and concentration gradient in the tank 10 during circulation of the residual oil after filtration.
원료 탱크 (10) 의 배출구와 막 모듈 (16) 사이에는 폐윤활유의 이송 및 가압을 위한 가압 순환 펌프 (20) 가 설치된다. 펌프 (20) 및 막 모듈 (16) 사이의 이송관에는 밸브들 (21), 유량계 (23) 및 압력 게이지 (22) 가 설치되어 폐윤활유의 유속 및 압력을 일정하게 조절한다.Between the outlet of the raw material tank 10 and the membrane module 16, the pressurized circulation pump 20 for conveying and pressurizing waste lubricating oil is provided. In the transfer pipe between the pump 20 and the membrane module 16, valves 21, a flowmeter 23 and a pressure gauge 22 are installed to constantly adjust the flow rate and pressure of the waste lubricant.
또한, 막 모듈 (16) 및 펌프 (20) 사이에 바이패스관 (25) 을 설치하여 고압 하에서 작동시 분리막으로 공급되는 유량이 많을 경우에 펌프 (20) 에서 나오는 폐윤활유를 원료 탱크 (10) 로 되돌릴 수 있도록 한다. 바람직하게는, 원료 탱크 (20), 이송관을 포함하는 모든 유체 이동 경로는 단열재로 단열시켜 고온 작동시 전체 장치 내에서 유체의 온도차를 최소화한다.In addition, a waste pipe 25 is installed between the membrane module 16 and the pump 20 to supply waste lubricant oil from the pump 20 when the flow rate supplied to the separator during operation under high pressure is large. To return. Preferably, all fluid flow paths, including feed tank 20, transfer tube, are insulated with thermal insulation to minimize the temperature difference of the fluid within the entire apparatus during high temperature operation.
원료 탱크 (10) 로부터 공급된 폐윤활유는 막 모듈 (16) 을 통과한다. 이때, 분리막 (17) 을 통하여 정제된 투과유는 배출구 (18) 를 통해 수집되고 투과하지 않은 오일은 다시 원료 탱크 (10) 로 회수된다. 투과량, 분리 효율 및 분리막의 내구성 등을 고려하여 정제 공정의 온도, 유속 및 막간 압력 등을 최적화시킨다.The waste lubricating oil supplied from the raw material tank 10 passes through the membrane module 16. At this time, the permeated oil purified through the separation membrane 17 is collected through the discharge port 18 and the oil which has not permeated is recovered to the raw material tank 10 again. Considering the permeation rate, separation efficiency and membrane durability, the temperature, flow rate and intermembrane pressure of the purification process are optimized.
이와 같은 정제 장치에서 본 발명에 의한 분리막을 사용하면, 폐윤활유의 투과율이 높아져 생산성이 증진될 뿐만 아니라 분리막의 분리 효율도 우수하여 재생연료유 및 윤활기유로 활용할 수 있을 정도로 낮은 애시 함량을 갖는 정제유를 얻을 수 있다.When the separation membrane according to the present invention is used in such a refining apparatus, the permeability of the waste lubricating oil is increased to improve productivity, and the separation efficiency of the separation membrane is also excellent, so that the refined oil having a ash content low enough to be utilized as recycled fuel oil and lube base oil can be used. You can get it.
본 발명에 의하면, 세라믹 지지체 및 여과용 세라믹막으로 구성된 세라믹 복층막을 금속으로 표면개질시킴으로써, 불순물의 분리 효율을 저하시키지 않으면서 폐윤활유의 투과율을 향상시킨 분리막을 제공할 수 있다. 이에 따라, 품질이 우수한 정제유를 효율적으로 생산할 수 있게 된다.According to the present invention, a surface of a ceramic multilayer film composed of a ceramic support and a filtration ceramic film can be surface-modified with a metal to provide a separation membrane having improved permeability of waste lubricating oil without reducing the separation efficiency of impurities. Accordingly, it is possible to efficiently produce refined oil having excellent quality.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7736493B2 (en) | 2007-08-28 | 2010-06-15 | Exxonmobil Research And Engineering Company | Deasphalter unit throughput increase via resid membrane feed preparation |
| US7815790B2 (en) | 2007-08-28 | 2010-10-19 | Exxonmobil Research And Engineering Company | Upgrade of visbroken residua products by ultrafiltration |
| US7867379B2 (en) | 2007-08-28 | 2011-01-11 | Exxonmobil Research And Engineering Company | Production of an upgraded stream from steam cracker tar by ultrafiltration |
| US7897828B2 (en) | 2007-08-28 | 2011-03-01 | Exxonmobile Research And Engineering Company | Process for separating a heavy oil feedstream into improved products |
| US8177965B2 (en) | 2007-08-28 | 2012-05-15 | Exxonmobil Research And Engineering Company | Enhancement of saturates content in heavy hydrocarbons utilizing ultrafiltration |
| KR101275265B1 (en) * | 2011-05-13 | 2013-06-17 | (주) 세라컴 | Titania asymmetric membrane and method for preparation thereof |
| US8864996B2 (en) | 2007-08-28 | 2014-10-21 | Exxonmobil Research And Engineering Company | Reduction of conradson carbon residue and average boiling points utilizing high pressure ultrafiltration |
| CN114432891A (en) * | 2022-03-03 | 2022-05-06 | 广西大学 | Processing method for camellia oil filtered by ceramic membrane |
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| JPH0745010B2 (en) * | 1990-03-16 | 1995-05-17 | 日本碍子株式会社 | Ceramic membrane filter |
| US5209838A (en) * | 1991-10-07 | 1993-05-11 | Aluminum Company Of America | Purification of an oil-containing liquid using a surface treated permeable inorganic membrane |
| JP3277549B2 (en) * | 1992-04-21 | 2002-04-22 | 株式会社ブリヂストン | Grease filter for kitchen |
| JPH06190253A (en) * | 1992-12-25 | 1994-07-12 | Nikko Kogyo Kk | Film member and its production |
| JP3546567B2 (en) * | 1995-11-21 | 2004-07-28 | 株式会社ブリヂストン | Grease filter and manufacturing method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7736493B2 (en) | 2007-08-28 | 2010-06-15 | Exxonmobil Research And Engineering Company | Deasphalter unit throughput increase via resid membrane feed preparation |
| US7815790B2 (en) | 2007-08-28 | 2010-10-19 | Exxonmobil Research And Engineering Company | Upgrade of visbroken residua products by ultrafiltration |
| US7867379B2 (en) | 2007-08-28 | 2011-01-11 | Exxonmobil Research And Engineering Company | Production of an upgraded stream from steam cracker tar by ultrafiltration |
| US7897828B2 (en) | 2007-08-28 | 2011-03-01 | Exxonmobile Research And Engineering Company | Process for separating a heavy oil feedstream into improved products |
| US8177965B2 (en) | 2007-08-28 | 2012-05-15 | Exxonmobil Research And Engineering Company | Enhancement of saturates content in heavy hydrocarbons utilizing ultrafiltration |
| US8864996B2 (en) | 2007-08-28 | 2014-10-21 | Exxonmobil Research And Engineering Company | Reduction of conradson carbon residue and average boiling points utilizing high pressure ultrafiltration |
| KR101275265B1 (en) * | 2011-05-13 | 2013-06-17 | (주) 세라컴 | Titania asymmetric membrane and method for preparation thereof |
| CN114432891A (en) * | 2022-03-03 | 2022-05-06 | 广西大学 | Processing method for camellia oil filtered by ceramic membrane |
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