CN113117685A - 一种废润滑油脱铁剂及其制备方法 - Google Patents
一种废润滑油脱铁剂及其制备方法 Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 54
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- 238000010409 ironing Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052742 iron Inorganic materials 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005507 spraying Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- 239000002002 slurry Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
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- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- 238000001179 sorption measurement Methods 0.000 description 4
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- 239000002253 acid Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical group [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- 238000005461 lubrication Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
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- 101150019148 Slc7a3 gene Proteins 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
- C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明公开了一种废润滑油脱铁剂及其制备方法，通过制备一种含活性组分Ni的SiO2‑TiO2‑ZnO复合载体，再定向喷涂含Cu‑Eu的甲醇溶液，将活性组分Cu‑Eu负载于复合载体的表面。该脱铁剂以复合氧化物为载体，能较好的分散活性金属，具有有序孔道结构，特定孔径，孔容较大，能有效的脱除废润滑油中的铁元素，延长后续的废润滑油加氢装置的运行周期。
Description
技术领域
本发明涉及一种废润滑油脱铁剂及其制备方法，属于油品精制领域。
背景技术
润滑油使用过程中引入大量的Fe元素，导致废润滑油中Fe含量过高。过渡金属Fe元素具有空的d轨道，容易吸附烯烃形成络合物，在反应过程废润滑油中的烯烃被过渡金属中心吸附，导致催化剂生产大量的焦炭，堵塞加氢催化剂孔道，降低催化剂孔容。环烷酸铁随废润滑油进入加氢精制装置，在氢气和硫化氢的作用下，生成硫化铁，沉积在催化剂的颗粒之间聚集起来，堵塞了精制反应器的顶部床层，使反应物难以通过，造成装置因压降过大而被迫停工撇头，所以对废润滑油进行脱铁预处理，意义重大。
专利CN106398748B公开了一种烃油脱铁剂，含有有机酸、聚醚改性硅油、硫胺酯和/或硫氮酯以及溶剂，在电脱盐条件下，将烃油与烃油脱铁剂接触进行脱铁，所述烃油脱铁剂，对烃油中的铁有良好的脱除效果，能够有效脱除烃油中的油溶性铁和非油溶性铁，不会造成脱后烃油中金属的局部富集，该专利采用的液相溶液进行混合洗脱的方式。专利CN107754755B公开了一种固定床脱除异氰酸酯产品中铁分的吸附剂及其制备方法和粗异氰酸酯产品铁分快速脱除方法，制备了一种采用浸渍法并经过表面改性的方式制备高效铁分吸附剂，装填到设计的一种吸附处理装置中，含有少量的铁分杂质的粗异氰酸酯进入处理装置，进行脱除铁分，该专利中介绍的异氰酸酯组分相对单一稳定，原料含有的铁分的组成相对简单，同时原料中铁含量较低，该专利中未对脱铁吸附剂的铁容进行针对性的说明。专利CN1236667A公开了一种脱除原料气中羰基铁的吸附剂，主要活性组分为铝酸钙水泥，他可以和载体、粘结剂及扩孔剂经捏合、成型、干燥、焙烧而成，载体为硅藻土或拟薄水铝石，活性组分为铝酸钙或者铝酸钙与稀土或硝酸锆硝酸锶。该催化剂在常温下具有良好的吸附铁的性能，对于煤气、合成气等原料气中的羰基铁等毒物有良好的吸附性能，吸附率能达到95%，该专利中报道的吸附剂主要用于气相中，对羰基铁的吸附。目前针对废润滑这种铁含量相对较高的，固定床使用的脱铁剂目前未见报道，本发明的脱铁催化剂具有大量的机械孔道，能有效脱除废润滑油中的Fe元素，保护后续工段的废润滑油加氢催化剂。
发明内容
本发明提供了一种废润滑油脱铁剂及其制备方法，主要适用于铁含量较高的废润滑油固定床加氢装置，该脱铁催化剂具有大量的机械孔道，能够分解有机铁并转化为硫化铁吸附脱除，保护后续的废润滑油加氢催化剂。
本发明的脱铁剂是以硅源、钛源和锌源合成的复合氧化物为载体，以Cu、Ni、Eu为活性组分；脱铁剂活性组分含量以脱铁剂总质量计，其活性组分中CuO含量为3.1-6.4%，NiO含量为1.2-5.6%，Eu2O3含量为0.08-0.2%。
所述的脱铁剂的硅源、钛源和锌源合成的复合氧化物，按重量百分比计TiO2含量为3%~10%，ZnO含量为9.2~18.9%，其余为SiO2。
所述的脱铁剂的比表面积为326~419m2/g，孔容为0.88~1.3ml/g，孔径为18-27nm。
所述的脱铁剂的制备方法如下：将一定量的硅源、钛源、锌源、可溶性的镍盐、表面活性剂和水混合均匀，得到初始溶胶凝胶混合物移入合成釜中密封，在150~220℃晶化8~24小时，将晶体浆液的pH值调节至中性，待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，经100~150℃干燥2~4小时，在喷涂装置中喷入一定量的含Cu-Eu的甲醇溶液对脱铁剂进行修饰，喷涂完毕后，500~700℃焙烧3~6小时，然后通入含一定量水蒸气的空气，在600℃条件下恒温2h，然后停止通入水蒸气，在空气中700℃继续焙烧3h，制得特定孔径，较大孔容，定向负载活性组分Cu-Ni-Eu的废润滑油脱铁剂。
所述的脱铁剂中Cu-Ni-Eu活性组分的前驱物为其氯化物、硫酸盐、硝酸盐或铵盐。
本发明的上述技术方案与现有技术相比具有以下优点，
（1）制备一种适用于铁含量较高的废润滑油的脱铁剂，能应用于废润滑油固定床加氢装置的预处理。
（2）TiO2具有B酸和L酸两种酸位以及Ti4+可还原，TiO2-SiO2复合载体中Ti-O-Si键由于电荷不平衡导致形成Ti-O(H)-Si键，Ti-O(H)-Si键是新的B酸中心，增加了B酸中心，增加了吸附铁的活性位，提高了脱铁剂脱铁的活性。
（3）将环境友好型的镍-氨溶液作为模板剂使用，成功的将活性组分镍嵌入微孔催化剂前驱体中，为后续的Cu-Ni-Eu为活性组分催化剂的合成提供的保证。由于镍嵌入微孔中，在温度升高时能较好的保护镍原子，保证脱铁剂上的镍免于Fe中毒，同时镍将吸附在脱铁剂上的有机铁Fe激活转化。并防止高温下废润滑油在脱铁剂的作用下发生裂解反应，导致润滑油的收率下降。
（4）将干燥后的复合载体在喷涂装置喷涂一定体积的含Cu-Eu活性组分的甲醇溶液修饰，通过喷涂装置对脱铁剂进行定向喷涂，能在载体的表面形成活性组分Cu-Eu的富集与定位，保证活性组分在吸附废润滑油中铁的过程中不被覆盖，引起脱铁剂失活。
具体实施方式
下面结合具体实施案例来详述本发明脱铁剂的特点、制备方法及其脱铁性能，但是本发明不仅限于这些例子，也不构成对发明实施范围的任何限定。
实施例1：
将236.3g硅溶胶（SiO2的含量30%）、13.5g氯化锌、26.4g硫酸钛、13.7g硝酸镍、2.5g四乙基溴化铵和300g水，搅拌6h，混合均匀，得到初始溶胶凝胶混合物，初始溶胶凝胶物料移入合成釜中密封，在220℃晶化8小时，将晶体浆液的pH值调节至中性，待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，经150℃干燥2小时，在喷涂装置中喷入330g质量分数为3.9%的硫酸铜和0.1%三水合硫酸铕的甲醇溶液对脱铁剂进行修饰，喷涂完毕后，500℃焙烧6 h，然后通入水蒸气，水蒸气与空气的体积比为1:10，在600℃条件下再恒温2h，然后停止通入水蒸气，在空气中700℃继续焙烧3h，制得特定孔径，较大孔容，定向负载活性组分Cu-Ni-Eu的废润滑油脱铁剂Cat1。
实施例2：
将236.3g硅溶胶（SiO2的含量30%）、35.8g硫酸锌、8.6g硫酸钛、3.82g六水合二氯化镍、2.5g四乙基溴化铵和300g水，搅拌6h，混合均匀，得到初始溶胶凝胶混合物，初始溶胶凝胶物料移入合成釜中密封，在150℃晶化24小时，将晶体浆液的pH值调节至中性，待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，经100℃干燥4小时，在喷涂装置中喷入130g质量分数为4.8%的硫酸铜和0.1%三水合硫酸铕的甲醇溶液对脱铁剂进行修饰，喷涂完毕后，500℃焙烧6 h，然后通入水蒸气，水蒸气与空气的体积比为1:10，在600℃条件下再恒温2h，然后停止通入水蒸气，在空气中500℃继续焙烧6h，制得特定孔径，较大孔容，定向负载活性组分Cu-Ni-Eu的废润滑油脱铁剂Cat2。
实施例3：
将242.3g硅溶胶（SiO2的含量30%）、28.6g硝酸锌、19.8g硫酸钛、13.1g镍氨络合物（Ni（NH3）6SO4）、2.5g四乙基溴化铵和300g水，搅拌6h，混合均匀，得到初始溶胶凝胶混合物，初始溶胶凝胶物料移入合成釜中密封，在180℃晶化18小时，将晶体浆液的pH值调节至中性，待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，经120℃干燥3小时，在喷涂装置中喷入180g质量分数为5%的硫酸铜和0.1%三水合硫酸铕的甲醇溶液对脱铁剂进行修饰，喷涂完毕后，600℃焙烧6 h，然后通入水蒸气，水蒸气与空气的体积比为1:10，在600℃条件下再恒温2h，然后停止通入水蒸气，在空气中600℃继续焙烧4h，制得特定孔径，较大孔容，定向负载活性组分Cu-Ni-Eu的废润滑油脱铁剂Cat3。
对实施例中脱铁剂与市售脱铁剂的孔性质进行分析，分析结果如表1
表1 不同脱铁剂的物化性质
从表1可以看出本发明提供的脱铁剂Cat1~3通过特定的制备工艺，相比同等组成下的市售脱铁剂Cat4具有更大的孔径和孔容。
将各实施例制备的脱铁剂分别取30ml装入Φ27×3.5的反应管，脱铁剂床层高度48mm，所用原料油为废润滑油性质见下表2。
表2 废润滑油性质：
采用灼烧灰化的前处理方式来消解样品，并通过ICP-AES法测定合成油中的铁含量。取30ml脱铁剂装入固定床反应器，进行器内活化，通入氢气，调整系统压力为0.7MP，氢气量为50ml/min，以10℃/min升温至230℃，恒温2h，然后再以相同升温速率升温到400℃，恒温4h使脱铁剂完全活化。活化结束后，升温至230℃，通入含硫0.5%的直链烷烃对脱铁剂进行灭活，然后降温至140℃，泵入废润滑油，进油空速为1.5h-1，反应温度为150℃，反应压力为7MPa，氢气/油比100:1进行脱铁实验，脱铁后产品采用灼烧灰化的前处理方式来消解样品，并通过ICP-AES法测定合成油中的铁含量，记录反应结果如表3所示：
表3 脱铁活性测定结果总铁，μg/g
从表3的数据可知，Cat1，Cat2，Cat3和市场现有脱铁催化剂，在废润滑油的铁含量约368μg/g原料中进行脱除实验，有机铁脱除达到98.9%以上，而对比市售的脱铁剂Cat4在废润滑油中脱除铁的效果较差。发明人还采用上述方法对其他各实施例所得的脱铁剂进行了240小时长周期实验，均能得到较好的结果，表明本发明脱铁剂具有较好的活性和稳定性。
Claims (5)
1.一种废润滑油脱铁剂及其制备方法，其特征在于：该脱铁剂是以硅源、钛源和锌源合成的复合氧化物为载体，以Cu、Ni、Eu为活性组分；脱铁剂活性组分含量以脱铁剂总质量计，其活性组分中CuO含量为3.1-6.4%，NiO含量为1.2-5.6%，Eu2O3含量为0.08-0.2%。
2.根据权利要求1所述的脱铁剂，其特征在于：所述的硅源、钛源和锌源合成的复合氧化物，按重量百分比计TiO2含量为3%~10%，ZnO含量为9.2~18.9%，其余为SiO2。
3.根据权利要求1所述的脱铁剂，其特征在于：该脱铁剂的比表面积为326~419m2/g，孔容为0.88~1.3ml/g，孔径为18-27nm。
4.根据照权利要求1~3任一项所述的脱铁剂的制备方法，其特征在于：所述的一种废润滑油脱铁剂的制备方法如下：
将一定量的硅源、钛源、锌源、可溶性镍源、表面活性剂和水混合均匀，得到初始溶胶凝胶混合物移入合成釜中密封，在150~220℃晶化8~24小时，将晶体浆液的pH值调节至中性，待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，经100~150℃干燥2~4小时，在喷涂装置中喷入一定量的含Cu-Eu的甲醇溶液对脱铁剂进行修饰，喷涂完毕后，500~700℃焙烧3~6小时，然后通入含一定量水蒸气的空气，在600℃条件下恒温2h，然后停止通入水蒸气，在空气中700℃继续焙烧3h，制得特定孔径，较大孔容，定向负载活性组分Cu-Ni-Eu的废润滑油脱铁剂。
5.根据权利要求4所述的脱铁剂的制备方法，其特征在于： Cu-Ni-Eu活性组分的前驱物为其氯化物、硝酸盐、硫酸盐或铵盐。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1998011183A1 (en) * | 1996-09-12 | 1998-03-19 | Kvaerner Technology And Research Limited | Process for removing fine iron containing particles from liquids containing the same |
| CN107794086A (zh) * | 2016-09-07 | 2018-03-13 | 中国石油化工股份有限公司 | 一种烃类加氢脱铁系统及其方法 |
| CN109868180A (zh) * | 2019-04-23 | 2019-06-11 | 湖北润驰环保科技有限公司 | 一种环保的废润滑油连续再生的预处理工艺 |
| CN111151263A (zh) * | 2020-01-15 | 2020-05-15 | 浙江三龙催化剂有限公司 | 一种脱除烟气中二噁英的催化剂及其制备方法和应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1998011183A1 (en) * | 1996-09-12 | 1998-03-19 | Kvaerner Technology And Research Limited | Process for removing fine iron containing particles from liquids containing the same |
| CN107794086A (zh) * | 2016-09-07 | 2018-03-13 | 中国石油化工股份有限公司 | 一种烃类加氢脱铁系统及其方法 |
| CN109868180A (zh) * | 2019-04-23 | 2019-06-11 | 湖北润驰环保科技有限公司 | 一种环保的废润滑油连续再生的预处理工艺 |
| CN111151263A (zh) * | 2020-01-15 | 2020-05-15 | 浙江三龙催化剂有限公司 | 一种脱除烟气中二噁英的催化剂及其制备方法和应用 |
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