CN110813333A - 一种燃料油加氢精制催化剂的制法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000295 fuel oil Substances 0.000 title claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 125000001741 organic sulfur group Chemical group 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 27
- 239000002245 particle Substances 0.000 description 7
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- -1 Transition metal sulfide Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HDUHSISAGHHYRW-UHFFFAOYSA-N [N].N1=CC=CC2=CC=CC=C21 Chemical compound [N].N1=CC=CC2=CC=CC=C21 HDUHSISAGHHYRW-UHFFFAOYSA-N 0.000 description 1
- AOLMGDPIQZITEU-UHFFFAOYSA-N [P]=S.[Ni] Chemical compound [P]=S.[Ni] AOLMGDPIQZITEU-UHFFFAOYSA-N 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明公开了一种含高分散Ni‑P‑S活性物种的燃料油加氢精制催化剂的制备方法，属多相催化技术领域。制备的加氢精制催化剂以Ni2P为主要物相，含有一定量的硫。磷与镍的摩尔比为0.3～2，硫含量为0.5～5wt％。由于采用了高分散的Ni2P为前体，所获得的含Ni‑P‑S活性物种的加氢精制催化剂具有很高的活性。
Description
技术领域
本发明涉及一种加氢精制催化剂的制法，属多相催化技术领域。
技术背景
燃料油的加氢精制过程传统上以过渡金属硫化物作为催化剂，但随着环保要求的日趋严苛，这类传统催化剂越来越难以满足法规要求，必须开发新型的高效加氢精制催化剂。近二十年来，过渡金属碳化物、氮化物和磷化物等非硫化物催化剂成为研究人员关注的重点，尤其是磷化镍(Ni2P)催化剂具有比传统金属硫化物更高的加氢脱硫(HDS)活性和稳定性，被视为有望取代传统硫化物催化剂的新一代加氢精制催化剂。
研究发现，磷化镍在加氢脱硫反应中会与生成的H2S作用，在催化剂表面形成Ni-P-S物种，该物种很可能是HDS反应的活性相(Oyama等，J.Catal.，2004年第221卷，263-273页)。因此，一些研究人员试图在制备Ni2P催化剂时就在表面引入Ni-P-S活性物种，以提高催化剂的HDS活性。例如，CN1850335A公开了一种金属硫磷化物加氢精制催化剂，所述催化剂以担载金属氧化物和磷酸盐先制备出磷化物前体，再将前体在H2S/H2气氛中预硫化，然后在H2气氛中还原得到金属硫磷化物催化剂。CN102994142A公开了一种裂解汽油加氢精制的方法，所用催化剂的活性组分是金属Co、Mo、Ni和W中的一种或多种金属硫化物和Ni2P的复合催化剂。该催化剂的制备过程实质上仍是先合成含有Ni2P物相的催化剂前体，再用H2S预硫化而得。CN104174418A公开了一种基于硫化镍合成磷化镍催化剂的方法，以硫化镍和次磷酸钠的机械混合物为前体，利用镍离子和磷化氢反应形成磷化镍，同时生成的硫化氢可在磷化镍表面构建Ni-P-S活性物种。CN104941673A也公开了一种含硫的磷化镍催化剂，所述催化剂通过磷化镍的硫化处理或对磷硫化物的低温还原反应制得，并优选后者。但从已公开的报导看，制备上述含硫的磷化镍催化剂时，Ni2P催化剂均采用程序升温还原法(TPR)制得，涉及高温反应，最终得到的催化剂分散度较低，单位表面积的活性中心数目较低，因而加氢精制活性不够理想。先制得镍的磷硫化物再用氢气进行还原也是如此。究其原因，是因为无论何种方法得到的Ni-P-S活性物种的分散度，都决定于其前驱体Ni2P或NiS的分散度。上述文献中使用的制备方法获得的Ni2P或NiS的粒径，由于其制备方法本身的限制，都比较大，因而Ni-P-S活性物种的分散度较低，导致其加氢精制活性不高。
基于上述分析可知，如果要制备高分散度的Ni-P-S活性物种，必须先制备高分散的Ni2P或NiS前体。本发明提供一种制备高分散Ni-P-S复合加氢精制催化剂的方法：通过制备高分散的担载型镍催化剂为前驱体，将其转化为高分散的Ni2P或NiS前体，再进一步转化为Ni-P-S复合催化剂。所述方法获得的Ni-P-S活性物种分散度高，粒径小(6～12nm)，HDS活性和稳定性很高。
发明内容
本发明的技术方案如下：
一种用于燃料油加氢精制反应的含高分散Ni-P-S活性物种的磷化镍催化剂的制法，其特征是：以高分散的磷化镍催化剂为前体，将其硫化，硫化后的磷化镍催化剂中硫含量为0.5～5wt％。
所述的高分散的磷化镍催化剂中磷与镍的摩尔比为0.3～2。
所述的高分散的磷化镍催化剂是通过将高分散的镍催化剂前体磷化的方法制得，高分散的镍催化剂优选采用共沉淀法制备。
所述高分散的磷化镍催化剂的硫化方法是通过在一定温度下的流动气氛中，将含一定量有机硫的有机溶液通过磷化镍催化剂床层来实现。其过程可采用本技术领域已公开的方法，如CN104772154A所描述的方法来进行。
采用本发明的技术方案，工艺简单，操作简便，所得的含高分散Ni-P-S活性物种的磷化镍催化剂中Ni-P-S活性物种分散度高，具有更高的二苯并噻吩的加氢脱硫反应活性。
具体实施方式
用以下的实施例对本发明作进一步说明：
实施例1
称取39.6g Ni(NO3)2·6H2O和14.7g Al(NO3)3·9H2O溶于水，制成100ml溶液；另取15.2g Na2CO3溶于水，制成100ml溶液。在搅拌下将上述两份溶液同时滴加到400ml蒸馏水中，生成绿色沉淀，将该沉淀用蒸馏水洗涤后，加入200ml正丁醇，水浴蒸干，然后在393K烘箱中烘干。将所得催化剂在马沸炉中623K条件下焙烧3h即得担载的高分散镍催化剂前体，粒径3～4nm。
实施例2
称取实施例1的高分散镍催化剂前体3g装填到反应器中，通入含2wt％的PPh3正庚烷溶液593K条件下磷化36h，正庚烷溶液流量为8ml/h，所得催化剂记为A，其XRD物相组成和粒径见表1。
实施例3
称取3g实施例2所得的催化剂A装填到反应器中，通入含2wt％的CS2正庚烷溶液在583K条件下硫化4h，正庚烷溶液流量为8ml/h，所得催化剂记为B，其XRD物相组成和粒径见表1。
实施例4
称取实施例1的高分散镍催化剂前体3g装填到反应器中，通入含2wt％的PPh3正庚烷溶液在593K条件下磷化36h，正庚烷溶液流量为8ml/h，然后再通入含2wt％的CS2正庚烷溶液在583K条件下硫化4h，正庚烷溶液流量为8ml/h，所得催化剂记为C，其XRD物相组成和粒径见表1。
实施例5
称取实施例1的高分散镍催化剂前体3g装填到反应器中，通入含2wt％PPh3和2wt％CS2的正庚烷溶液，在593K条件下处理36h，正庚烷溶液流量为8ml/h，所得催化剂记为D，其XRD物相组成和粒径见表1。
实施例6～9
将实施例2～5所得催化剂A、B、C和D用于模型柴油的加氢精制反应。模型柴油为含3000ppmw二苯并噻吩硫、200ppmw喹啉氮、5wt％四氢萘和0.5wt％正辛烷(内标)的正十四烷溶液。反应压力3.1MPa，液体空速2h-1，氢油比1500(V/V)。反应24h后取样分析反应产物中的硫含量和烃组成。评价结果见表2～表4。
表1.催化剂的XRD物相组成和粒径
表2.二苯并噻吩的加氢脱硫活性和选择性(573K)
表3.喹啉的加氢脱氮活性和选择性(573K)
表4.四氢萘的转化率和选择性(573K)
注：表中十氢萘包括反式和顺式两种同分异构体。
Claims (4)
1.一种用于燃料油加氢精制反应的含高分散Ni-P-S活性物种的磷化镍催化剂的制法，其特征是：以高分散的磷化镍催化剂为前体，将其硫化，硫化后的磷化镍催化剂中硫含量为0.5～5wt％。
2.根据权利要求1，所述的高分散的磷化镍催化剂中磷与镍的摩尔比为0.3～2。
3.根据权利要求1，所述的高分散的磷化镍催化剂是通过将高分散的镍催化剂前体磷化的方法制得。
4.根据权利要求1，所述高分散的磷化镍催化剂的硫化是通过在流动气氛中，将含计量有机硫的有机溶液通过磷化镍催化剂床层来实现。
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| WO2008107445A1 (en) * | 2007-03-05 | 2008-09-12 | Institut Català D'investigació Química (Iciq) | Gold-based catalysts for selective hydrogenation of unsaturated compounds |
| CN103769103A (zh) * | 2012-10-17 | 2014-05-07 | 南京大学连云港高新技术研究院 | 一种蒽醌加氢制双氧水的担载型镍催化剂及制备方法 |
| CN103801317A (zh) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | 一种加氢脱硫催化剂及其制备方法 |
| CN105312071A (zh) * | 2014-07-28 | 2016-02-10 | 南京大学 | 一种复合氧化物担载的Ni2P催化剂的制备方法 |
| CN104941673A (zh) * | 2015-05-13 | 2015-09-30 | 大连理工大学 | 含硫的磷化镍催化剂及其应用 |
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