CN106902825A - 一种包覆Ni‑Al2 O3@SiO2 催化剂及制备方法和应用 - Google Patents
一种包覆Ni‑Al2 O3@SiO2 催化剂及制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005253 cladding Methods 0.000 title claims abstract description 7
- 229910018404 Al2 O3 Inorganic materials 0.000 title 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 64
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 51
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 51
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 51
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 17
- 150000002815 nickel Chemical class 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- NMTBZBPWKJALHU-UHFFFAOYSA-N O=C.C#C Chemical compound O=C.C#C NMTBZBPWKJALHU-UHFFFAOYSA-N 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 19
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 10
- 150000001241 acetals Chemical class 0.000 description 9
- NMPJHMFXHISVBR-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butan-1-ol Chemical compound OCCCCOC1CCCO1 NMPJHMFXHISVBR-UHFFFAOYSA-N 0.000 description 7
- 229910003849 O-Si Inorganic materials 0.000 description 7
- 229910003872 O—Si Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical class OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 150000002373 hemiacetals Chemical class 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- -1 1,4- butynediols 1,4- butylene glycols Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical compound CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 description 1
- INDXRDWMTVLQID-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO.OCCCCO INDXRDWMTVLQID-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VXPFEVUAMVPPQU-UHFFFAOYSA-N dioxosilane nickel Chemical compound [Ni].O=[Si]=O VXPFEVUAMVPPQU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
一种包覆Ni‑Al2O3@SiO2催化剂，其特征在于催化剂各组分的质量比为Al2O3:SiO2:Ni＝100:0.1～3:4～26，比表面积98m2/g～245m2/g，孔容0.25cm3/g～1.1cm3/g；Ni颗粒以无定形或高分散状态存在于载体Al2O3表面，晶粒尺寸小于8nm；SiO2层填充于Ni颗粒之间。本发明具有制备简单，选择性好的优点。
Description
技术领域
本发明涉及一种包覆Ni-Al2O3@SiO2催化剂及制备方法和应用。
背景技术
Reppe法1,4-丁炔二醇加氢制备1,4-丁二醇，从表面看是一个C≡C以及C＝C键加氢制备饱和二元醇的过程：
HO-CH2-C≡C-CH2-OH+H2→HO-CH2-CH＝CH-CH2-OH+154.8KJ/mol (1)
1,4-丁炔二醇 1,4-丁烯二醇
HO-CH2-CH＝CH-CH2-OH+H2→HO-CH2-CH2-CH2-CH2-OH+96.3KJ/mol (2)
1,4-丁烯二醇 1,4-丁二醇
而在实际反应过程中却是一个同时含有多种组分，伴随着众多副反应的复杂体系。该体系中，半加氢产物1,4-丁烯二醇可异构化为4-羟基丁醛：
4-羟基丁醛不稳定，可发生自缩合生成相应的半缩醛：
半缩醛与1,4-丁二醇反应生成缩醛2-(4′-羟基丁氧基)-四氢呋喃：
上述反应中1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛可以通过简单的催化加氢方法转化为1,4-丁二醇。而环状缩醛2-(4′-羟基丁氧基)-四氢呋喃无法通过直接加氢的方法脱除，而且与1,4－丁二醇形成共沸物，用常规的蒸馏法难以分离。缩醛2-(4′-羟基丁氧基)-四氢呋喃的残留严重影响1,4-丁二醇产品的纯度与色度，直接影响1,4-丁二醇品质及其在下游领域中的应用。
鉴于此，US6137016描述了一种纯化含有少量环状缩醛2-(4′-羟基丁氧基)-四氢呋喃的1,4-丁二醇的方法，该方法在1,4-丁二醇成品中配入少量的水，然后在加氢催化剂存在下进行加氢反应，经再一次的精馏后得到低的2-(4′-羟基丁氧基)-四氢呋喃含量的1,4-丁二醇产品。该方法需要对1,4-丁二醇成品进行进一步的加氢转化与产品分离，增加了额外设备的投入与能源的消耗，而且其使用的加氢催化剂为通用型加氢催化剂，其加氢效果并不理想。CN 102145286B公开了一种Ni-SiO2/Al2O3催化剂及制备方法，该催化剂在制备过程中首先在氧化铝载体表面引入了硅助剂等进行改性，后引入活性组分镍，由于SiO2与活性组分镍弱的相互作用，需采用浸渍沉积的方法引入镍，操作较为繁锁。
发明内容
本发明的目的是提供一种制备简单，选择性好的包覆Ni-Al2O3@SiO2催化剂及制备方法和应用。
本发明的催化剂各组分的质量比为Al2O3:SiO2:Ni＝100:0.1～3:4～26，比表面积98m2/g～245m2/g，孔容0.25cm3/g～1.1cm3/g；Ni颗粒以无定形或高分散状态存在于载体Al2O3表面，晶粒尺寸小于8nm；SiO2层填充于Ni颗粒之间。
如上所述Al2O3的比表面积为110m2/g～260m2/g，孔容为0.5cm3/g～1.3cm3/g。
本发明提供的Ni-Al2O3@SiO2催化剂的制备方法，其特征在于包括以下步骤：
(1)将Al2O3载体经100℃～150℃抽真空处理10min～30min，或直接在100℃～150℃加热1h～10h，后降至室温；
(2)配制镍含量0.05g/mL～0.2g/mL的镍盐水溶液；
(3)按每100g Al2O3载体取80mL～130mL镍盐水溶液的比例，将步骤(2)配制的镍盐水溶液浸渍到步骤(1)所述的载体上，静置20min～120min；然后升温至100℃～150℃烘干2h～24h，优选3h～12h；在空气或氮气气氛下，2℃/min～10℃/min升温至350℃～500℃，焙烧1h～24h；得到NiO/Al2O3前体；
(4)配制硅前驱物的乙醇-水溶液，以SiO2计，其浓度为0.0001g/mL～0.0015g/mL，以氨水调节其pH值在8.0～8.5之间；
(5)按NiO/Al2O3前体中每100g Al2O3取1000mL～2000mL硅前驱物的乙醇-水溶液的量，将步骤(3)得到的NiO/Al2O3前体悬浮于步骤(4)配制的溶液中，20℃～60℃恒温搅拌回流1h～24h，过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次～5次，样品于80℃～150℃烘干2h～24h，优选3h～12h；
(6)将步骤(5)所得的样品在空气或氮气气氛下焙烧：以2℃/min～10℃/min升温至400℃～550℃，恒温1h～24h；之后在350℃～650℃，氢气空速500/h～2000/h条件下还原1h～24h；得到催化剂。
步骤(2)所述的镍盐为硝酸镍、硫酸镍或氯化镍中的一种。
步骤(4)所述的硅前驱物为正硅酸乙酯、正硅酸甲酯中的一种，优选正硅酸乙酯；所述的乙醇-水溶液中乙醇：水的摩尔比为4～100:1。
本发明催化剂的应用包括如下步骤：
本发明制备的催化剂用于炔醛法合成1,4-丁二醇加氢过程，(1)适用于固定床反应器，原料为1,4-丁炔二醇水溶液经低温、低压预加氢后含25wt％～30wt％的1,4-丁二醇的水溶液(该溶液羰基值在7mg(KOH)/g～20mg(KOH)/g，含1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等杂质)，进料方式：上进下出；反应条件：反应温度105℃～150℃，氢气压力10MPa～22MPa，液体空速1.0/h～1.7/h。(2)在固定床反应器上,也可适用于原料为含25wt％～35的1,4-丁炔二醇的水溶液的直接加氢转化，采用外循环加氢反应工艺，进料方式：上进下出；反应条件：反应温度105℃～150℃，氢气压力10MPa～22MPa，液体空速1.0/h～1.7/h，循环比18～22:1。两种工艺加氢后的物料有机相中1,4-丁二醇含量≥96wt％，副产物丁醇含量≤1.2wt％，不饱和生色物质1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等总含量≤0.06wt％，其余为大分子聚合物，该物料羰基数：0.03mg(KOH)/g～0.05mg(KOH)/g。经精馏可得到产品纯度：99.6wt％～99.8wt％；羰基数：0.03mg(KOH)/g～0.05mg(KOH)/g；色度：≤5APHA。加氢催化剂的使用寿命可达到17个月。
本发明与现有技术相比，本发明具有的优点：
1、以浸渍法在氧化铝载体上引入活性组分Ni，Ni分布于氧化铝表面的四面体、八面体空穴，并以此为核生长成为微晶颗粒，该颗粒具有高的分散度。
2、在Ni/Al2O3催化剂表面，以嫁接方式引入SiO2层，由于SiO2与NiO间不发生反应，且相互作用极弱，SiO2仅与NiO颗粒间隙暴露的氧化铝反应生成相应的Al-O-Si键，随嫁接时间的延长，当暴露的氧化铝表面全部被单层SiO2覆盖后，将在暴露的单层SiO2表面进一步生长二、三、四……层的SiO2。
3、嫁接反应完成后的样品，先后经过无水乙醇、0.01M的稀硝酸、去离子水洗涤，有效去除了嫁接过程中残留于催化剂表面的弱吸附组分，特别是在NiO表面弱吸附的SiO2物种，保证了活性组分Ni物种的有效暴露。
4、传统催化剂制备过程中，由于NiO与Al2O3间强的相互作用，往往需要在较高的温度下才能将NiO还原为活性金属Ni，而高的还原温度又促使了金属Ni的迁移聚集，降低表面活性位点的数目，加氢活性也相应降低。本发明中，SiO2层存在于NiO颗粒的间隙，通过限域效应可以有效阻止高温还原过程中金属Ni的迁移聚集，使活性金属镍保持高的分散度，从而使催化剂表现出高的加氢活性。
5、SiO2层与载体氧化铝间形成的Al-O-Si结构，使其具有了特定的表面酸性质，可以促使环状缩醛2-(4′-羟基丁氧基)-四氢呋喃水解为4-羟基丁醛，后在相邻高活性暴露加氢中心Ni的催化作用下加氢转化为1,4-丁二醇。该催化剂中酸性中心与加氢活性中心的协同作用，实现了环状缩醛2-(4′-羟基丁氧基)-四氢呋喃的高效转化，最终达到降低环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量，提高1,4-丁二醇的产品品质，降低产品色度的目的。
6、SiO2层包覆于氧化铝表面，阻止了水对氧化铝载体的进攻，抑制了载体氧化铝的水合脱结构，有效提高了催化剂在含水体系中的水热稳定性，延长了催化剂使用寿命。
具体实施方式
实施例1
(1)取比表面积为110m2/g，孔容为0.5cm3/g的Al2O3载体经100℃抽真空处理10min，后降至室温备用；配制镍含量0.05g/mL的硝酸镍水溶液；取80mL上述配制的镍盐水溶液，浸渍到100g前述的Al2O3载体上，静置20min，升温至100℃烘干2h；在空气气氛下焙烧以2℃/min升温至350℃，恒温1h；得到Al2O3:Ni质量比为100:4的NiO/Al2O3前体。
称取正硅酸乙酯配制以SiO2计算其浓度为0.0001g/mL的硅前驱物的乙醇-水溶液，乙醇-水溶液中乙醇/水的摩尔比为4:1，以氨水调节其pH值在8.0；取上述制备的NiO/Al2O3前体悬浮于1000mL硅前驱物的乙醇-水溶液中，20℃恒温搅拌回流1h，过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次，样品于80℃烘干2h；所得的样品置于焙烧炉中，在空气气氛下焙烧：以2℃/min升温至400℃，恒温1h；后经氢气空速500/h于350℃还原1h；得到质量组成为Al2O3:SiO2:Ni＝100:0.1:4的Ni-Al2O3@SiO2催化剂，该催化剂比表面积105m2/g，孔容0.45cm3/g，Ni颗粒以无定形，SiO2层填充于Ni颗粒之间，且与Al2O3间形成Al-O-Si键。该催化剂编号为1#。
实施例2
(1)取比表面积为110m2/g，孔容为0.5cm3/g的Al2O3载体经150℃抽真空处理30min，后降至室温备用；配制镍含量0.2g/mL的硫酸镍的镍盐水溶液；取130mL上述配制的镍盐水溶液，浸渍到100g前述的Al2O3载体上，静置120min，升温至150℃烘干24h；在氮气气氛下焙烧以10℃/min升温至500℃，恒温24h；得到Al2O3:Ni质量比为100:26的NiO/Al2O3前体。
称取正硅酸甲酯,配制以SiO2计算其浓度为0.0015g/mL的硅前驱物的乙醇-水溶液，乙醇-水溶液中乙醇/水的摩尔比为100:1，以氨水调节其pH值在8.5；取上述制备的Al2O3:Ni质量比为100:26的NiO/Al2O3前体悬浮于2000mL硅前驱物的乙醇-水溶液中，60℃恒温搅拌回流24h，过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤5次，样品于150℃烘干24h；所得的样品置于焙烧炉中，在氮气气氛下焙烧：以10℃/min升温至550℃，恒温24h；后经氢气空速2000/h于650℃还原24h；得到质量组成为Al2O3:SiO2:Ni＝100:3:26的Ni-Al2O3@SiO2催化剂，该催化剂比表面积98m2/g，孔容0.25cm3/g，Ni颗粒以高分散状态存在于载体Al2O3表面，晶粒尺寸8nm，SiO2层填充于Ni颗粒之间，且与Al2O3间形成Al-O-Si键。该催化剂编号为2#。
实施例3
(1)取比表面积为260m2/g，孔容为1.3cm3/g的Al2O3载体100℃鼓风烘箱中加热1h，后降至室温备用；配制镍含量0.05g/mL的氯化镍的镍盐水溶液；取80mL上述配制的镍盐水溶液，浸渍到100g前述的Al2O3载体上，静置80min，升温至120℃烘干3h；在空气气氛下焙烧以8℃/min升温至350℃，恒温18h；得到Al2O3:Ni质量比为100:4的NiO/Al2O3前体。
称取正硅酸甲酯配制以SiO2计算其浓度为0.0001g/mL的硅前驱物的乙醇-水溶液，乙醇-水溶液中乙醇/水的摩尔比为10:1，以氨水调节其pH值在8.2；取上述制备的Al2O3:Ni质量比为100:4的NiO/Al2O3前体悬浮于1000mL硅前驱物的乙醇-水溶液中，40℃恒温搅拌回流12h，过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤4次，样品于150℃烘干3h；所得的样品置于焙烧炉中，在氮气气氛下焙烧：以8℃/min升温至500℃，恒温12h；后经氢气空速1000/h于550℃还原10h；得到质量组成为Al2O3:SiO2:Ni＝100:0.1:4的Ni-Al2O3@SiO2催化剂，该催化剂比表面积245m2/g，孔容1.10cm3/g，Ni颗粒以无定形状态存在于载体Al2O3表面，SiO2层填充于Ni颗粒之间，且与Al2O3间形成Al-O-Si键。该催化剂编号为3#。
实施例4
取比表面积为160m2/g，孔容为0.75cm3/g的Al2O3载体经150℃鼓风烘箱中加热10h，后降至室温备用；配制镍含量0.10g/mL的硝酸镍的镍盐水溶液；取95mL上述配制的镍盐水溶液，浸渍到100g前述的Al2O3载体上，静置80min，升温至120℃烘干12h；在空气气氛下焙烧以2℃/min升温至350℃，恒温5h；得到Al2O3:Ni质量比为100:9.5的NiO/Al2O3前体。
称取正硅酸乙酯配制以SiO2计算其浓度为0.0008g/mL的硅前驱物的乙醇-水溶液，乙醇-水溶液中乙醇/水的摩尔比为20:1，以氨水调节其pH值在8.4；取上述制备的Al2O3:Ni质量比为100:9.5的NiO/Al2O3前体悬浮于1300mL硅前驱物的乙醇-水溶液中，20℃恒温搅拌回流24h，过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤5次，样品于100℃烘干12h；所得的样品置于焙烧炉中，在氮气气氛下焙烧：以10℃/min升温至400℃，恒温1h；后经氢气空速1500/h于450℃还原24h；得到质量组成为Al2O3:SiO2:Ni＝100:1.04:9.5的Ni-Al2O3@SiO2催化剂，该催化剂比表面积145m2/g，孔容0.61cm3/g，Ni颗粒以高分散状态存在于载体Al2O3表面，晶粒尺寸6.3nm；SiO2层填充于Ni颗粒之间，且与Al2O3间形成Al-O-Si键。该催化剂编号为4#。
实施例5
取比表面积为210m2/g，孔容为1.0cm3/g的Al2O3载体直接在130℃鼓风烘箱中加热5h，后降至室温备用；配制镍含量0.15g/mL的硝酸镍的水溶液；取110mL上述配制的镍盐水溶液，浸渍到100g前述的Al2O3载体上，静置20min，升温至100℃烘干3h；在空气气氛下焙烧以10℃/min升温至350℃，恒温1h；得到Al2O3:Ni质量比为100:16.5的NiO/Al2O3前体。
称取正硅酸甲酯配制以SiO2计算其浓度为0.0012g/mL的硅前驱物的乙醇-水溶液，乙醇-水溶液中乙醇/水的摩尔比为4:1，以氨水调节其pH值在8.0；取上述制备的Al2O3:Ni质量比为100:16.5的NiO/Al2O3前体悬浮于1700mL硅前驱物的乙醇-水溶液中，20℃恒温搅拌回流24h，过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次，样品于80℃烘干3h；所得的样品置于焙烧炉中，在空气气氛下焙烧：以2℃/min升温至400℃，恒温1h；后经氢气空速750/h于350℃还原1h；得到质量组成为Al2O3:SiO2:Ni＝100:2.04:16.5的Ni-Al2O3@SiO2催化剂，该催化剂比表面积183m2/g，孔容0.85cm3/g，Ni颗粒以高分散状态存在于载体Al2O3表面，晶粒尺寸7.5nm；SiO2层填充于Ni颗粒之间，且与Al2O3间形成Al-O-Si键。该催化剂编号为5#。
实施例6
取上述1#～5#号催化剂及现有的商品催化剂(生产厂家：Degussa OctolystTM1003)(标记为6#)，(1)在固定床反应器上，以1,4-丁炔二醇水溶液经低温、低压预加氢后含25wt％～30wt％的1,4-丁二醇水溶液(该溶液羰基值在7mg(KOH)/g～20mg(KOH)/g，含1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等杂质)为原料，进料方式：上进下出；反应条件：反应温度105℃～150℃，氢气压力10MPa～22MPa，液体空速1.0/h～1.7/h。具体的反应条件及结果见表1。
(2)在固定床反应器上，以含25wt％～35wt％的1,4-丁炔二醇水溶液为原料，采用外循环加氢反应工艺，进料方式：上进下出；反应条件：反应温度105℃～150℃，氢气压力10MPa～22MPa，液体空速1.0/h～1.7/h，循环比18～22:1。具体的反应条件及结果见表2。
两种工艺加氢后的物料有机相中1,4-丁二醇含量≥96wt％，副产物丁醇含量≤1.2wt％，不饱和生色物质1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等总含量≤0.06wt％，其余为大分子聚合物，该物料羰基数：0.03mg(KOH)/g～0.05mg(KOH)/g。经精馏可得到产品纯度：99.6wt％～99.8wt％；羰基数：0.03mg(KOH)/g～0.05mg(KOH)/g；色度：≤5APHA。加氢催化剂的使用寿命可达到15-18个月。
表1
表2
Claims (13)
1.一种包覆Ni-Al2O3@SiO2催化剂，其特征在于催化剂各组分的质量比为Al2O3:SiO2:Ni＝100:0.1～3:4～26，比表面积98m2/g～245m2/g，孔容0.25cm3/g～1.1cm3/g；Ni颗粒以无定形或高分散状态存在于载体Al2O3表面，晶粒尺寸小于8nm；SiO2层填充于Ni颗粒之间。
2.如权利要求1所述的一种包覆Ni-Al2O3@SiO2催化剂，其特征在于所述Al2O3的比表面积为110m2/g～260m2/g，孔容为0.5cm3/g～1.3cm3/g。
3.如权利要求1或2所述的一种包覆Ni-Al2O3@SiO2催化剂的制备方法，其特征在于包括以下步骤：
(1)将Al2O3载体经100℃～150℃抽真空处理10min～30min，或直接在100℃～150℃加热1h～10h，后降至室温；
(2)配制镍含量0.05g/mL～0.2g/mL的镍盐水溶液；
(3)按每100g Al2O3载体取80mL～130mL镍盐水溶液的比例，将步骤(2)配制的镍盐水溶液浸渍到步骤(1)所述的载体上，静置20min～120min；然后升温至100℃～150℃烘干2h～24h，在空气或氮气气氛下，2℃/min～10℃/min升温至350℃～500℃，焙烧1h～24h；得到NiO/Al2O3前体；
(4)配制硅前驱物的乙醇-水溶液，以SiO2计，其浓度为0.0001g/mL～0.0015g/mL，以氨水调节其pH值在8.0～8.5之间；
(5)按前体中每100g Al2O3取1000mL～2000mL硅前驱物的乙醇-水溶液的量，将步骤(3)得到的NiO/Al2O3前体悬浮于步骤(4)配制的溶液中，20℃～60℃恒温搅拌回流1h～24h，过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次～5次，样品于80℃～150℃烘干2h～24h；
(6)将步骤(5)所得的样品在空气或氮气气氛下焙烧：以2℃/min～10℃/min升温至400℃～550℃，恒温1h～24h；之后在350℃～650℃，氢气空速500/h～2000/h条件下还原1h～24h；得到催化剂。
4.如权利要求3所述的一种包覆Ni-Al2O3@SiO2催化剂的制备方法，其特征在于步骤(2)所述的镍盐为硝酸镍、硫酸镍或氯化镍中的一种。
5.如权利要求3所述的一种包覆Ni-Al2O3@SiO2催化剂的制备方法，其特征在于步骤(3)所述的烘干时间为3h～12h。
6.如权利要求3所述的一种包覆Ni-Al2O3@SiO2催化剂的制备方法，其特征在于步骤(4)所述的硅前驱物为正硅酸乙酯、正硅酸甲酯中的一种。
7.如权利要求3所述的一种包覆Ni-Al2O3@SiO2催化剂的制备方法，其特征在于步骤(4)所述的硅前驱物为正硅酸乙酯。
8.如权利要求3所述的一种包覆Ni-Al2O3@SiO2催化剂的制备方法，其特征在于步骤(4)所述的乙醇-水溶液中乙醇：水的摩尔比为4～100:1。
9.如权利要求3所述的一种包覆Ni-Al2O3@SiO2催化剂的制备方法，其特征在于步骤(5)烘干时间为3h～12h。
10.如权利要求1或2所述的一种包覆Ni-Al2O3@SiO2催化剂的应用，其特征在于包括如下步骤：
催化剂用于炔醛法合成1,4-丁二醇加氢，适用于固定床反应器，原料为1,4-丁炔二醇水溶液经低温、低压预加氢后含25wt％～30wt％的含1,4-丁炔二醇，进料方式：上进下出；反应条件：反应温度105℃～150℃，氢气压力10MPa～22MPa，液体空速1.0/h～1.7/h。
11.如权利要求10所述的一种包覆Ni-Al2O3@SiO2催化剂的应用，其特征在于1,4-丁二醇的水溶液的羰基值在7mg(KOH)/g～20(KOH)/g。
12.如权利要求1或2所述的一种包覆Ni-Al2O3@SiO2催化剂的应用，其特征在于包括如下步骤：
催化剂用于炔醛法合成1,4-丁二醇加氢，适用于固定床反应器，原料为含25wt％～35wt％的1,4-丁炔二醇的水溶液的直接加氢转化，采用外循环加氢反应工艺，进料方式：上进下出；反应条件：反应温度105℃～150℃，氢气压力10MPa～22MPa，液体空速1.0/h～1.7/h，循环比18～22:1。
13.如权利要求10、11或12加氢后的物料有机相产品，其特征在于加氢后的物料有机相产品中1,4-丁二醇含量≥96wt％，副产物丁醇含量≤1.2wt％，不饱和生色物质总含量≤0.06wt％，其余为大分子聚合物，该物料羰基数：0.03mg(KOH)/g～0.05mg(KOH)/g。
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| PCT/CN2018/074142 WO2018157684A1 (zh) | 2017-02-28 | 2018-01-25 | 一种包覆Ni-Al2O3@SiO2催化剂及制备方法和应用 |
| EP18761419.3A EP3590595A4 (en) | 2017-02-28 | 2018-01-25 | NI COATED AL2O3 @ SIO2 CATALYST, ASSOCIATED PREPARATION AND APPLICATION PROCESS |
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| CN107715893A (zh) * | 2017-10-27 | 2018-02-23 | 西南化工研究设计院有限公司 | 一种1,4‑丁炔二醇选择性加氢的贝壳基催化剂及其制备方法 |
| WO2018157684A1 (zh) * | 2017-02-28 | 2018-09-07 | 山西大学 | 一种包覆Ni-Al2O3@SiO2催化剂及制备方法和应用 |
| WO2018157685A1 (zh) * | 2017-02-28 | 2018-09-07 | 山西大学 | 一种包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂及制备方法和应用 |
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| CN111097411B (zh) * | 2018-10-25 | 2024-01-23 | 中国石油化工股份有限公司 | 基于改性钯系负载型催化剂的1,5-戊二醇液相加氢合成方法 |
| CN114409504B (zh) * | 2022-01-15 | 2023-12-26 | 山西大学 | 1,4-丁炔二醇加氢制1,4-丁二醇的方法 |
| CN114534730B (zh) * | 2022-01-19 | 2023-03-28 | 南京航空航天大学 | 一种光热驱动镍基催化剂及其制备方法与应用 |
| CN114682266B (zh) * | 2022-04-14 | 2023-05-23 | 厦门大学 | 一种介孔二氧化硅包覆纳米氧化铝负载的镍钼催化剂及其制备方法与应用 |
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