CN106861700A - 一种镍‑炭‑二氧化硅粉体催化剂及制备方法和应用 - Google Patents
一种镍‑炭‑二氧化硅粉体催化剂及制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 15
- 239000003610 charcoal Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 56
- 239000001257 hydrogen Substances 0.000 claims description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 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 6
- 150000003839 salts Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000011435 rock Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- NMTBZBPWKJALHU-UHFFFAOYSA-N O=C.C#C Chemical compound O=C.C#C NMTBZBPWKJALHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 19
- 239000003708 ampul Substances 0.000 description 18
- 239000010453 quartz Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 11
- 238000000889 atomisation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- -1 methyl silicates Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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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
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Abstract
一种镍‑炭‑二氧化硅粉体催化剂组成为:镍:炭:二氧化硅的质量比为1:0.02~0.1:0.33~2。本发明具有高活性、高选择性,稳定性好,无污染的优点。
Description
技术领域
本发明涉及一种镍-炭-二氧化硅粉体催化剂及制备方法和应用。
背景技术
由炔醛法合成1,4-丁二醇是一种合成1,4-丁二醇的经典方法。该方法由甲醛、乙炔为原料,先合成1,4-丁炔二醇,后经加氢后得到1,4-丁二醇,催化加氢过程是重要的一环。
HOCH2C≡CCH2OH+2H2→HOCH2CH2CH2CH2OH
1,4-丁炔二醇加氢常采用镍基催化剂。专利US3449445报道了以Raney-Ni为催化剂,在低压与低温条件下采用淤浆床工艺进行1,4-丁炔二醇加氢制备1,4-丁二醇的方法。美国专利US2967893及US2948687则分别公开了以Cu与Mo为助剂的Raney-Ni催化剂,用于在温度20℃~140℃,压力0MPa~2MPa条件下进行丁炔二醇加氢制备1,4-丁二醇的方法。Raney Ni催化剂以其高的加氢活性被广泛采用。然而,Raney Ni催化剂为骨架催化剂,在使用过程中存在易流失的问题,导致催化剂循环利用性能较差;另外,该催化剂的制备过程经历了高温条件下获得NiAl合金,后进行碱溶、水洗的过程,其制备过程存在性状不易调控并产生大量的含碱废液,造成严重的环境污染。获得制备条件温和的新型替代催化剂成为研究者关注的研究领域。
发明内容
针对上述技术问题,本发明提供一种高活性、高选择性,稳定性好,无污染的镍-炭-二氧化硅粉体催化剂及其制备方法和在1,4-丁炔二醇加氢中的应用。
本发明催化剂组成为镍:炭:二氧化硅的质量比为1:0.02~0.1:0.33~2。
本发明提供的一种镍-炭-二氧化硅粉体催化剂的制备方法,包括如下步骤:
(1)配制镍含量0.05g/mL~0.15g/mL,有机炭源含量0.03g/mL~0.05g/mL的混合镍盐水溶液,超声处理30min~60min;
(2)配制SiO2含量0.05g/mL~0.10g/mL的有机硅盐的醇水混合溶液,加冰醋酸调节pH值4~5,室温下预聚1h~5h,超声处理30min~60min;
(3)取相同体积的步骤(1)与(2)所配溶液,经超声雾化后与氢气混合,其中调节步骤(1)与(2)所配溶液出雾流量相等,步骤(1)所配溶液出雾流量与氢气流量之比为0.5~2:1,将混合气加热至350℃~450℃,在氢气氛下,雾化溶液脱除其中的水份,得到的盐前驱物热解为金属镍及助剂;
(4)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品。
步骤(1)所述镍盐为硝酸镍、氯化镍和硫酸镍中的一种;
步骤(1)所述的有机碳源为聚乙二醇、蔗糖、葡萄糖、柠檬酸中的一种;
步骤(2)所述的有机硅盐为正硅酸甲酯、正硅酸乙酯中的一种;
步骤(2)所述的醇水混合溶液中醇为甲醇或乙醇,醇与水的体积比为1:0.1~0.3。
本发明催化剂应用包括如下步骤:
该催化剂适用于炔醛法合成1,4-丁二醇低压加氢过程,在浆态床或悬浮床反应器中,对含量28wt%~35wt%的1,4-丁炔二醇水溶液进行催化加氢,催化剂用量按每克原料取0.5g~1g催化剂,反应温度50℃~70℃,氢气压力0.5MPa~2MPa,反应时间2h~3h。可以使1,4-丁炔二醇转化率≥93%,1,4-丁二醇选择性≥98%。
与现有技术相比本发明的优点和效果:
(1)利用含有机炭源的镍溶液与二氧化硅溶液,通过雾化超声技术使液体形成蒸汽,后在氢气气氛下原位分解、还原得到镍:炭:二氧化硅粉体,实现了温和条件下高分散加氢催化剂的合成,催化剂在1,4-丁炔二醇加氢过程中表现出优异的催化性能。
(2)催化剂制备方法工艺简单,重复性好,易于操作,能耗低、环境友好,活性金属含量低,载体廉价易得,便于大规模工业化使用。
具体实施方式
实施例1
(1)取24.78g六水合硝酸镍,5g柠檬酸,加去离子水配成100mL溶液,超声处理30min;(2)取17.36g正硅酸乙酯,加乙醇:水体积比为1:0.1的乙醇水溶液,配制100mL溶液,加冰酸酸调节pH值4,室温下预聚1h,超声处理30min。(3)将带有加热装置的石英管,分别与含有相同体积的步骤(1)、步骤(2)所配溶液的超声雾化装置以及氢气相联。(4)将石英管温度加热至350℃,开启氢气,调整氢气流速100mL/min,并开启超声雾化装置,调节步骤(1)与(2)所配溶液的出雾量均在100mL/min,使氢气与经雾化的溶液共同进入石英管,雾化后的液体在氢气氛下热解为金属镍、助剂。(5)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品1#。得到的催化剂,镍:炭:二氧化硅的质量比为1:0.1:1。
实施例2
(1)取40.50g六水合氯化镍,5g葡萄糖,加去离子水配成100mL溶液,超声处理60min。(2)取20.29g正硅酸甲酯,加醇:水体积比为1:0.3的甲醇水溶液,配制100mL溶液,加冰酸酸调节pH值5,室温下预聚5h,超声处理60min。(3)将带有加热装置的石英管,分别与含有相同体积的步骤(1)、步骤(2)所配溶液的超声雾化装置以及氢气相联。(4)将石英管温度加热至450℃,开启氢气,调整氢气流速100mL/min,并开启超声雾化装置,调节步骤(1)与(2)所配溶液的出雾量均在200mL/min,使氢气与经雾化的溶液共同进入石英管,雾化后的液体在氢气氛下热解为金属镍、助剂。(5)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品2#。由上述方法得到的催化剂,镍:炭:二氧化硅的质量比为1:0.05:0.8。
实施例3
(1)取67.17g六水合硫酸镍,3g蔗糖,加去离子水配成100mL溶液,超声处理40min。(2)取34.72g正硅酸乙酯,加醇:水体积比为1:0.2的甲醇水溶液,配制100mL溶液,加冰酸酸调节pH值4.5,室温下预聚4h,超声处理50min。(3)将带有加热装置的石英管,分别与含有相同体积的步骤(1)、步骤(2)所配溶液的超声雾化装置以及氢气相联。(4)将石英管温度加热至400℃,开启氢气,调整氢气流速100mL/min,并开启超声雾化装置,调节步骤(1)与(2)所配溶液的出雾量均在50mL/min,使氢气与经雾化的溶液共同进入石英管,雾化后的液体在氢气氛下热解为金属镍、助剂。(5)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品3#。由上述方法得到的催化剂,镍:炭:二氧化硅的质量比为1:0.02:0.67。
实施例4
(1)取22.39g六水合硫酸镍,5g聚乙二醇,加去离子水配成100mL溶液,超声处理50min。(2)取25.37g正硅酸甲酯,加醇:水体积比为1:0.1的甲醇水溶液,配制100mL溶液,加冰酸酸调节pH值4.5,室温下预聚3h,超声处理30min。(3)将带有加热装置的石英管,分别与含有相同体积的步骤(1)、步骤(2)所配溶液的超声雾化装置以及氢气相联。(4)将石英管温度加热至350℃,开启氢气,调整氢气流速100mL/min,并开启超声雾化装置,调节步骤(1)与(2)所配溶液的出雾量均在150mL/min,使氢气与经雾化的溶液共同进入石英管,雾化后的液体在氢气氛下热解为金属镍、助剂。(5)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品4#。由上述方法得到的催化剂,镍:炭:二氧化硅的质量比为1:0.1:2。
实施例5
(1)取59.45g六水合硝酸镍,4g蔗糖,加去离子水配成100mL溶液,超声处理50min。(2)取20.29g正硅酸甲酯,加醇:水体积比为1:0.3的乙醇水溶液,配制100mL溶液,加冰酸酸调节pH值5,室温下预聚2h,超声处理40min。(3)将带有加热装置的石英管,分别与含有相同体积的步骤(1)、步骤(2)所配溶液的超声雾化装置以及氢气相联。(4)将石英管温度加热至450℃,开启氢气,调整氢气流速100mL/min,并开启超声雾化装置,调节步骤(1)与(2)所配溶液的出雾量均在150mL/min,使氢气与经雾化的溶液共同进入石英管,雾化后的液体在氢气氛下热解为金属镍、助剂。(5)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品5#。由上述方法得到的催化剂,镍:炭:二氧化硅的质量比为1:0.033:0.67。
实施例6
(1)取60.74g六水合氯化镍,3g葡萄糖,加去离子水配成100mL溶液,超声处理60min。(2)取17.36g正硅酸乙酯,加醇:水体积比为1:0.2的乙醇水溶液,配制100mL溶液,加冰酸酸调节pH值4,室温下预聚1h,超声处理60min。(3)将带有加热装置的石英管,分别与含有相同体积的步骤(1)、步骤(2)所配溶液的超声雾化装置以及氢气相联。(4)将石英管温度加热至400℃,开启氢气,调整氢气流速100mL/min,并开启超声雾化装置,调节步骤(1)与(2)所配溶液的出雾量均在75mL/min,使氢气与经雾化的溶液共同进入石英管,雾化后的液体在氢气氛下热解为金属镍、助剂。(5)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品6#。由上述方法得到的催化剂,镍:炭:二氧化硅的质量比为1:0.02:0.33。
实施例7
取上述1#-6#号催化剂在浆态床或悬浮床反应器中,对含量28wt%~35wt%的1,4-丁炔二醇水溶液进行催化加氢,催化剂用量按每克原料取0.5g~1g催化剂,反应温度50℃~70℃,氢气压力0.5MPa~2MPa,反应时间2h~3h。可以使1,4-丁炔二醇(BD)转化率≥93%,1,4-丁二醇(BDO)选择性≥98%。具体的反应条件及结果见表1
表1
Claims (8)
1.一种镍-炭-二氧化硅粉体催化剂,其特征在于催化剂组成为镍:炭:二氧化硅的质量比为1:0.02~0.1:0.33~2。
2.如权利要求1所述的一种镍-炭-二氧化硅粉体催化剂的制备方法,其特征在于包括如下步骤:
(1)配制镍含量0.05g/mL~0.15g/mL,有机炭源含量0.03g/mL~0.05g/mL的混合镍盐水溶液,超声处理30min~60min;
(2)配制SiO2含量0.05g/mL~0.10g/mL的有机硅盐的醇水混合溶液,加冰醋酸调节pH值4~5,室温下预聚1h~5h,超声处理30min~60min;
(3)取相同体积的步骤(1)与(2)所配溶液,经超声雾化后与氢气混合,其中调节步骤(1)与(2)所配溶液出雾流量相等,步骤(1)所配溶液出雾流量与氢气流量之比为0.5~2:1,将混合气加热至350℃~450℃,在氢气氛下,雾化溶液脱除其中的水份,得到的盐前驱物热解为金属镍及助剂;
(4)雾化完成后,在氢气氛下降至室温,停止氢气,得到最终产品。
3.如权利要求2所述的一种镍-炭-二氧化硅粉体催化剂的制备方法,其特征在于步骤(1)所述镍盐为硝酸镍、氯化镍和硫酸镍中的一种。
4.如权利要求2所述的一种镍-炭-二氧化硅粉体催化剂的制备方法,其特征在于步骤(1)所述的有机碳源为聚乙二醇、蔗糖、葡萄糖、柠檬酸中的一种。
5.如权利要求2所述的一种镍-炭-二氧化硅粉体催化剂的制备方法,其特征在于步骤(2)所述的有机硅盐为正硅酸甲酯、正硅酸乙酯中的一种。
6.如权利要求2所述的一种镍-炭-二氧化硅粉体催化剂的制备方法,其特征在于步骤(2)所述的醇水混合溶液中醇为甲醇或乙醇。
7.如权利要求2所述的一种镍-炭-二氧化硅粉体催化剂的制备方法,其特征在于步骤(2)所述的醇水混合溶液中醇与水的体积比为1:0.1~0.3。
8.如权利要求1所述的一种镍-炭-二氧化硅粉体催化剂的应用,其特征在于包括如下步骤:
催化剂用于炔醛法合成1,4-丁二醇低压加氢,在浆态床或悬浮床反应器中,对含量28wt%~35wt%的1,4-丁炔二醇水溶液进行催化加氢,催化剂用量按每克原料取0.5g~1g催化剂,反应温度50℃~70℃,氢气压力0.5MPa~2MPa,反应时间2h~3h。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3449445A (en) * | 1967-03-17 | 1969-06-10 | Gaf Corp | Process of preparing 1,4-butanediol |
CN1548226A (zh) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | 一种用于卤代芳烃加氢脱卤的催化剂及其制备和应用 |
CN101306368A (zh) * | 2008-07-09 | 2008-11-19 | 山西大学 | 丁炔二醇两步法加氢制丁二醇二段加氢催化剂的制备方法 |
CN103418409A (zh) * | 2013-07-20 | 2013-12-04 | 大连理工大学 | 一种选择加氢1,4-丁炔二醇的金属硅化物催化剂及应用 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3449445A (en) * | 1967-03-17 | 1969-06-10 | Gaf Corp | Process of preparing 1,4-butanediol |
CN1548226A (zh) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | 一种用于卤代芳烃加氢脱卤的催化剂及其制备和应用 |
CN101306368A (zh) * | 2008-07-09 | 2008-11-19 | 山西大学 | 丁炔二醇两步法加氢制丁二醇二段加氢催化剂的制备方法 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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