CN113952958A - Silicon dioxide loaded nickel-iron catalyst, preparation method and application thereof in turpentine hydrogenation - Google Patents
Silicon dioxide loaded nickel-iron catalyst, preparation method and application thereof in turpentine hydrogenation Download PDFInfo
- Publication number
- CN113952958A CN113952958A CN202111350819.7A CN202111350819A CN113952958A CN 113952958 A CN113952958 A CN 113952958A CN 202111350819 A CN202111350819 A CN 202111350819A CN 113952958 A CN113952958 A CN 113952958A
- Authority
- CN
- China
- Prior art keywords
- nickel
- silica
- silicon dioxide
- iron
- iron catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 70
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 241000779819 Syncarpia glomulifera Species 0.000 title claims abstract description 20
- 239000001739 pinus spp. Substances 0.000 title claims abstract description 20
- 229940036248 turpentine Drugs 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 28
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- XOKSLPVRUOBDEW-DJLDLDEBSA-N (1r,4s,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@H]1CC[C@H]2C(C)(C)[C@@H]1C2 XOKSLPVRUOBDEW-DJLDLDEBSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims description 42
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 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 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 16
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 11
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 229940045919 sodium polymetaphosphate Drugs 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000012692 Fe precursor Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 27
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 23
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 14
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 229930006728 pinane Natural products 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- 229930006722 beta-pinene Natural products 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- FUDNBFMOXDUIIE-UHFFFAOYSA-N 3,7-dimethylocta-1,6-diene Chemical compound C=CC(C)CCC=C(C)C FUDNBFMOXDUIIE-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000006359 Vitis rotundifolia var rotundifolia Nutrition 0.000 description 1
- 244000013146 Vitis rotundifolia var. rotundifolia Species 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 229930003642 bicyclic monoterpene Natural products 0.000 description 1
- 150000001604 bicyclic monoterpene derivatives Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
Images
Classifications
-
- 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
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silicon dioxide loaded nickel-iron catalyst, a preparation method and application thereof in turpentine hydrogenation, and relates to the technical field of turpentine hydrogenation catalyst preparation, wherein the preparation method of the catalyst comprises the following steps: treating silicon dioxide by adopting an auxiliary agent a, and then adding a nickel and iron precursor solution into a silicon dioxide carrier treated by the auxiliary agent; adding an auxiliary agent b to obtain a suspension, heating and depositing the suspension, then cooling to room temperature, filtering, washing with deionized water, drying, and then roasting; and activating the obtained roasted product in a hydrogen atmosphere to obtain the silicon dioxide loaded nickel-iron catalyst. According to the invention, the auxiliary agent is added in the preparation process of the silicon dioxide loaded nickel and iron catalyst, so that the acting force between nickel and iron and the carrier is improved, the catalytic activity of the nickel-based catalyst is improved, the service life of the nickel-based catalyst is prolonged, and the content of the obtained cis-pinane is more than 90% in the process of catalytically hydrogenating turpentine.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of preparation of turpentine hydrogenation catalysts, and particularly relates to a silicon dioxide supported nickel-iron catalyst, a preparation method and application thereof in turpentine hydrogenation.
[ background of the invention ]
Turpentine is a rich renewable resource, and is a terpenoid substance with low boiling point separated from turpentine processing production. The chemical structure mainly takes bicyclic monoterpene compounds alpha-pinene and beta-pinene as main components, and the total content of pinene is over 90 percent. The hydrogenation of turpentine is mainly the catalytic hydrogenation of pinene. The hydrogenation of alpha-pinene and beta-pinene attacks the side with small site resistance, so that cis-pinane is mainly generated.
The pinane has one cyclobutane with high tension in its molecule, which is easy to open or expand, so that pinane has high chemical activity and can be used to synthesize various perfumes and essences. For example, pinane can be cracked to obtain various perfumes such as dihydromyrcene, citronellol, citronellal, muscadine and the like.
In the early research, common noble metal catalysts Pd/C, Pt/C and the like are used, and the catalysts are expensive and have low cis-isomer content in the product. Later, non-noble metal catalysts such as RanneyNi and the like are developed and applied, but the defects of poor activity, unsafe use, low selectivity, low conversion rate and the like exist.
Silica is a highly stable, common catalyst support. The nickel-based catalyst is a common hydrogenation catalyst and is low in price. However, the conventional nickel-based catalyst has poor stability and is easily deactivated. Therefore, it would be of particular value to develop and prepare high activity, long life nickel-based catalysts.
[ summary of the invention ]
The invention aims to provide a silicon dioxide loaded nickel-iron catalyst, a preparation method and application thereof in turpentine hydrogenation, and solves the technical problems of unstable catalyst, low activity and short service life caused by unstable carrier surface adsorption and low dispersion degree in the prior art. Meanwhile, hydrogenation of turpentine is applied to realize the generation of high cis-pinane.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a silica-supported nickel-iron catalyst comprises the following steps:
step 1: preparation of silica support
Soaking silicon dioxide in an auxiliary agent a water solution with the mass percent concentration of 0.1-1.0%, and stirring for 1-2h at the temperature of 65-73 ℃ to obtain a silicon dioxide carrier suspension, wherein the auxiliary agent a is composed of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000;
step 2: preparing nickel nitrate and ferric nitrate into a solution with the mass percentage of 10-30% to prepare a nickel-iron solution;
and step 3: adding the ferronickel solution prepared in the step 2 into the silicon dioxide carrier suspension prepared in the step 1 under stirring, simultaneously adding an auxiliary agent b with the total mass of 0.05-0.2% of the liquid, and stirring for 2.5-3.2 hours to prepare a suspension, wherein the auxiliary agent b consists of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose;
and 4, step 4: heating the suspension prepared in the step 3 to 60-100 ℃, depositing for 1-7h, then cooling to room temperature, filtering to obtain a precipitate, washing the precipitate with deionized water to prepare a washed precipitate;
and 5: drying the washed precipitate obtained in the step 4 at the temperature of 116 ℃ and 122 ℃ for 22-24h, and then roasting the dried precipitate at the temperature of 400 ℃ and 600 ℃ for 4.6-5.2h to obtain a roasted precipitate;
step (ii) of6: activating the roasted precipitate prepared in the step 5 in a hydrogen atmosphere at 490-510 ℃ for 2.8-3.2h to prepare the silicon dioxide loaded nickel-iron catalyst NiFen/SiO2。
Further, in the step 1, the assistant a is composed of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 according to the molar ratio of 0.9-1.1:0.8-1.3: 0.4-0.6.
Further, Ni (NO) is adopted as the nickel nitrate in the step 23)·6H2O。
Further, in the step 2, Fe (NO) is adopted as ferric nitrate3)·9H2O。
Further, the mass ratio of the nickel nitrate to the ferric nitrate to the silicon dioxide is 1-2:0.02-0.09: 1.
Furthermore, in the step 3, the auxiliary agent b is composed of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose according to the molar ratio of 0.8-1:0.9-1.2:0.5-0.6: 0.4-0.7.
Preferably, the suspension prepared in step 4 is deposited by heating, and the optimal condition is that the suspension is deposited for 5 hours at the temperature of 80 ℃.
Preferably, the conditions for the optimal calcination in step 5 are: roasting at 500 deg.c for 5 hr.
Further, in step 6, n is 0.03,0.05, 0.07.
Further, the molar ratio of the nickel iron in the step 6 is 1: 0.03-0.07.
Preferably, the optimum n is 0.05 and the ferronickel molar ratio is 1: 0.05.
The invention also provides a silicon dioxide supported nickel-iron catalyst prepared by the method, and the specific surface area of the catalyst is 223.9-355.5m2/g。
The invention also provides application of the silicon dioxide loaded nickel-iron catalyst in turpentine hydrogenation, and the content of the obtained cis-pinane is more than 90%.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the auxiliary agent is added in the preparation process of the silicon dioxide loaded nickel and iron catalyst, so that the acting force between nickel and iron and the carrier is improved, the catalytic activity and the service life of the nickel-based catalyst are improved (the nickel-based catalyst is circularly used for 5 times), and the content of the obtained cis-pinane is more than 90% in the process of catalytically hydrogenating turpentine.
(2) Compared with the existing catalyst, the silicon dioxide supported nickel-iron catalyst prepared by the invention has the advantages of low cost, safe use, high selectivity and the like, and the technology of the invention is remarkably improved and can be popularized and applied.
[ description of the drawings ]
FIG. 1 is an electron micrograph of a silica-supported nickel-iron catalyst prepared in example 2 according to the present invention magnified 200 times.
FIG. 2 is an electron micrograph of the silica-supported nickel-iron catalyst prepared in example 2 according to the present invention, magnified 2000 times.
FIG. 3 is an electron micrograph of the silica-supported nickel-iron catalyst prepared in example 2 of the present invention magnified 50000 times.
FIG. 4 is a gas chromatogram of pinane obtained by catalytic hydrogenation of turpentine with the silica-supported nickel-iron catalyst prepared in example 2 of the present invention.
[ detailed description ] embodiments
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In an embodiment, the preparation method of the silica supported nickel-iron catalyst comprises the following steps:
step 1: preparation of silica support
Soaking silicon dioxide in an auxiliary agent a water solution with the mass percent concentration of 0.1-1.0%, and stirring for 1-2h at the temperature of 65-73 ℃ to obtain a silicon dioxide carrier suspension, wherein the auxiliary agent a is composed of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 according to the molar ratio of 1:1: 0.5;
step 2: preparing nickel nitrate and ferric nitrate into a solution with the mass percentage of 10-30% to prepare a nickel-iron solution, wherein the nickel nitrate adopts Ni (NO)3)·6H2O, using Fe (NO) as ferric nitrate3)·9H2O, of said nickel nitrate, iron nitrate, silicon dioxideThe mass ratio is 1-2:0.02-0.09: 1;
and step 3: adding the ferronickel solution prepared in the step 2 into the silicon dioxide carrier suspension prepared in the step 1 under stirring, simultaneously adding an auxiliary agent b with the total liquid mass of 0.05-0.2%, and stirring for 2.5-3.2 hours to prepare a suspension, wherein the auxiliary agent b is composed of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose according to the molar ratio of 1:1:0.5: 0.5;
and 4, step 4: heating the suspension prepared in the step 3 to 60-100 ℃, depositing for 1-7h, then cooling to room temperature, filtering to obtain a precipitate, washing the precipitate with deionized water to prepare a washed precipitate;
and 5: drying the washed precipitate obtained in the step 4 at the temperature of 116 ℃ and 122 ℃ for 22-24h, and then roasting the dried precipitate at the temperature of 400 ℃ and 600 ℃ for 4.6-5.2h to obtain a roasted precipitate;
step 6: activating the roasted precipitate prepared in the step 5 in a hydrogen atmosphere at 490-510 ℃ for 2.8-3.2h to prepare the silicon dioxide loaded nickel-iron catalyst NiFen/SiO2Wherein n is 0.03,0.05, 0.07; the molar ratio of the ferronickel is 1: 0.03-0.07.
The present invention is illustrated by the following more specific examples.
Example 1
A preparation method of a silica-supported nickel-iron catalyst comprises the following steps:
step 1: preparation of silica support
Soaking silicon dioxide in an auxiliary agent a water solution with the mass percent concentration of 0.2%, and stirring for 1.8 hours at the temperature of 67 ℃ to obtain a silicon dioxide carrier suspension, wherein the auxiliary agent a is composed of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 according to the molar ratio of 0.9:1.1: 0.4;
step 2: preparing nickel nitrate and ferric nitrate into a solution with the mass percentage of 13% to prepare a nickel-iron solution, wherein the nickel nitrate adopts Ni (NO)3)·6H2O, using Fe (NO) as ferric nitrate3)·9H2O, wherein the mass ratio of the nickel nitrate to the ferric nitrate to the silicon dioxide is 1:0.04: 1;
and step 3: adding the ferronickel solution prepared in the step 2 into the silicon dioxide carrier suspension prepared in the step 1 under stirring, simultaneously adding an auxiliary agent b with the total liquid mass of 0.07%, and stirring for 2.6 hours to prepare a suspension, wherein the auxiliary agent b is composed of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose according to the molar ratio of 0.8:1.1:0.5: 0.4;
and 4, step 4: heating the suspension prepared in the step 3 to 70 ℃ for deposition for 6h, then cooling to room temperature, filtering to obtain a precipitate, washing the precipitate with deionized water to obtain a washed precipitate;
and 5: drying the washed precipitate obtained in step 4 at 116 ℃ for 24h, and then roasting the dried precipitate at 400 ℃ for 5.2h to obtain a roasted precipitate;
step 6: activating the roasted precipitate prepared in the step 5 at 490 ℃ for 3.2h in hydrogen atmosphere to prepare silicon dioxide loaded nickel-iron catalyst NiFen/SiO2Wherein n is 0.03; the molar ratio of ferronickel is 1:0.03, and the specific surface area of the silicon dioxide supported nickel-silicon catalyst is 288.7m2/g。
Example 2
A preparation method of a silica-supported nickel-iron catalyst comprises the following steps:
step 1: preparation of silica support
Soaking silicon dioxide in an auxiliary agent a water solution with the mass percent concentration of 0.6%, and stirring for 1.6h at the temperature of 70 ℃ to obtain a silicon dioxide carrier suspension, wherein the auxiliary agent a is composed of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 according to the molar ratio of 1:1: 0.5;
step 2: preparing a solution with the mass percent of 22% by nickel nitrate and ferric nitrate to prepare a nickel-iron solution, wherein the nickel nitrate adopts Ni (NO)3)·6H2O, using Fe (NO) as ferric nitrate3)·9H2O, wherein the mass ratio of the nickel nitrate to the ferric nitrate to the silicon dioxide is 1.2:0.07: 1;
and step 3: adding the ferronickel solution prepared in the step 2 into the silicon dioxide carrier suspension prepared in the step 1 under stirring, simultaneously adding an auxiliary agent b with the total liquid mass of 1.2%, and stirring for 3 hours to prepare a suspension, wherein the auxiliary agent b is composed of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose according to the molar ratio of 1:1:0.5: 0.5;
and 4, step 4: heating the suspension prepared in the step 3 to 80 ℃, depositing for 5 hours, then cooling to room temperature, filtering to obtain a precipitate, washing the precipitate with deionized water to obtain a washed precipitate;
and 5: drying the washed precipitate obtained in the step 4 at 120 ℃ for 24 hours, and then roasting the dried precipitate at 500 ℃ for 5 hours to obtain a roasted precipitate;
step 6: activating the roasted precipitate prepared in the step 5 for 3 hours at 500 ℃ in a hydrogen atmosphere to prepare a silicon dioxide loaded nickel-iron catalyst NiFen/SiO2Wherein n is 0.05; the molar ratio of ferronickel is 1:0.05, and the specific surface area of the silicon dioxide supported nickel-silicon catalyst is 355.5m2The electron micrographs are shown in FIGS. 1 to 3.
In addition, the silica supported nickel-iron catalyst prepared in example 2 is used for catalyzing and hydrogenating turpentine, and the gas chromatography detection is adopted to obtain pinane gas chromatography data as shown in the following table:
from the gas chromatography data in the table above, the prepared gas chromatogram 4, and as can be seen from the table and fig. 4, when the silicon dioxide supported nickel-iron catalyst prepared in example 2 is used for catalyzing and hydrogenating turpentine, the obtained cis-pinane content is 94.35%, which indicates that the silicon dioxide supported nickel-iron catalyst prepared in the invention has extremely high catalytic activity and can meet the application requirements.
Example 3
A preparation method of a silica-supported nickel-iron catalyst comprises the following steps:
step 1: preparation of silica support
Soaking silicon dioxide in an auxiliary agent a water solution with the mass percent concentration of 1.0%, and stirring for 1.1h at the temperature of 72 ℃ to obtain a silicon dioxide carrier suspension, wherein the auxiliary agent a is composed of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 according to the molar ratio of 1.1:1.2: 0.6;
step 2: preparing nickel nitrate and ferric nitrate into a solution with the mass percentage of 28% to prepare a nickel-iron solution, wherein the nickel nitrate adopts Ni (NO)3)·6H2O, using Fe (NO) as ferric nitrate3)·9H2O, wherein the mass ratio of the nickel nitrate to the ferric nitrate to the silicon dioxide is 1.2:0.09: 1;
and step 3: adding the ferronickel solution prepared in the step 2 into the silicon dioxide carrier suspension prepared in the step 1 under stirring, simultaneously adding an auxiliary agent b with the total liquid mass of 0.15%, and stirring for 2.9 hours to prepare a suspension, wherein the auxiliary agent b is composed of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose according to the molar ratio of 0.9:1.1:0.5: 0.6;
and 4, step 4: heating the suspension prepared in the step 3 to 100 ℃ for deposition for 1h, then cooling to room temperature, filtering to obtain a precipitate, washing the precipitate with deionized water to obtain a washed precipitate;
and 5: drying the washed precipitate obtained in step 4 at 122 ℃ for 22h, and then roasting the dried precipitate at 600 ℃ for 4.6h to obtain a roasted precipitate;
step 6: activating the roasted precipitate prepared in the step 5 for 2.9h at 507 ℃ in a hydrogen atmosphere to prepare silicon dioxide loaded nickel-iron catalyst NiFen/SiO2Wherein n is 0.07; the molar ratio of ferronickel is 1:0.07, and the specific surface area of the silicon dioxide supported nickel-silicon catalyst is 319.4m2/g。
Comparative example 1
The procedure for the preparation of the silica supported nickel-iron catalyst of example 2 is essentially the same, except that the silica is not modified with the aid of a, but is passed directly to step (2).
Comparative example 2
The procedure for the preparation of a silica supported nickel-iron catalyst in example 2 was essentially the same except that the auxiliary a in step (1) was sodium stearate.
Comparative example 3
The process for preparing the silica supported nickel-iron catalyst in example 2 was substantially the same except that the auxiliary agent a in step (1) was sodium dodecylsulfate.
Comparative example 4
The process for preparing the silica supported nickel-iron catalyst in example 2 was substantially the same except that the assistant a in step (1) was polyethylene glycol 2000.
Comparative example 5
Chinese patent application document "A method for preparing cis-pinane by catalyzing selective hydrogenation of alpha-pinene (publication No. CN 105481633A)" is adopted, and the catalyst Fe in example 13O4-NH2-Ru。
The catalysts of examples 1-3 and comparative examples 1-5 were used to catalytically hydrogenate turpentine, and the conversion of alpha-pinene was determined by gas chromatography, the results of which are shown in the following table.
| Group of | Conversion of alpha-pinene (%) |
| Example 1 | 94.7 |
| Example 2 | 97.9 |
| Example 3 | 96.1 |
| Comparative example 1 | 71.3 |
| Comparative example 2 | 79.4 |
| Comparative example 3 | 81.6 |
| Comparative example 4 | 76.5 |
| Comparative example 5 | 96.4 |
From the above table, it can be seen that: (1) as can be seen from the data of the conversion rate (94.7-97.9%) of the alpha-pinene measured in the group examples 1-3, the silica supported nickel-iron catalyst prepared by the invention has extremely high catalytic activity; compared with the conversion rate of alpha-pinene obtained by catalytically hydrogenating turpentine by using the existing catalyst (comparative example 5), the level is equivalent, but the composition and the preparation process of the catalyst are different, namely the inventive concept of the silicon dioxide supported nickel-iron catalyst is different from the existing technology, so that the technology of the invention meets the requirement of judging remarkable progress in patent law examination guidelines.
(2) As can be seen from the data of the conversion rate of alpha-pinene measured in the group examples 1-3, the example 2 is the best example of the invention, and the conversion rate of the obtained alpha-pinene is the highest and reaches 97.9%.
(3) From the data on the conversion of α -pinene measured in example 2 and comparative examples 1 to 4, it can be seen that:
1) the effect value of the conversion rate of alpha-pinene generated by using sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 together is 97.9-71.3-26.6 (%);
2) sodium stearate alone gave a value of 79.4-71.3-8.1 (%) for the conversion effect of α -pinene;
3) sodium dodecyl sulfate used together produced a-pinene conversion effect value of 81.6-71.3-10.3 (%);
4) the polyethylene glycol 2000 used together produced a-pinene conversion effect value of 76.5-71.3-5.2 (%);
5) then, the sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 are used alone and then added to produce the alpha-pinene with the conversion effect value of 8.1+10.3+ 5.2-23.6 (%);
in summary, the percent of the effect value of the conversion rate of α -pinene generated by using sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 together is (26.6-23.6) ÷ 23.6 × 100% ═ 12.7% higher than the effect value of the conversion rate of α -pinene generated by adding sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 after being used alone, which indicates that the value is greater than 10%, which indicates that the sodium stearate, sodium dodecyl sulfate and polyethylene glycol are used together in the preparation of the silica-supported nickel-iron catalyst to play a synergistic role and synergistically improve the conversion rate of α -pinene. It can be seen that the combination of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000 in combination meets the creative requirements of the invention in the patent law review guidelines.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a silica-supported nickel-iron catalyst is characterized by comprising the following steps:
step 1: preparation of silica support
Soaking silicon dioxide in an auxiliary agent a water solution with the mass percent concentration of 0.1-1.0%, and stirring for 1-2h at the temperature of 65-73 ℃ to obtain a silicon dioxide carrier suspension, wherein the auxiliary agent a is composed of sodium stearate, sodium dodecyl sulfate and polyethylene glycol 2000;
step 2: preparing nickel nitrate and ferric nitrate into a solution with the mass percentage of 10-30% to prepare a nickel-iron solution;
and step 3: adding the ferronickel solution prepared in the step 2 into the silicon dioxide carrier suspension prepared in the step 1 under stirring, simultaneously adding an auxiliary agent b with the total mass of 0.05-0.2% of the liquid, and stirring for 2.5-3.2 hours to prepare a suspension, wherein the auxiliary agent b consists of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose;
and 4, step 4: heating the suspension prepared in the step 3 to 60-100 ℃, depositing for 1-7h, then cooling to room temperature, filtering to obtain a precipitate, washing the precipitate with deionized water to prepare a washed precipitate;
and 5: drying the washed precipitate obtained in the step 4 at the temperature of 116 ℃ and 122 ℃ for 22-24h, and then roasting the dried precipitate at the temperature of 400 ℃ and 600 ℃ for 4.6-5.2h to obtain a roasted precipitate;
step 6: activating the roasted precipitate prepared in the step 5 in a hydrogen atmosphere at 490-510 ℃ for 2.8-3.2h to prepare the silicon dioxide loaded nickel-iron catalyst NiFen/SiO2。
2. The method for preparing the silica-supported nickel-iron catalyst according to claim 1, wherein the assistant a in step 1 comprises sodium stearate, sodium dodecyl sulfate, and polyethylene glycol 2000 in a molar ratio of 0.9-1.1:0.8-1.3: 0.4-0.6.
3. The method for preparing a silica-supported nickel-iron catalyst according to claim 1, wherein Ni (NO) is used as the nickel nitrate in the step 23)·6H2O。
4. The method for preparing the silica-supported nickel-iron catalyst according to claim 1, wherein the iron nitrate in the step 2 is Fe (NO)3)·9H2O。
5. The preparation method of the silica-supported nickel-iron catalyst according to claim 1, wherein the mass ratio of the nickel nitrate to the iron nitrate to the silica is 1-2:0.02-0.09: 1.
6. The preparation method of the silica-supported nickel-iron catalyst according to claim 1, wherein the assistant b in step 3 is composed of sodium orthophosphate, sodium polymetaphosphate, sodium silicate and sodium carboxymethylcellulose in a molar ratio of 0.8-1:0.9-1.2:0.5-0.6: 0.4-0.7.
7. The method for preparing a silica-supported nickel-iron catalyst according to claim 1, wherein n is 0.03,0.05,0.07 in step 6.
8. The method for preparing a silica-supported nickel-iron catalyst according to claim 1, wherein the molar ratio of nickel to iron in step 6 is 1: 0.03-0.07.
9. A silica-supported nickel-iron catalyst prepared according to any one of claims 1 to 8, wherein the catalyst has a specific surface area of 223.9 to 355.5m2/g。
10. Use of the silica supported nickel-iron catalyst of claim 9 in the hydrogenation of turpentine, wherein the obtained cis-pinane content is greater than 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111350819.7A CN113952958B (en) | 2021-11-15 | 2021-11-15 | Silicon dioxide loaded nickel-iron catalyst, preparation method and application thereof in turpentine hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111350819.7A CN113952958B (en) | 2021-11-15 | 2021-11-15 | Silicon dioxide loaded nickel-iron catalyst, preparation method and application thereof in turpentine hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113952958A true CN113952958A (en) | 2022-01-21 |
| CN113952958B CN113952958B (en) | 2024-03-26 |
Family
ID=79470763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111350819.7A Active CN113952958B (en) | 2021-11-15 | 2021-11-15 | Silicon dioxide loaded nickel-iron catalyst, preparation method and application thereof in turpentine hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113952958B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108917A (en) * | 1976-10-04 | 1978-08-22 | Shell Oil Company | Isomerization of terpene compounds |
| CN102671711A (en) * | 2012-04-13 | 2012-09-19 | 昆明理工大学 | Supported nano amorphous alloy catalyst and preparation method and application |
| CN103191742A (en) * | 2013-04-11 | 2013-07-10 | 济南市供排水监测中心 | Carbon material loaded nano zero valence metal catalyst and preparation method and application thereof |
| CN104003835A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Method for preparing pinane by catalytic hydrogenation of turpentine |
-
2021
- 2021-11-15 CN CN202111350819.7A patent/CN113952958B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108917A (en) * | 1976-10-04 | 1978-08-22 | Shell Oil Company | Isomerization of terpene compounds |
| CN102671711A (en) * | 2012-04-13 | 2012-09-19 | 昆明理工大学 | Supported nano amorphous alloy catalyst and preparation method and application |
| CN103191742A (en) * | 2013-04-11 | 2013-07-10 | 济南市供排水监测中心 | Carbon material loaded nano zero valence metal catalyst and preparation method and application thereof |
| CN104003835A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Method for preparing pinane by catalytic hydrogenation of turpentine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113952958B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111085199A (en) | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof | |
| US4532351A (en) | Process for hydrogenating organic compounds by use of Group VIII aluminum-silicate catalysts | |
| Lin et al. | Improved chemoselective hydrogenation of crotonaldehyde over bimetallic AuAg/SBA-15 catalyst | |
| EP2682380B1 (en) | Method for producing alicyclic carboxylic acid and catalyst used in same | |
| CN109482192B (en) | Preparation method and application of catalyst for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation | |
| CN107349956B (en) | Catalyst for hydrogen production by reforming ethanol steam and preparation method thereof | |
| CN105061176B (en) | A kind of fixed bed synthetic method of 3,3,5 trimethylcyclohexanone | |
| WO2022012061A1 (en) | Preparation method for copper-based hydrogenation catalyst, catalyst prepared therefrom, and use thereof | |
| CN107970929B (en) | A kind of alkynes and alkadienes liquid phase selective hydrogenation catalyst, preparation method and application | |
| CN113952958A (en) | Silicon dioxide loaded nickel-iron catalyst, preparation method and application thereof in turpentine hydrogenation | |
| CN112237946B (en) | Terephthalic acid hydrofining reaction and catalyst thereof | |
| CN105461526A (en) | Method for preparing cyclopentanone through dehydrogenation of cyclopentanol | |
| US4273939A (en) | Process for hydrogenating organic compounds by use of non-ferrous group VIII aluminum coprecipitated catalysts | |
| CN112473679B (en) | Nickel-phyllosilicate structure catalyst and preparation method thereof | |
| CN112536033B (en) | Catalyst for preparing o-toluidine by hydrogenation of o-nitrotoluene and preparation method thereof | |
| CN110845301B (en) | Production method of 1, 2-pentanediol | |
| US4593014A (en) | Catalyst support compositions | |
| JPH02216A (en) | Chemical reaction method and proper catalyst for said reaction | |
| EP0097047A2 (en) | A process for hydrogenating organic compounds by the use of group VIII aluminum-silicate catalysts | |
| CN101195553B (en) | Hydrocarbon synthesizing method | |
| CN110963901A (en) | Preparation method of 3,3, 5-trimethylcyclohexanone | |
| US4497907A (en) | Coprecipitated Si-Al-metal-particle catalyst | |
| CN114192142B (en) | Catalyst for dinonyl phenol hydrogenation and preparation method thereof | |
| CN115814794B (en) | Copper/silicon oxide catalyst and preparation method and application thereof | |
| CN114433127B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic acid by maleic anhydride hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |