CN1415413A - Catalyzer for hydrogenization of nano nickel and its preparation method - Google Patents
Catalyzer for hydrogenization of nano nickel and its preparation method Download PDFInfo
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- CN1415413A CN1415413A CN 01133372 CN01133372A CN1415413A CN 1415413 A CN1415413 A CN 1415413A CN 01133372 CN01133372 CN 01133372 CN 01133372 A CN01133372 A CN 01133372A CN 1415413 A CN1415413 A CN 1415413A
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- nickel
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Abstract
A nano nickel hydrocatalyst is prepared from the nano nickel and carrier strip made up of alumina or the mixture of alumina and amorphous Si-Al through uniformly coating the nano nickel particles on the surface of said carrier strips by mechanical vibration method, and calcining. Its advantages are less consumption of nickel and high activity.
Description
1, technical field
The present invention is a kind of hydrogenation catalyst and preparation method thereof, particularly a kind of catalyzer for hydrogenization of nano nickel and preparation method thereof.The invention belongs to the nickel hydrogenation catalyst technical field, specifically belong to nano level nickel hydrogenation catalyst technical field.
2, background technology
Because Ni/Al
2O
3The class catalyzer has very high hydrogenation activity and is widely used in hydrogenation reactions such as aromatic hydrogenation, solvent oil hydrogenation.Ni/Al
2O
3The general employing of catalyzer is coprecipitated, dipping or mix the method preparation of pinching, and the nickel source of employing is generally nickelous chloride, nickelous nitrate etc., the Cl that produces in the preparation
-, NO
xCan produce environment and pollute.The catalyzer nickel content of method for preparing is higher, generally at 15-50m%.
USP4490480 has introduced a kind of Ni/Al
2O
3Hydrogenation catalyst, catalyzer adopt the preparation of nickel amine complex dipping method, the nickeliferous 5-40W% of this catalyzer, and nickel content is about 18w% among the embodiment.The crystalline dispersion inside of 95% nickel at aluminum oxide.This patent prepares catalyzer when roasting, can generate the NO of environmental pollution
x, and the catalyzer nickel content is higher, and the Preparation of Catalyst cost is higher.
It is the method for feedstock production nanometer Ni-Pd alloy ultro-micro partical catalyzer with two kinds of close refractory metal nickel and palladiums of fusing point that CN94115078 discloses a kind of, in the vacuum chamber of specific equipment, earlier the nickel plate is placed on the anode planes plate, with the palladium thin slice be placed on the nickel plate above compress, heating also feeds argon gas and ignites, and contacts starting arc with nickel shot, makes the evaporation of nickel and palladium produce atom and runs foul of each other, generate the Ni-Pd alloy ultro-micro partical and be deposited on the cold-trap, collect and just get catalyst prod.But this belongs to alloy ultra micron catalyzer, does not have solid shape, and (as fixed bed reaction) can't be used under many conditions.
3, summary of the invention
The nickel content height of the nickel hydrogenation catalyst of immersion process for preparing in the prior art, the preparation process complexity, there are problems such as environmental pollution in the cost height; Nano level nickel alloy catalyst Application Areas is restricted, as can not being used for fixing bed reaction, and has the problem on the engineering, as separation, loss etc.The objective of the invention is to address the above problem, the catalyzer for hydrogenization of nano nickel that a kind of nickel content is low, active high, can advance to be used for fixing the bed reaction is provided, and another object of the present invention is to provide the preparation method of low, the simple and easy to do catalyzer for hydrogenization of nano nickel of a kind of non-environmental-pollution, cost.
Nickel hydrogenation catalyst of the present invention is a carrier with the refractory inorganics, nickeliferous by weight 3-6%, and nickel mainly is distributed in the outside surface of catalyzer, and nickel crystal mean diameter is 10-90nm, is preferably 20-50nm.
Preparation of catalysts method of the present invention is bright to be: the carrier of the inorganics raw material being made suitable granularity and shape, with mechanical vibration method the nano-nickel powder of nickel crystallite diameter 10-90nm, preferred 20-50nm is dispersed in carrier surface then, again 450-550 ℃ of roasting 0.5～4 hour.
The catalyzer of the inventive method preparation is no any material generation that contaminate environment is arranged in preparation process.Catalyzer nickel content 3-6m% is significantly less than the catalyzer that pickling process or kneading method prepare, and support of the catalyst can be selected cheap refractory inorganics in addition, so the cost of catalyzer of the present invention is lower.The catalyzer of the present invention preparation obviously improves than catalyst prepared hydrogenation performance, and since catalyzer of the present invention for having definite shape and granularity, institute can be used for fixing bed and react so that use.
4, embodiment
The shape of catalyzer of the present invention and granularity can specifically be determined according to application need, generally can select the sphere of diameter 0.1-20mm, the bar shaped of diameter 0.1-10mm, length 2-10mm etc.
The refractory inorganics that is used for support of the catalyst mainly is selected from one or more oxide compound such as the element that contains aluminium, silicon, titanium, zirconium, boron, phosphorus, as in the materials such as aluminum oxide, silicon oxide, amorphous silicon aluminium, molecular sieve one or more, these inorganicss can crude substance, it also can be the synthetic material, because this catalyzer mainly utilizes the outside surface of carrier, so aluminum oxide that can be most preferably cheap, silicon oxide etc.
The concrete preparation method of catalyst prod of the present invention is as follows:
1, with inorganics raw material such as aluminum oxide powder or contain the aluminum oxide powder of amorphous silicon aluminium and tackiness agent mixes and pinches, extruded moulding, 100-120 ℃ of drying, carrier is made in 500-550 ℃ of roasting; Wherein the content of aluminum oxide is 70-90m%, tackiness agent consist of 10-30m%.
2, prepare nano-nickel powder (nickel crystallite diameter 10-90nm, preferred 20-50nm) with the hydrogen arc process;
3, the bar shaped carrier of step 1 preparation and the nano-nickel powder of step 2 preparation are dispersed in carrier surface with mechanical vibration method with nanometer nickel;
4, the catalyzer of step 3 preparation was 450-550 ℃ of roasting 0.5～4 hour.
The used aluminum oxide form of the present invention is a pseudo-boehmite, and the content of amorphous silicon aluminium in aluminum oxide is 0-50%, and tackiness agent is that common little porous aluminum oxide and the kneading of rare nitric acid forms, and content is 10-30%.
Mechanical vibration method of the present invention is about to support of the catalyst and nano-nickel powder end and puts into any container that can roll or rotate, and makes nano-nickel powder be evenly coated in carrier surface.
Among the present invention, the catalyzer of gained detects through high-resolution electron microscopy (HRTEM) after 450-550 ℃ of roasting, and the nickel particle size is between 10-90nm, usually between 20-50nm.
Prove characteristics of the present invention below by some embodiment.
Embodiment 1
278 grams are intended water thin aluminium stone aluminum oxide (butt 72%, pore volume 0.513ml/g, specific surface area 194m
2/ g) put into rolling machine with 250 tackiness agents made of gram (butt 20%) aluminum oxide, add suitable quantity of water, mixed grind 1 hour is ground and can be squeezed paste, extrusion diameter 0.5mm, length 4-6mm.Extrude 110 ℃ of dryings of bar, 550 ℃ of roastings 4 hours.The nano-nickel powder and the above-mentioned roasting bar that prepare 20-50nm with the hydrogen arc process are put into the rotation Glass Containers, and mechanical vibration all are coated in the carrier strip surface with nano-nickel powder.Then 500 ℃ of following roastings 4 hours.Detect through high-resolution electron microscopy (HRTEM), the nickel particle size of catalyst surface is between 20-50nm, and the nickel content of catalyzer is 4.5m%.Catalyzer is numbered NHC-1C.
Embodiment 2
83.3 gram is intended water thin aluminium stone aluminum oxide (butt 72%, pore volume 0.513ml/g, specific surface area 194m
2/ g), 28.6 gram amorphous silicon aluminium (pore volume 2.80ml/g, specific surface 280m
2/ g, butt 70%), 100 gram tackiness agent (butt 20%) mixed grinds 1 hour are ground and can be squeezed paste, extrusion diameter 0.5mm, length 4-6mm.Extrude 110 ℃ of dryings of bar, 550 ℃ of roastings 4 hours.The nano-nickel powder and the above-mentioned roasting bar that prepare 20-50nm with the hydrogen arc process are put into the Glass Containers of rotation, and mechanical vibration all are coated in the carrier strip surface with nano-nickel powder.Then 500 ℃ of following roastings 4 hours.Detect through high-resolution electron microscopy (HRTEM), the nickel particle size of catalyst surface is between 20-50nm, and the nickel content of catalyzer is 4.3m%.Catalyzer is numbered NHC-1C.Catalyzer is numbered NHC-2C.
Comparative example 1
Compound concentration be the nickel amine complex aqueous solution dipping of 21g/100ml nickel oxide with the alumina supporter bar among the embodiment 1,110 ℃ of dryings, 500 ℃ of roastings 4 hours.Again with the nickel amine complex aqueous solution of nickel oxide dipping, 110 ℃ of dryings, 500 ℃ of roastings 4 hours.The catalyzer that makes contains NiO 24w%.Catalyzer numbering RC-1.
Embodiment 3
Put into catalyzer 10 grams in 2 liter autoclaves, logical hydrogen reducing is 1 hour under 220 ℃, adds toluene 100ml.At H
2Pressure 45atm, 200 ℃ of reactions down, sampling analysis in the time of 6 hours, 11 hours, result such as following table.
| Catalyzer | ????NHC-1 | ????NHC-2 | ????RC-1 |
| Toluene conversion, m% 6 hours 11 hours | ? ????37.58 ????63.11 | ? ????36.80 ????63.17 | ? ????32.49 ????61.13 |
From the table the result as can be seen, NHC-1 and NHC-2 have better hydrogenation activity than the RC-1 catalyzer.
Claims (10)
1. a catalyzer for hydrogenization of nano nickel is a carrier with the refractory inorganics, is active constituent with nickel, it is characterized in that described active constituent nickel is distributed in the carrier outside surface with the 10-90nm crystalline form, by weight the nickeliferous 3%-6% of catalyzer.
2. according to the described catalyzer for hydrogenization of nano nickel of claim 1, it is characterized in that described refractory inorganics is the oxide compound that contains in aluminium, silicon, titanium, zirconium, boron, the phosphoric one or more.
3. according to claim 1 or 2 described catalyzer for hydrogenization of nano nickel, it is characterized in that described refractory inorganics is one or more in aluminum oxide, silicon oxide, the amorphous silicon aluminium.
4. according to the described catalyzer for hydrogenization of nano nickel of claim 1, it is characterized in that described active constituent nickel is distributed in the carrier outside surface with the crystalline form of 20-50nm.
5. according to the described catalyzer for hydrogenization of nano nickel of claim 1, it is characterized in that described catalyst shape is the sphere of diameter 0.1-20mm or the bar shaped of diameter 0.1-10mm, length 2-10mm.
6. the preparation method of the described catalyzer for hydrogenization of nano nickel of claim 1, the inorganics raw material is made the carrier of suitable granularity and shape, with mechanical vibration method the nano-nickel powder of nickel crystallite diameter 10-90nm is dispersed in carrier surface then, made catalyzer in 0.5～4 hour 450-550 ℃ of roasting again.
7. according to the described preparation method of claim 6, the preparation process that it is characterized in that described carrier is: with inorganics raw material such as aluminum oxide powder or contain the aluminum oxide powder of amorphous silicon aluminium and tackiness agent mixes and pinches extruded moulding, 100-120 ℃ of drying, carrier is made in 500-550 ℃ of roasting; Wherein the content of aluminum oxide is 70-90m%, tackiness agent consist of 10-30m%.
8. according to the described preparation method of claim 6, it is characterized in that described nano-nickel powder is prepared by the hydrogen arc process.
9. according to the described preparation method of claim 6, it is characterized in that described mechanical vibration method is that carrier and nano-nickel powder are put into the container that rolls or rotate, and makes nano-nickel powder be evenly coated in carrier surface.
10. according to the described preparation method of claim 6, the crystal grain diameter that it is characterized in that described nano-nickel powder is 20-50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01133372 CN1132685C (en) | 2001-10-30 | 2001-10-30 | Catalyzer for hydrogenization of nano nickel and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01133372 CN1132685C (en) | 2001-10-30 | 2001-10-30 | Catalyzer for hydrogenization of nano nickel and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1415413A true CN1415413A (en) | 2003-05-07 |
| CN1132685C CN1132685C (en) | 2003-12-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01133372 Expired - Lifetime CN1132685C (en) | 2001-10-30 | 2001-10-30 | Catalyzer for hydrogenization of nano nickel and its preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301792C (en) * | 2003-05-14 | 2007-02-28 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
| RU2479562C1 (en) * | 2012-03-20 | 2013-04-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВогГТУ) | Method of producing straight-chain alkanes |
-
2001
- 2001-10-30 CN CN 01133372 patent/CN1132685C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301792C (en) * | 2003-05-14 | 2007-02-28 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
| RU2479562C1 (en) * | 2012-03-20 | 2013-04-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВогГТУ) | Method of producing straight-chain alkanes |
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| Publication number | Publication date |
|---|---|
| CN1132685C (en) | 2003-12-31 |
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