CN115709071A - Nickel catalyst and preparation method thereof - Google Patents
Nickel catalyst and preparation method thereof Download PDFInfo
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- CN115709071A CN115709071A CN202211423412.7A CN202211423412A CN115709071A CN 115709071 A CN115709071 A CN 115709071A CN 202211423412 A CN202211423412 A CN 202211423412A CN 115709071 A CN115709071 A CN 115709071A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 238000002360 preparation method Methods 0.000 title description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 238000005086 pumping Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 150000002815 nickel Chemical class 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical compound CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention provides a nickel catalyst, which comprises a carrier and an active component nickel, wherein the content of the active component nickel is 5-30 wt% based on the total weight of the nickel catalyst. Based on the total weight of nickel, the nickel with the particle size of 2 nm-5 nm accounts for 75wt% -100 wt%. The nickel catalyst provided by the invention has the advantages of high active component content, good dispersibility of the active component nickel and good catalytic performance.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a nickel catalyst and a preparation method thereof.
Background
The nickel is widely applied to hydrogenation reaction catalysts due to good hydrogenation activity and impurity resistance, and the impregnation method for preparing the supported nickel-based catalyst is simple and low in price, so that the method is the most common method for producing the nickel catalyst. However, the impregnation process is a process in which the active component enters the porous carrier in the form of a salt solution and permeates into the inner surface, and when the catalyst is prepared by adopting a conventional impregnation method, the carrier usually contains a large number of mesopores with the pore diameter of 2-50nm, and many of the abundant pore channels are closed, and impregnation liquid cannot enter due to surface tension in the impregnation process, so that the pore channels of the carrier cannot be fully utilized, the active component cannot be completely and uniformly spread and dispersed on the carrier, and active metal particles on the carrier are easy to aggregate, thereby reducing the activity of the catalyst.
For example, CN 110860290A discloses a preparation method of an activated carbon supported nickel catalyst, which comprises: putting activated carbon in a solvent, and carrying out ultrasonic oscillation; (2) Slowly dropwise adding a silylation reagent into the material obtained in the step (1) under the stirring condition; (3) carrying out ultrasonic oscillation on the material obtained in the step (2) under high frequency; (4) Carrying out suction filtration on the material obtained in the step (3), washing the obtained solid with alcohol, and drying under a vacuum condition; (5) preparing a nickel salt aqueous solution; (6) Putting the material obtained in the step (4) into the nickel salt solution obtained in the step (5), and stirring and dipping the material at the room temperature in the same volume; (7) And (4) drying, calcining and pre-reducing the solid in the material obtained in the step (6) to obtain the active carbon-loaded nickel catalyst.
CN 110961111A discloses a technical scheme of impregnation under vacuum condition, in particular to a preparation method of a supported catalyst for glycol hydrofining, which comprises the preparation of an alumina carrier and the impregnation, drying and roasting of active components, wherein the impregnation working procedure of the active components is as follows: preparing ammonia water complex solution of nickel nitrate, soaking the prepared alumina carrier in the nickel nitrate complex solution, vacuum pressure soaking at 65-85 deg.c for 4-6 hr, filtering, drying, and roasting at 350-450 deg.c for 3-5 hr; and obtaining the catalyst precursor. However, the technical scheme still has the defect that the loading effect of the active component is not ideal, such as the active component is easy to agglomerate.
Disclosure of Invention
One of the purposes of the present invention is to overcome the defects of the prior art and provide a nickel catalyst. The nickel catalyst provided by the invention has high active component content and good dispersibility of the active component nickel.
The second purpose of the invention is to provide a preparation method of the nickel catalyst.
The invention also aims to provide the application of the nickel catalyst in selective hydrogenation.
The fourth purpose of the invention is to provide a method for selectively hydrogenating pyrolysis gasoline, such as a method for hydrogenating hydroxybutyraldehyde.
In order to realize the purpose, the invention adopts the following technical scheme:
a nickel catalyst comprising a carrier and an active component nickel, wherein the active component nickel is present in an amount of 5wt% to 30wt%, preferably 10wt% to 25wt%, based on the total weight of the nickel catalyst.
In the nickel catalyst, the active component nickel is dispersed on the carrier in the form of amorphous nickel. Furthermore, the nickel content with the particle size of 2 nm-5 nm is 75wt% -100 wt%, preferably 85wt% -97 wt% based on the total weight of the nickel. According to the present invention, the nickel content having a particle size of 2nm to 5nm may be enumerated by 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, and any value therebetween, based on the total weight of nickel.
In some preferred embodiments of the present invention, the support is present in an amount of 75wt% to 95wt%, preferably 80wt% to 92wt%, based on the total weight of the nickel catalyst.
In the nickel catalyst, the carrier is an alumina carrier, preferably alpha-Al 2 O 3 、β-Al 2 O 3 、γ-Al 2 O 3 And the like. According to the present invention, the shape of the carrier is not limited.
In some preferred embodiments of the invention, the pore size of the support is between 5nm and 25nm, preferably between 8nm and 20nm. According to the invention, the pore size of the support may be 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm and any value in between.
In some preferred embodiments of the present invention, the specific surface area of the support is 20m 2 /g～200m 2 A/g, preferably of 30m 2 /g～100m 2 /g。
In some preferred embodiments of the invention, the support has a pore volume of from 0.2mL/g to 1.0mL/g, preferably from 0.3mL/g to 0.7mL/g.
In some preferred embodiments of the present invention, the average particle size of the support is 0.5mm to 10mm, preferably 1mm to 5mm, more preferably 1mm to 3mm. According to the present invention, the average particle diameter of the carrier may be 0.5mm, 1.0mm, 1.5mm, 2.0mm, 2.5mm, 3.0mm, 3.5mm, 4.0mm, 4.5mm, 5.0mm, 5.5mm, 6.0mm, 6.5mm, 7.0mm, 7.5mm, 8.0mm, 8.5mm, 9.0mm, 9.5mm, 10.0mm and any value therebetween.
In some preferred embodiments of the invention, the water absorption of the carrier is from 0.2g/g to 1.5g/g, preferably from 0.5g/g to 1.0g/g. In some preferred embodiments of the present invention, the bulk density of the support is 0.1g/cm 3 ～1.0g/cm 3 Is selected to be 0.3g/cm 3 ～0.8g/cm 3 。
The preparation method of the nickel catalyst comprises the following steps:
(1) Pretreating the carrier under vacuum condition;
(2) Adding a nickel-containing solution to the pretreated support;
(3) Performing vacuum pumping treatment and pressurization treatment on the system prepared in the step (2), wherein the vacuum pumping treatment and the pressurization treatment are performed for 1 to 10 times, and preferably for 3 to 8 times;
(4) Drying the system prepared in the step (3) to obtain a catalyst precursor;
(5) And (5) roasting and reducing the catalyst precursor prepared in the step (4) to obtain the nickel catalyst.
According to the invention, the nickel-containing solution is prepared by dissolving a nickel source in a solvent. Further, the nickel salt is a soluble nickel salt, and preferably, the nickel salt is at least one selected from nickel nitrate, nickel chloride, nickel bromide, nickel acetate, nickel sulfate and the like. Preferably, the solvent is water. The method provided by the invention is also suitable for preparing other impregnated carriers.
Specifically, in the step (1), the vacuum condition comprises that the absolute pressure is 0-0.5 atm; the pretreatment time is not less than 5min. Step (2) is carried out at an absolute pressure of 0 to 0.5 atm.
Further, in the step (3), the vacuum-pumping treatment condition includes that the absolute pressure is 0 to 0.5atm; the time is 5min to 30min.
Specifically, in the step (3), the conditions of the pressurization treatment include: absolute pressure is 1-20 atm; the time is 5 min-30 min. Preferably, the evacuation treatment and the pressurization treatment are performed under an oscillation condition, preferably an oscillation of up-down amplitude, left-right amplitude, and more preferably an amplitude of the oscillation is not less than 3cm.
Specifically, in the step (4), the drying conditions include: the drying temperature is 80-120 ℃.
Further, in the step (5), the roasting treatment temperature is 200-500 ℃, and the roasting time is 2-20 h; the temperature of the reduction treatment is 300-500 ℃, and the reduction time is 2-20 h; the reducing gas used in the reduction treatment is a mixed gas of nitrogen and hydrogen, and the molar ratio of nitrogen to hydrogen is preferably (0.1-1): 1.
The invention provides an application of the nickel catalyst in the field of selective hydrogenation, in particular to the field of selective hydrogenation.
The invention also provides a method for selective hydrogenation of pyrolysis gasoline, which uses the nickel catalyst to contact and react with hydrogen and pyrolysis gasoline, wherein the reaction pressure is 2.0-6.0 MPa, and the airspeed is 1.0h -1 。
For example, a method for hydrogenating 4-hydroxybutyraldehyde comprises contacting the nickel catalyst with hydrogen and 4-hydroxybutyraldehyde. In some preferred embodiments of the present invention, the conditions of the contact reaction include: the contact pressure is 4.0-6.0MPa, the temperature is 170-220 ℃, and the proportion of the catalyst is 2-5%.
Compared with the prior art, the invention has the beneficial effects that:
firstly, in the nickel catalyst and the nickel catalyst prepared by the preparation method provided by the invention, the content of the active component nickel is higher, and the content of nickel with the particle size of 2 nm-5 nm is more than 75%;
secondly, the nickel catalyst provided by the invention and the nickel catalyst prepared by the preparation method provided by the invention have higher hydrogenation activity and selectivity and good catalytic performance.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The raw material reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be obtained by commercial routes.
Example 1
The carrier used in example 1 was spherical alpha-Al 2 O 3 An alumina carrier with an average particle diameter of 2.2mm, a pore diameter of 16nm and a specific surface area of 140m 2 Per g, pore volume of 0.79mg/g, water absorption of 0.78g/g, bulk density of 0.53g/cm 3 。
A method for preparing a nickel catalyst, comprising the steps of:
1) Weighing 200g of nickel nitrate, and fixing the volume to 100mL by using deionized water to prepare a nickel-containing solution;
2) Placing 200g of the carrier in a pressure-resistant reaction kettle, vacuumizing the reaction kettle to 0.3atm, and keeping the vacuum degree for 10min;
3) Adding the nickel-containing solution prepared in the step 1) into a reaction kettle under the vacuum degree (namely 0.3 atm), keeping the vacuum degree for 10min, and greatly oscillating the reaction kettle up and down during the vacuum degree, thereby finishing the vacuum pumping treatment;
4) The reaction kettle is firstly restored to normal pressure and then pressurized to 10atm, the pressure is kept for 10min, and the reaction kettle is greatly vibrated up and down during the period, so that the pressurization treatment is completed;
5) The vacuum-pumping treatment of the step 3) and the pressurizing treatment of the step 4) are repeated for 5 times in total, namely the vacuum-pumping treatment and the pressurizing treatment are performed for 6 times in total in the embodiment;
6) Drying the system obtained in the step 5) at 100 ℃ for about 6 hours to obtain a catalyst precursor;
7) Roasting the catalyst precursor prepared in the step 6) at 450 ℃ for 8 hours;
8) With N 2 ：H 2 Reducing the calcined product obtained in step 7) at 450 ℃ for 12 hours by using a mixed gas having a molar ratio =0.3 of 1, so as to reduce the nickel oxide to elemental nickel, thereby obtaining a supported nickel catalyst.
ICP analysis is carried out on the prepared nickel catalyst, and the nickel content in the nickel catalyst is measured to be 16.7wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with the particle size of 2 nm-5 nm is 92wt%.
Example 2
The preparation process in example 1 was followed except that the average particle diameter of the carrier used in this example was 0.5mm.
ICP analysis is carried out on the prepared nickel catalyst, and the nickel content in the nickel catalyst is measured to be 16.9wt%; TEM analysis of the prepared catalyst shows that the content of nickel with the particle size of 2-5nm is 88wt%.
Example 3
The preparation process in example 1 was followed except that the average particle diameter of the carrier used in this example was 10mm.
ICP analysis is carried out on the prepared nickel catalyst, and the content of nickel in the nickel catalyst is measured to be 16.6wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with the particle size of 2-5nm is 86wt%.
Example 4
The preparation process in example 1 was followed except that the average particle diameter of the support used in this example was 7nm.
ICP analysis is carried out on the prepared nickel catalyst, and the content of nickel in the nickel catalyst is measured to be 16.5wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with the particle size of 2-5nm is 85wt%.
Example 5
The preparation process in example 1 was followed except that the average particle diameter of the support used in this example was 23nm.
ICP analysis is carried out on the prepared nickel catalyst, and the content of nickel in the nickel catalyst is measured to be 16.3wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with a particle size of 2-5nm is 82wt%.
Example 6
The production process in example 1 was referred to, except that the evacuation treatment and the pressurization treatment were performed 1 time in total in this example.
ICP analysis is carried out on the prepared nickel catalyst, and the content of nickel in the nickel catalyst is measured to be 17.0wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with the particle size of 2-5nm is 76wt%.
Example 7
The production process in example 1 was referred to, except that the evacuation treatment and the pressurization treatment were performed 2 times in total in this example.
ICP analysis is carried out on the prepared nickel catalyst, and the content of nickel in the nickel catalyst is measured to be 16.9wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with the particle size of 2 nm-5 nm is 78wt%.
Example 8
The production process in example 1 was referred to, except that the evacuation treatment and the pressurization treatment were performed 10 times in total in this example.
ICP analysis is carried out on the prepared nickel catalyst, and the nickel content in the nickel catalyst is measured to be 15.7wt%; TEM analysis of the prepared nickel catalyst shows that the nickel content in the catalyst with a particle size of 2-5nm is 88wt%.
Comparative example 1
The support used in this comparative example was the same as in example 1.
1) Same as example 1;
2) Placing the carrier in a container with normal pressure;
3) Adding the nickel-containing solution prepared in the step 1) into the container filled with the carrier in the step 2) under normal pressure, and keeping for 15min;
4) Drying, calcination and reduction treatment were carried out in the same manner as in example 1.
ICP analysis is carried out on the prepared nickel catalyst, and the nickel content in the nickel catalyst is measured to be 15.0wt%; TEM analysis of the prepared catalyst shows that the content of nickel with the particle size of 2-5nm is 58wt%.
Comparative example 2
The support used in this comparative example was the same as in example 1.
1) Same as example 1;
2) Adding the carrier into a reaction kettle without carrying out vacuum treatment on the carrier;
3) Adding the nickel-containing solution prepared in the step 1) into a reaction kettle under 0.3atm, keeping the vacuum degree for 10min, and greatly oscillating the reaction kettle up and down during the vacuum degree, thereby finishing the vacuum pumping treatment;
4) The subsequent process was the same as in example 1.
ICP analysis is carried out on the prepared nickel catalyst, and the content of nickel in the nickel catalyst is 14.3wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with the particle size of 2 nm-5 nm is 72wt%.
Comparative example 3
The support used in this comparative example was the same as in example 1.
1) Same as example 1;
2) Same as example 1;
3) Adding the nickel-containing solution prepared in the step 1) into a reaction kettle under the vacuum degree (namely 0.3 atm), maintaining for 60min under the vacuum degree, and greatly oscillating the reaction kettle up and down during the period, thereby finishing the vacuum pumping treatment;
4) No pressurization treatment is carried out;
5) The system obtained in step 3) was subjected to drying, firing and reduction treatment in the same manner as in example 1.
ICP analysis is carried out on the prepared nickel catalyst, and the nickel content in the nickel catalyst is 14.0wt%; TEM analysis of the prepared nickel catalyst shows that the content of nickel with the particle size of 2-5nm is 76wt%.
Example of catalytic test
The nickel catalysts prepared in the above examples and comparative examples were subjected to selective hydrogenation performance test. The test method comprises the following steps: the raw material is 4-hydroxy butyraldehyde; 100g of 4-hydroxybutyraldehyde is put into a high-pressure reaction kettle, 3g of nickel catalyst is added, and hydrogenation reaction is carried out under the conditions that the pressure is 4-6Mpa, the temperature is 200 ℃ and the reaction time is 6 hours. The test results are shown in table 1.
TABLE 1 catalytic Properties of different catalysts
As can be seen from the data of the examples in Table 1, the catalyst obtained by selecting the carrier with the average particle size of 2-5nm and performing vacuum pumping treatment and pressurization treatment more than 5 times has better effect; it can be seen from the comparative example data in table 1 that a high-pressure vessel should be used, the carrier needs to be pressurized, and the reaction kettle is returned to normal pressure through step 4), and then the catalyst obtained after pressurization treatment has better effect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the appended claims, and changes can be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A nickel catalyst is characterized by comprising a carrier and an active component nickel, wherein the content of the active component nickel is 5-30 wt% based on the total weight of the nickel catalyst.
2. The nickel catalyst according to claim 1, wherein the nickel having a particle size of 2nm to 5nm is present in an amount of 75wt% to 100wt%, based on the total weight of nickel.
3. The nickel catalyst of claim 2, wherein the support is alpha-Al 2 O 3 、β-Al 2 O 3 、γ-Al 2 O 3 One or more of; the pore diameter of the carrier is 5 nm-20 nm.
4. A method for preparing the nickel catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) Pretreating the carrier under vacuum condition;
(2) Adding a nickel-containing solution to the pretreated support;
(3) Carrying out vacuum pumping treatment and pressurization treatment on the system prepared in the step (2),
(4) Drying the system prepared in the step (3) to obtain a catalyst precursor;
(5) And (5) roasting and reducing the catalyst precursor prepared in the step (4) to obtain the nickel catalyst.
5. The method for preparing a nickel catalyst according to claim 4, wherein in the step (3), the vacuuming conditions include an absolute pressure of 0 to 0.5atm; the time is 5min to 30min.
6. The method for producing a nickel catalyst according to claim 4, wherein the pressure treatment conditions in the step (3) include: absolute pressure is 1-20 atm; the time is 5min to 30min.
7. The method for producing a nickel catalyst according to claim 4, wherein in the step (4), the conditions of the drying treatment include: the drying temperature is 80-120 ℃.
8. The method for preparing the nickel catalyst according to claim 4, wherein in the step (5), the roasting temperature is 200-500 ℃, and the roasting time is 2-20 h; the temperature of the reduction treatment is 300-500 ℃, and the reduction time is 2-20 h; the reducing gas used for the reduction treatment is a mixed gas of nitrogen and hydrogen.
9. Use of a nickel catalyst according to any of claims 1 to 3 in hydrogenation.
10. A method for selective hydrogenation of pyrolysis gasoline, characterized in that, the nickel catalyst of any one of claims 1 to 3 is used to contact and react with hydrogen and pyrolysis gasoline, and the reaction pressure is 2.0 MPa-3.0 MPa.
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| CN108855128A (en) * | 2017-05-15 | 2018-11-23 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN112691671A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method thereof |
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| CN113087595A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Method for preparing alcohol compound by hydrogenation of carbonyl-containing compound |
| CN114433095A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
| CN114433094A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | High-activity nickel catalyst and preparation method and application thereof |
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| CN112691671A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method thereof |
| CN112691672A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Eggshell catalyst and preparation method and application thereof |
| CN113087595A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Method for preparing alcohol compound by hydrogenation of carbonyl-containing compound |
| CN114433095A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
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