CN117899875A - High-selectivity reforming generated oil hydrogenation catalyst and preparation method and application thereof - Google Patents

High-selectivity reforming generated oil hydrogenation catalyst and preparation method and application thereof Download PDF

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CN117899875A
CN117899875A CN202311835620.2A CN202311835620A CN117899875A CN 117899875 A CN117899875 A CN 117899875A CN 202311835620 A CN202311835620 A CN 202311835620A CN 117899875 A CN117899875 A CN 117899875A
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nio
catalyst
mass ratio
hydrogenation
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楼巧琳
曹澎锐
罗海林
奚俊
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Ningbo Zhongjin Petrochemical Co ltd
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    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalytic materials, and discloses a hydrogenation catalyst for high-selectivity reforming generated oil, a preparation method and application thereof. The catalyst of the invention comprises an alumina carrier, and monocrystal Ni particles, ni-Si and Ni-Si/SiO 2 loaded on the carrier. The carrier of the catalyst is loaded with the monocrystal Ni particles, ni-Si and NiSi/SiO 2, and the Ni-Si and NiSi/SiO 2 play a role in blocking the monocrystal Ni particles and the NiSi and SiO 2 in the NiSi/SiO 2 have strong interaction, so that the catalyst is applied to hydrogenation catalytic de-olefine of reforming generated oil, and has the advantages of high catalytic activity, high hydrogenation selectivity of olefine, difficult carbon deposition and low cost, thereby effectively improving the efficiency, reducing the aromatic hydrocarbon loss and remarkably prolonging the service life in the de-olefine process of reforming generated oil.

Description

High-selectivity reforming generated oil hydrogenation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalytic materials, in particular to a hydrogenation catalyst for high-selectivity reforming generated oil, a preparation method and application thereof.
Background
Catalytic reforming is one of the main processes for producing aromatic hydrocarbon, and the reformed oil can be used for producing products such as benzene, toluene, xylene (BTX) and the like after extraction and separation. Currently 70-80% of the world's BTX is derived from catalytic reforming processes. With the continuous development of catalyst technology and catalytic reforming technology, especially the progress of multi-metal catalyst and low-pressure continuous reforming technology, the yield and production efficiency of aromatic hydrocarbon are improved, and meanwhile, the content of olefin in the reformed oil is increased. These olefins not only affect the quality of the reformate, but also contaminate the subsequent extraction solvent; in the processing process, olefin is easily deposited on the surface of the heat exchanger through polymerization, so that the working efficiency of the heat exchanger is reduced; during the adsorption separation of the xylene, the olefin can enter the pore canal of the molecular sieve adsorbent, thereby influencing the separation effect of the adsorbent. Therefore, the olefins contained in the reformate must be removed to a low level to ensure the quality of the aromatic product and to reduce the impact on subsequent processing equipment.
There are two current methods for removing olefins from reformate: firstly, a catalytic adsorption method (molecular sieve, clay and modified clay), wherein the used adsorbent has short service life, frequent replacement, unrenewable clay and other adsorbents, and high solid waste treatment pressure; the other method is a hydrogenation catalysis method, which generally adopts noble metals such as Pt, la and the like as active components to carry out hydrogenation catalysis on reformed oil, and the method has the advantages of high catalyst activity, low reaction temperature, small reaction pressure and high volume space velocity ratio, but the catalyst of the method has the problems of high price, easy carbon deposition, short operation period and the like.
In order to reduce the production cost, the scholars have also studied a hydrogenation catalytic method for reforming the generated oil by using Ni, co, mo and the like as active components, such as Zhang Kongyuan and the like, and a NiO/Al2O 3 catalyst is prepared by adopting a wet mixing and kneading method and is applied to the dealkenation of the reformed generated oil (Zhang Kongyuan, zheng Yun, he Jinkang and the like). The metal elements have abundant reserves and relatively low price, and are suitable for large-scale industrialized application. However, the method needs to be carried out under the conditions of higher reaction temperature and lower volume-space ratio, has large aromatic hydrocarbon loss and higher energy consumption, and can also generate the problems of carbon deposition deactivation and the like along with the operation of the reaction.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hydrogenation catalyst for high-selectivity reforming generated oil, and a preparation method and application thereof. The carrier of the catalyst is loaded with the monocrystal Ni particles, ni-Si and Ni-Si/SiO 2, and the Ni-Si/SiO 2 play a role in blocking the monocrystal Ni particles and have strong interaction with the SiO 2 in the Ni-Si/SiO 2, so that the catalyst is applied to hydrogenation catalytic de-olefine of reformed oil, and has the advantages of high catalytic activity, high hydrogenation selectivity of olefine, difficult carbon deposition and low cost, thereby effectively improving efficiency, reducing aromatic hydrocarbon loss and remarkably prolonging service life in the de-olefine process of reformed oil.
The specific technical scheme of the invention is as follows:
In a first aspect, the present invention provides a high selectivity reformate hydrogenation catalyst comprising an alumina support and monocrystalline Ni particles, ni-Si and Ni-Si/SiO 2 supported on the alumina support; the Ni-Si and Ni-Si/SiO 2 are spaced apart between single crystal Ni particles.
The catalyst takes alumina as a carrier, single crystal Ni particles, ni-Si and Ni-Si/SiO 2 are uniformly loaded on the alumina (along with the increase of the silicidation temperature, the formed silicide relates to the following change Buddhist: ni 2Si、NiSi、NiSi2, the Ni-Si in the catalyst of the invention represents the mixture of the compounds, wherein the NiSi is the main component), and a large number of single crystal Ni particles are blocked by the Ni-Si and the Ni-Si/SiO 2. In the hydrogenation olefin removal process of Ni catalytic reforming generated oil, in general, the smaller the grain size of single crystal Ni, the better the dispersibility and the higher the hydrogenation activity. In the catalyst, part of Ni and Si are combined and converted into Ni-Si, so that a certain isolation effect is achieved on monocrystal Ni particles, the Ni particle size is reduced, and the reaction activity is improved. Furthermore, more importantly, we have found that the above barrier effect can also significantly improve the selectivity of the catalyst for the hydrogenation of olefins. The reason is that the reforming generated oil mainly comprises aromatic hydrocarbon and a small amount of olefin, and in the hydrogenation olefin removal process, the olefin is adsorbed in units, namely, the olefin can be activated after occupying one active point on the catalyst, and hydrogenation reaction is carried out; the arene is multi-site adsorption, and the arene needs to occupy a plurality of active sites on the catalyst to be hydrogenated. According to the invention, due to the interval effect of the Ni-Si compound on the monocrystal Ni particles, different active sites are far apart, and arene molecules are not easy to occupy a plurality of active sites of monocrystal Ni at the same time, so that the reactivity of arene molecules can be effectively reduced while the reactivity of olefin is improved, the selectivity of hydrogenation and olefin removal of reformed oil is improved, and the loss of arene is reduced. Meanwhile, the interval action of the Ni-Si compound on the monocrystal Ni particles can also prevent the monocrystal Ni particles from being combined with each other so as to avoid reduction of active sites of olefin hydrogenation reaction, thereby delaying deactivation or carbon deposition and effectively prolonging the service life of the catalyst.
In addition, the present invention selects Ni-Si and Ni-Si/SiO 2 because it can readjust the catalytic activity of the catalyst in the hydrogenation of olefins. (1) First, in the ni—si compound, when Si atoms are inserted into the lattice of Ni, d-orbitals of the Ni atoms and p-orbitals of the Si atoms interact, resulting in an integer decrease in energy jump, narrowing of d-energy band, and shift of resonance energy level in a direction of high binding energy, thereby causing coupling between the energy state of Si and the Ni orbitals, and finally forming a unique bonding state which is more compact than both the original states. The bonding tracks are filled to strengthen bonds, so that the Ni-Si compound has higher electric conductivity and heat conductivity and strong stability. Moreover, the geometry and the electronic structure of Ni are changed, so that the Ni has good reactivity and high chemical stability; (2) Second, the present invention has found that Ni-Si in Ni-Si/SiO 2 and SiO 2 have strong interactions in olefin hydrogenation reactions. The strong interaction refers to a special synergistic effect existing between the Ni-Si interface and the SiO 2 interface, and the essence of the strong interaction is that the redistribution of charges and the mass transmission occur at the Ni-Si interface and the SiO 2 interface, so that the electronic structure and the morphology of the catalyst are changed, the adsorption behavior of reactants and the formation of reaction intermediates are further influenced, and the whole reaction path and the catalytic performance of the catalyst are finally changed. After the Ni-Si is compounded with the SiO 2, the redistribution of charges occurs at the interface between the Ni-Si and the SiO 2, so that the electronic structure and the morphology of the catalyst are changed. Specifically: when Ni-Si is combined with SiO 2, siO 2 imparts some charge to Ni-Si and can affect the electron cloud density of the adsorbed gas, thereby adjusting the catalytic activity of the catalyst. According to the invention, researches show that Ni-Si/SiO 2 with strong interaction can promote the adsorption capacity to hydrogen in the hydrogenation catalytic reaction of the reformed oil, improve the reaction activity, and facilitate reducing the generation of byproducts such as polyolefin, heavy aromatic hydrocarbon and the like, thereby reducing the carbon deposition risk of the catalyst.
Preferably, the specific surface area of the high-selectivity reforming generated oil hydrogenation catalyst is 150-260m 2/g, the pore volume is 0.3-0.7cm 3/g, wherein the pores with the pore diameter of 5-10nm account for 60-80% of the total pore volume of the catalyst.
In a second aspect, the present invention provides a method for preparing a hydrogenation catalyst for high selectivity reformate, comprising the steps of:
1) Mixing SiO 2 powder with modified nickel solution, regulating pH to be alkaline, heating for reaction, and carrying out aftertreatment, calcination and crushing to obtain NiO/SiO 2 composite powder.
The modified nickel solution contains nickel acetylacetonate, ethylene glycol has the functions of a solvent and a dispersing agent, siO 2 powder is added and mixed, then the pH is regulated to be alkaline and the mixture is heated for reaction, at the moment, the nickel acetylacetonate undergoes hydrolysis reaction, nickel hydroxide is separated out from the solvent and is uniformly deposited or adsorbed on the surface of SiO 2 powder, the solvent, generated organic byproducts and the like are removed after post treatment, nickel hydroxide can be dehydrated to generate nickel oxide through calcination, impurities are further removed, nickel oxide can be firmly loaded on SiO 2, and NiO/SiO 2 composite powder can be obtained after crushing.
2) The alumina powder and the NiO/SiO 2 composite powder are uniformly mixed, ni (NO 3)2 aqueous solution is added and stirred into paste, and the paste is dried, ground, molded and calcined to obtain the alumina loaded with NiO and NiO/SiO 2.
The paste in the step 2) contains alumina, niO/SiO 2 composite powder and Ni (NO 3)2 and water, after drying, the water is removed, the obtained solid mixture is ground, pressed into tablets and formed, and then calcined, and the formed solid mixture contains Ni (NO 3)2 is decomposed at high temperature to produce NiO and is loaded in the alumina and NiO/SiO 2 composite powder, so that the alumina loaded with NiO and NiO/SiO 2 is prepared.
In the application of the invention, a two-step method is adopted to load Ni element on the catalyst, namely in the step 1) and the step 2), and the following reasons are mainly adopted: firstly, if all Ni elements are added in the step 1), the NiO content in the prepared NiO/SiO 2 composite powder is too high, the composite powder is easy to form tablets on SiO 2, the particle size of the produced NiO is too large, niO cannot be effectively and uniformly dispersed in the subsequent step 2), and the effect of Ni components in the catalyst is seriously reduced; secondly, if all Ni elements are added in step 2), i.e., the nickel nitrate aqueous solution containing all Ni elements is added after the alumina powder is mixed with the SiO 2 component, although it is possible to produce alumina loaded with NiO uniformly dispersed, it may result in a relatively low NiO content adsorbed on SiO 2, so that the ni—si/SiO 2 component generated in step 3) is too small to effectively exert a strong interaction effect.
3) The method comprises the steps of firstly carrying out reduction treatment on the alumina loaded with NiO and NiO/SiO 2 in a reducing atmosphere, then carrying out siliconizing treatment in an SiH 4/H2 -containing atmosphere, then carrying out reduction treatment in the reducing atmosphere and cooling to obtain the alumina loaded with monocrystal Ni particles and NiSi/SiO 2, namely the hydrogenation catalyst for reforming generated oil.
Under the condition of high-temperature reducing atmosphere, niO is firstly reduced into single Ni metal particles, then part of Ni reacts with silane to generate silicide (called Ni-Si compound) of Ni metal, and firstly, ni-Si can play a role in blocking the single-crystal Ni particles, so that the selectivity and the service life of the catalyst are improved; secondly, ni-Si has a strong interaction effect with SiO 2, so that the catalytic performance can be adjusted.
Preferably, in the step 1), the mass ratio of NiO in the NiO/SiO 2 composite powder is 20-30%.
If the proportion is too high, niO crystal grains loaded in SiO 2 are too large, even connected into slices, and cannot be effectively dispersed, so that the catalytic effect is affected; if the proportion is too low, the content of Ni-Si/SiO 2 in the finally prepared catalyst is too small, and the effect of improving the reaction effect by utilizing strong interaction is not achieved.
Preferably, in the step 1), the modified nickel solution is glycol solution of nickel acetylacetonate, and the mass ratio of glycol to nickel acetylacetonate is 20-30:1.
Preferably, in step 1), the alkaline pH is 9-10.
Preferably, in step 1), the heating reaction is carried out at a temperature of 110-130 ℃ for a time of 1-2h.
Preferably, in step 1), the post-treatment is cooling, filtering and washing to neutrality.
Preferably, in step 1), the calcination temperature is 500-600 ℃ and the time is 2-3h.
In step 1), calcination at this temperature can remove moisture, including adsorbed water and NiO crystal water, and the NiO is supported on SiO 2, and prevents sintering, while keeping NiO relatively reactive and relatively easy for hydrogen reduction.
Preferably, in the step 2), the mass ratio of Al 2O3 in the alumina loaded with NiO and NiO/SiO 2 is 60-70%, the mass ratio of NiO is 20-30%, and the mass ratio of SiO 2 is 10-20%.
If the NiO content is too high, ni particles are easy to aggregate, so that the Ni particle size in the catalyst is too large, and the catalytic effect is affected; if the NiO content is too low, it results in too low a Ni particle content in the catalyst, affecting the catalytic activity. If the SiO 2 content is too high, the Ni-Si/SiO 2 content with relatively large particle size in the catalyst is more, and the diffusion of adverse reaction gas in the catalyst is influenced, and meanwhile, the uniform distribution of Ni is influenced; if the SiO 2 content is too low, the Ni-Si/SiO 2 content in the catalyst is small, and the effect of strong interaction cannot be effectively exerted.
Preferably, in step 2), the drying temperature is 100-120 ℃ and the drying time is 10-15h.
Preferably, in step 2), the calcination temperature is 500-600 ℃ and the time is 4-6h.
In step 2), the calcination conditions can further remove moisture, while decomposing Ni (NO 3)2 to form NiO, and maintaining the reactivity of NiO, without changing the NiO properties on the original supported SiO 2).
Preferably, in the step 3), the alumina loaded with NiO and NiO/SiO 2 is firstly slowly heated to 350-380 ℃ in the hydrogen atmosphere for reduction treatment for 4-6H, then is siliconized for 20-30min in the SiH 4/H2 atmosphere with the volume ratio of SiH 4 to H 2 being 5-15%, and then is cooled to normal temperature in the hydrogen atmosphere.
In a third aspect, the invention provides an application of the high-selectivity reformate hydrogenation catalyst in hydrogenation catalytic olefin removal of reformate.
Compared with the prior art, the invention has the following technical effects:
(1) The carrier of the catalyst is loaded with the monocrystal Ni particles, the Ni-Si and the Ni-Si/SiO 2, wherein the Ni-Si and the Ni-Si/SiO 2 play a role in blocking the monocrystal Ni particles, so that the catalytic activity of the catalyst in the hydrogenation catalytic de-olefine process of reforming generated oil is high, the hydrogenation selectivity of olefin is improved, carbon deposition is reduced, and the service life is prolonged.
(2) Part of Ni in the catalyst is siliconized into Ni-Si compound, and the geometrical structure and the electronic structure of Ni are readjusted to change; meanwhile, the Ni-Si and the SiO 2 have strong interaction, so that the catalytic activity and chemical stability of the catalyst can be improved.
(3) The catalyst does not use noble metal elements, so the catalyst has the advantage of low cost and is suitable for industrialized popularization.
Detailed Description
The invention is further described below with reference to examples.
A hydrogenation catalyst for high-selectivity reforming generated oil comprises an alumina carrier, and monocrystal Ni particles, ni-Si and Ni-Si/SiO 2 loaded on the alumina carrier; the Ni-Si and Ni-Si/SiO 2 are spaced apart between single crystal Ni.
Preferably, the specific surface area of the catalyst is 150-260m 2/g, the pore volume is 0.3-0.7cm 3/g, wherein the pores with the pore diameter of 5-10nm account for 60-80% of the total pore volume of the catalyst.
The preparation method of the hydrogenation catalyst for the high-selectivity reforming generated oil comprises the following steps:
1) Mixing SiO 2 powder and modified nickel solution (prepared from glycol and nickel acetylacetonate with the mass ratio of 20-30:1), regulating pH to be alkaline (preferably 9-10), heating for reaction (preferably 110-130 ℃ C., 1-2 h), cooling, filtering, washing to be neutral, calcining (preferably 500-600 ℃ C., 2-3 h), and crushing to obtain NiO/SiO 2 composite powder (the mass ratio of NiO is preferably 20-30%).
2) The Al 2O3 powder and the NiO/SiO 2 composite powder are uniformly mixed, ni (NO 3)2 aqueous solution is added and stirred into paste, and the paste is dried (preferably 100-120 ℃ C., 10-15 h), ground, formed and calcined (preferably 500-600 ℃ C., 4-6 h) to obtain the alumina loaded with NiO/SiO 2 (the mass ratio of Al 2O3 is preferably 60-70%, the mass ratio of NiO is preferably 20-30%, and the mass ratio of SiO 2 is preferably 10-20%).
3) The alumina loaded with NiO/SiO 2 is firstly slowly heated to 350-380 ℃ in hydrogen atmosphere for reduction treatment for 4-6h, then is siliconized for 20-30min in SiH 4/H2 with the volume ratio of 5-15%, and then is reduced and cooled in hydrogen atmosphere, thus obtaining the alumina loaded with monocrystal Ni particles and Ni-Si/SiO 2, namely the oil hydrogenation catalyst for reforming.
Example 1
1) Dissolving nickel acetylacetonate in glycol according to the mass ratio of 1:25 to obtain a modified nickel solution, adding white carbon black powder into the modified nickel solution according to the mass ratio of 1:26 under stirring, slowly adding 10% sodium carbonate aqueous solution with the mass ratio concentration until the pH value is 9.5 under continuous stirring, heating the obtained mixed solution to 120 ℃, reacting for 1.5h, cooling, filtering, washing until the reaction is completed, heating the obtained solid to 550 ℃, calcining for 2.5h, and grinding to obtain NiO/SiO 2 composite powder (the mass ratio of NiO is 25.3%).
2) Mixing Al 2O3 dry glue powder and NiO/SiO 2 composite powder prepared in the step 1) according to the mass ratio of 3:1:6, adding Ni (NO 3)2 aqueous solution with the concentration of 40wt% into a lake shape, stirring, drying at 110 ℃ for 12 hours, grinding, tabletting and forming, and calcining the obtained formed product at 550 ℃ for 5 hours to obtain a composition (the mass ratio of Al 2O3 is 60.2%, the mass ratio of NiO is 25.5% and the mass ratio of SiO 2 is 14.3%).
3) And (3) slowly heating the composition prepared in the step (2) to 360 ℃ in an H 2 atmosphere for reduction for 5 hours, continuously introducing SiH 4/H2 atmosphere with the volume ratio of 10% for siliconizing for 25 minutes, and continuously cooling to normal temperature in the H 2 atmosphere to prepare the reformed oil hydrogenation catalyst.
Example 2
1) Dissolving nickel acetylacetonate into glycol according to the mass ratio of 1:30 to obtain a modified nickel solution, and stirring according to the mass ratio of 1:22.5 adding white carbon black powder into modified nickel solution, slowly adding sodium carbonate aqueous solution with mass ratio concentration of 10% until pH value is 9 under continuous stirring, heating the obtained mixed solution to 110 ℃, reacting for 1h, cooling, filtering, washing until neutral after the reaction is finished, heating the obtained solid to 500 ℃ for calcining for 2h, and grinding to obtain NiO/SiO 2 composite powder (the mass ratio of NiO is 20.4%).
2) Mixing Al 2O3 dry glue powder and NiO/SiO 2 composite powder prepared in the step 1) uniformly according to the mass ratio of 5.6:1:8.4, adding Ni (NO 3)2 aqueous solution with the concentration of 40wt% into a lake shape, drying at 100 ℃ for 10 hours, grinding, tabletting and forming, and calcining the obtained formed product at 500 ℃ for 4 hours to obtain a composition (the mass ratio of Al 2O3 is 69.7%, the mass ratio of NiO is 20.2% and the mass ratio of SiO 2 is 10.1%).
3) And (3) slowly heating the composition prepared in the step (2) to 350 ℃ under the H 2 atmosphere for reduction for 5 hours, continuously introducing SiH 4/H2 atmosphere with the volume ratio of 10% for siliconizing for 20 minutes, and continuously cooling to normal temperature under the H 2 atmosphere to prepare the reformed oil hydrogenation catalyst.
Example 3
1) Dissolving nickel acetylacetonate in glycol according to the mass ratio of 1:20 to obtain a modified nickel solution, adding white carbon black powder into the modified nickel solution according to the mass ratio of 1:27 under stirring, slowly adding 10% sodium carbonate aqueous solution with the mass ratio concentration until the pH value is 10 under continuous stirring, heating the obtained mixed solution to 130 ℃, reacting for 2 hours, cooling, filtering, washing until the reaction is neutral, heating the obtained solid to 600 ℃ to calcine for 3 hours, and grinding to obtain NiO/SiO 2 composite powder (the mass ratio of NiO is 29.8%).
2) Mixing Al 2O3 dry rubber powder and NiO/SiO 2 composite powder prepared in the step 1) uniformly in sequence according to the mass ratio of 2.1:1:2.4, adding Ni (NO 3)2 aqueous solution with the concentration of 40wt% into a lake shape, drying at 120 ℃ for 15 hours, grinding, tabletting and forming, and calcining the obtained formed product at 600 ℃ for 6 hours to obtain a composition (the mass ratio of Al 2O3 is 60.6%, the mass ratio of NiO is 20.6%, and the mass ratio of SiO 2 is 18.8%).
3) And (3) slowly heating the composition prepared in the step (2) to 380 ℃ under the H 2 atmosphere for reduction for 6 hours, continuously introducing SiH 4/H2 atmosphere with the volume ratio of 10% for siliconizing for 30 minutes, and continuously cooling to normal temperature under the H2 atmosphere to prepare the reformed oil hydrogenation catalyst.
Comparative example 1
Compared with example 1, the difference is that step 1) in example 1 is omitted, i.e., the prepared reformate hydrogenation catalyst does not contain Ni-Si/SiO 2, i.e., al 2O3 is used as a carrier, and Ni-Si are used as active ingredients.
1) Adding Ni (NO 3)2 aqueous solution with concentration of 40wt% into Al 2O3 dry glue powder according to mass ratio of 7:18, stirring into lake shape, drying at 110 ℃ for 12 hours, grinding, tabletting and forming, and calcining the obtained formed product at 550 ℃ for 5 hours to obtain a composition (the mass ratio of Al 2O3 is 70.2% and the mass ratio of NiO is 29.8%).
2) And (3) slowly heating the composition prepared in the step (2) to 360 ℃ in an H 2 atmosphere for reduction for 5 hours, continuously introducing SiH 4/H2 atmosphere with the volume ratio of 10% for siliconizing for 25 minutes, and continuously cooling to normal temperature in the H 2 atmosphere to prepare the reformed oil hydrogenation catalyst.
Comparative example 2
In comparison with example 1, the difference is that Ni (NO 3)2 aqueous solution) was not added in step 2), but replaced with pure water, so that the prepared reformate hydrogenation catalyst contained too low Ni and ni—si active ingredients.
1) Dissolving nickel acetylacetonate in glycol according to the mass ratio of 1:25 to obtain a modified nickel solution, adding white carbon black powder into the modified nickel solution according to the mass ratio of 1:26 under stirring, slowly adding 10% sodium carbonate aqueous solution with the mass ratio concentration until the pH value is 9.5 under continuous stirring, heating the obtained mixed solution to 120 ℃, reacting for 1.5h, cooling, filtering, washing until the reaction is completed, heating the obtained solid to 550 ℃, calcining for 2.5h, and grinding to obtain NiO/SiO 2 composite powder (the mass ratio of NiO is 25.3%).
2) Mixing Al 2O3 dry glue powder and NiO/SiO 2 composite powder prepared in the step 1) according to the mass ratio of 3:1:6, adding the mixture into pure water, stirring the mixture into a lake shape, drying the mixture at 110 ℃ for 12 hours, grinding and tabletting the mixture to form, and calcining the formed product at 550 ℃ for 5 hours to obtain the composition (the mass ratio of Al 2O3 is 75.0%, the mass ratio of NiO is 6.2%, and the mass ratio of SiO 2 is 18.8%).
3) And (3) slowly heating the composition prepared in the step (2) to 360 ℃ in an H 2 atmosphere for reduction for 5 hours, continuously introducing SiH 4/H2 atmosphere with the volume ratio of 10% for siliconizing for 25 minutes, and continuously cooling to normal temperature in the H 2 atmosphere to prepare the reformed oil hydrogenation catalyst.
Comparative example 3
The only difference compared to example 1 is that the calcination temperatures in step 1) and step 2) are too low:
1) Dissolving nickel acetylacetonate in glycol according to the mass ratio of 1:25 to obtain a modified nickel solution, adding white carbon black powder into the modified nickel solution according to the mass ratio of 1:26 under stirring, slowly adding 10% sodium carbonate aqueous solution with the mass ratio concentration until the pH value is 9.5 under continuous stirring, heating the obtained mixed solution to 120 ℃, reacting for 1.5h, cooling, filtering, washing until the reaction is completed, heating the obtained solid to 400 ℃, calcining for 2.5h and grinding to obtain NiO/SiO 2 composite powder (the mass ratio of NiO is 25.1%).
2) Mixing Al 2O3 dry glue powder and NiO/SiO 2 composite powder prepared in the step 1) according to the mass ratio of 3:1:6, adding Ni (NO 3)2 aqueous solution with the concentration of 40wt% into a lake shape, stirring, drying at 110 ℃ for 12 hours, grinding, tabletting and forming, and calcining the obtained formed product at 400 ℃ for 5 hours to obtain a composition (the mass ratio of Al 2O3 is 60.3%, the mass ratio of NiO is 25.2%, and the mass ratio of SiO 2 is 14.5%).
3) And (3) slowly heating the composition prepared in the step (2) to 360 ℃ in an H 2 atmosphere for reduction for 5 hours, continuously introducing SiH 4/H2 atmosphere with the volume ratio of 10% for siliconizing for 25 minutes, and continuously cooling to normal temperature in the H 2 atmosphere to prepare the reformed oil hydrogenation catalyst.
Comparative example 4
The only difference compared to example 1 is that the calcination temperatures in step 1) and step 2) are too high:
1) Dissolving nickel acetylacetonate in glycol according to the mass ratio of 1:25 to obtain a modified nickel solution, adding white carbon black powder into the modified nickel solution according to the mass ratio of 1:26 under stirring, slowly adding 10% sodium carbonate aqueous solution with the mass ratio concentration until the pH value is 9.5 under continuous stirring, heating the obtained mixed solution to 120 ℃, reacting for 1.5h, cooling, filtering, washing until the reaction is completed, heating the obtained solid to 900 ℃ to calcine for 2.5h, and grinding to obtain NiO/SiO 2 composite powder (the mass ratio of NiO is 25.3%).
2) Mixing Al 2O3 dry glue powder and NiO/SiO 2 composite powder prepared in the step 1) according to the mass ratio of 3:1:6, adding Ni (NO 3)2 aqueous solution with the concentration of 40wt% into a lake shape, stirring, drying at 110 ℃ for 12 hours, grinding, tabletting and forming, and calcining the obtained formed product at 900 ℃ for 5 hours to obtain a composition (the mass ratio of Al 2O3 is 60.2%, the mass ratio of NiO is 25.2%, and the mass ratio of SiO 2 is 14.6%).
3) And (3) slowly heating the composition prepared in the step (2) to 360 ℃ in an H 2 atmosphere for reduction for 5 hours, continuously introducing SiH 4/H2 atmosphere with the volume ratio of 10% for siliconizing for 25 minutes, and continuously cooling to normal temperature in the H 2 atmosphere to prepare the reformed oil hydrogenation catalyst.
Performance testing
The hydrogenation catalysts prepared in each example and comparative example are adopted to carry out the test of removing olefin from the reformed oil, and the specific method is as follows: in a hydrogenation reactor, filling a hydrogenation catalyst, firstly, pretreating the hydrogenation catalyst by utilizing hydrogen, and under the condition of the pressure of 1.0MPa, raising the reduction temperature to 400 ℃ from room temperature at the speed of 2 ℃/min, and reducing the reaction temperature after the treatment for 4 hours. The reformed oil is conveyed to a depentanizer (the tower top pressure is 0.95MPa, the tower top temperature is 87 ℃, the tower bottom temperature is 215 ℃, the tower tray temperature is 160 ℃, the reflux ratio is 0.2), and the depentanizer is used for processing, and then the depentanized tower bottom oil (the main properties are shown in table 1) and hydrogen are respectively conveyed to a hydrogenation reactor; the experimental conditions are that the reaction temperature is 130 ℃, the reaction pressure is 1.1MPa, the volume space velocity is 10h -1, and the hydrogen-oil ratio is 23:1. And (5) after stabilizing for 6 hours, emptying, and taking a 2-hour accumulated sample.
TABLE 1
The pore structure parameters of the catalyst were analyzed by using a Tristar 3020 type adsorber from Micromertics in the united states, and the conditions were measured: the adsorption temperature is 350 ℃, the vacuum environment is 0.95 multiplied by 10 -6～0.12×10-5 MPa, and the adsorption time is 12 hours. The bromine index of the product of catalytic hydrogenation of the reformate is measured according to the GB/T1815-2019 national standard, and an AK-BR-1A bromine valence bromine index measuring instrument of Dalian Australian analytical instruments Co is adopted, wherein the unit of the bromine index of the sample is 100g Br/mg.
Firstly, an Agilent 7890A-PONA gas chromatograph of Agilent company of America is adopted to measure components such as aromatic hydrocarbon before and after catalytic hydrogenation of the reformate, and then a formula is utilized to calculate the damage rate of the aromatic hydrocarbon after catalytic hydrogenation of the reformate. Measurement conditions: the diameter of the PONA column is 50mm, the carrier gas is nitrogen, the initial temperature of the column box is 30 ℃, the temperature is raised to 150 ℃, the temperature raising rate is 5 ℃/min, the final temperature is kept for 2min, the flow rate of the capillary column is 2.5mL/min, and the split ratio of the sample inlet is 50:1. The temperature of the FID detector is 220 ℃, the hydrogen flow is 40mL/min, the air flow is 380mL/min, the carrier gas of the gas path connected with the FID for hydrocarbon analysis is nitrogen, the flow of the capillary column is 3mL/min, and the split ratio of the sample inlet is 50:1. The temperature of the TCD detector is 150 ℃, the gas path carrier gas connected with the TCD for inorganic gas analysis is helium, and the flow of the packed column is 20mL/min. The calculated formula of the aromatic hydrocarbon loss rate (x) is x= (1-w 1/w 2) x 100%, wherein w1 is the mass fraction of the aromatic hydrocarbon in the oil before catalytic hydrogenation after the reforming, w2 is the mass fraction of the aromatic hydrocarbon in the oil after catalytic hydrogenation after the reforming.
TABLE 2
As can be seen from Table 2, the catalysts prepared in examples 1-3 are used in the hydrogenation process of the reformate, and the bromine index and the aromatic hydrocarbon loss rate are both low, which indicates that the catalyst prepared by the invention has a high olefin hydrogenation effect, but the aromatic hydrocarbon hydrogenation effect is not obvious, so that the hydrogenation selectivity of the reformate is greatly improved.
The catalyst prepared in comparative example 1 does not contain Ni-Si/SiO 2 components, and only contains Ni and Ni-Si active components on an Al 2O3 carrier, but does not have strong interaction of Ni-Si/SiO 2, so that the performances of the catalyst such as hydrogen adsorption and the like are greatly reduced, and the bromine index and the aromatic hydrocarbon loss rate are higher in the hydrogenation process of the reformed oil.
The catalyst prepared in comparative example 2 contains too low Ni and Ni-Si active ingredients, and thus the catalytic hydrogenation activity of metallic Ni is not fully exerted, so that the bromine index and the aromatic hydrocarbon loss rate are high in the hydrogenation process of the reformed oil.
The catalyst prepared in comparative example 3 has low NiO load strength due to low calcination temperature, and the pore structure parameter of the finally generated catalyst has large change, and has high aromatic hydrocarbon loss rate and poor reaction selectivity due to high reaction activity in the hydrogenation process of the reformed oil; the catalyst prepared in comparative example 4 has the advantages that NiO is easy to sinter together and difficult to reduce due to the over-calcination temperature, the active ingredients of the catalyst prepared finally are unevenly distributed, the pore structure is compact, and the bromine index is larger due to low reactivity in the hydrogenation process of the reformed oil.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (10)

1. A high selectivity reformate hydrogenation catalyst characterized by: comprises an alumina carrier, and monocrystal Ni particles, ni-Si and Ni-Si/SiO 2 loaded on the alumina carrier; the Ni-Si and Ni-Si/SiO 2 are spaced apart between single crystal Ni particles.
2. The highly selective reformate hydrogenation catalyst of claim 1 wherein: the specific surface area is 150-260m 2/g, the pore volume is 0.3-0.7cm 3/g, wherein the pores with the pore diameter of 5-10nm account for 40-50% of the total pore volume of the catalyst.
3. A process for preparing a highly selective reformate hydrogenation catalyst according to claim 1 or 2, characterized by comprising the steps of:
1) Mixing SiO 2 powder with modified nickel solution, regulating pH to be alkaline, heating for reaction, and carrying out aftertreatment, calcination and crushing to obtain NiO/SiO 2 composite powder;
2) Uniformly mixing the aluminum oxide powder and the NiO/SiO 2 composite powder, adding Ni (NO 3）2 aqueous solution, stirring to form paste, drying, grinding, tabletting and forming, and calcining to obtain the aluminum oxide loaded with NiO and NiO/SiO 2;
3) The alumina loaded with NiO and NiO/SiO 2 is firstly reduced in a reducing atmosphere, then siliconized in an SiH 4/H2 -containing atmosphere, then reduced in a reducing atmosphere and cooled to obtain the alumina loaded with monocrystal Ni particles, ni-Si and Ni-Si/SiO 2, namely the hydrogenation catalyst for the reformed oil.
4. A method of preparation according to claim 3, characterized in that: in the step 1), the mass ratio of NiO in the NiO/SiO 2 composite powder is 20-30%.
5. The method according to claim 3 or 4, wherein: in the step 1), the modified nickel solution is glycol solution of nickel acetylacetonate, and the mass ratio of glycol to nickel acetylacetonate is 20-30:1.
6. The method according to claim 3 or 4, wherein: in the step (1) of the process,
The alkaline pH is 9-10;
The temperature of the heating reaction is 110-130 ℃ and the time is 1-2h;
the post-treatment comprises cooling, filtering and washing to neutrality;
the calcination temperature is 500-600 ℃ and the calcination time is 2-3h.
7. A method of preparation according to claim 3, characterized in that: in the step 2), the mass ratio of Al 2O3 in the alumina loaded with NiO and NiO/SiO 2 is 60-70%, the mass ratio of NiO is 20-30%, and the mass ratio of SiO 2 is 10-20%.
8. The preparation method according to claim 3 or 7, characterized in that: in the step 2) of the process, the process is carried out,
The drying temperature is 100-120 ℃ and the drying time is 10-15h;
The calcination temperature is 500-600 ℃ and the calcination time is 4-6h.
9. A method of preparation according to claim 3, characterized in that: in the step 3), firstly, the alumina loaded with NiO and NiO/SiO 2 is slowly heated to 350-380 ℃ in the hydrogen atmosphere for reduction treatment for 4-6H, then is siliconized for 20-30min in the SiH 4/H2 atmosphere with the volume ratio of SiH 4 to H 2 being 5-15%, and then is cooled to normal temperature in the hydrogen atmosphere.
10. Use of the highly selective reformate hydrogenation catalyst according to claim 1 or 2 or the highly selective reformate hydrogenation catalyst obtained by the method of any one of claims 3-9 in the hydrogenation-catalyzed dealkenation of reformate.
CN202311835620.2A 2023-12-27 2023-12-27 High-selectivity reforming generated oil hydrogenation catalyst and preparation method and application thereof Pending CN117899875A (en)

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