CN112844398B - Catalyst for hydrogenation of carbon four-superimposed product and preparation method thereof - Google Patents
Catalyst for hydrogenation of carbon four-superimposed product and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention relates to a catalyst for hydrogenation of a carbon four-stacked product and a preparation method thereof, wherein the catalyst comprises the following components in percentage by mass: 40-80wt% of gamma aluminum oxide, 0.5-40wt% of nickel oxide, 1-10wt% of lanthanum oxide, 0.1-6wt% of magnesium oxide and 0.1-6wt% of titanium dioxide; wherein, gamma alumina is used as a carrier, magnesium element, titanium element and lanthanum element are used as auxiliary agents, and nickel element is used as an active component. After the Ti modified alumina carrier is introduced, the interaction between the surface of the carrier and the metal active component Ni is enhanced, and the dispersion degree is obviously improved; the introduction of Mg reduces olefin polymerization and improves the coking resistance of the catalyst; the lanthanum is added to make nickel crystal grain smaller and contact surface of nickel oxide increased, crystal grain smaller, lattice defect, dislocation and the like are produced in recombination process, reducing temperature of catalyst is reduced, and at the same time promoting activity of catalyst.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for hydrogenation of a carbon four-stacked product and a preparation method thereof.
Background
The C4 resource in China is rich, the production capacity of oil refining chemical industry such as ethylene preparation by naphtha pyrolysis in petrochemical industry is greatly improved, and a large amount of by-products C4 are generated. At present, domestic utilization of C4 hydrocarbon is mainly focused on producing gasoline blending components of vehicle oil products such as alkylate, methyl tert-butyl ether (MTBE) and the like, but the MTBE can pollute underground water after leakage, and cause harm to human bodies and the environment. In 2017, the national promulgating two standards of GB 18351 "ethanol gasoline (E10) for vehicles" and GB 22030 "ethanol gasoline blending component oil for vehicles" prescribes that other organic oxygen-containing compounds must not be added into the ethanol gasoline for vehicles, which means that MTBE cannot be used as a gasoline blending component. The MTBE is mainly produced by using isobutene in China, and the isobutene is greatly excessive due to popularization of ethanol gasoline, so that the industrial chain of the downstream of C4 is interrupted. Conversion of isooctane as a high quality, high octane gasoline blending component is one of the effective solutions to solve the current dilemma by utilizing "superposition-hydrogenation" (indirect alkylation) technology.
The indirect alkylation technology integrates two processes of C4 olefin catalytic polymerization and hydrogenation saturation of a polymerization product, and hydrogenation of the polymerization product is an important step for guaranteeing that the content of olefin in blending components of the refinery gasoline meets the requirement. Compared with reforming of a superposition device, research on catalyst development and process improvement, the method has relatively less research on hydrogenation of superposition products, the content of olefin in the superposition products almost reaches 100%, and in the hydrogenation reaction process, the key is to regulate the reaction activity of the catalyst, control the reaction temperature rise and inhibit side reactions such as polymerization, isomerization and cracking.
CN1211458C discloses a method for producing isooctane and liquefied petroleum gas for vehicles by mixing carbon tetraoligomerization-hydrogenation. The solid phosphoric acid catalyst is used for carrying out superposition reaction, the catalyst of nickel, molybdenum or nickel and tungsten loaded by alumina is used for carrying out hydrogenation reaction on a fixed bed hydrogenation device, and isooctene is hydrogenated to generate isooctane under proper reaction conditions and the action of the hydrogenation catalyst. At the reaction temperature of 200-300 ℃, the reaction pressure of 2.5-6.0MPa, the hydrogen-oil ratio of 100:1-800:1 and the airspeed of 1.0-5.0h -1 Under the condition of (2) carrying out hydrogenation test to obtain the isooctane, wherein the octane number of the isooctane is equivalent to the octane number level of the isooctane of the existing product.
CN109293466a proposes a method for preparing isooctane by using isobutene, in the hydrogenation process, isooctene is added into a reaction kettle, palladium/active catalyst is added, reaction is carried out under the conditions of 120-150 ℃ and hydrogen pressure of 5-8MPa, and the yield of isooctane is about 92%.
CN106732620a discloses a nickel hydrogenation catalyst and a preparation method thereof, nickel-containing alumina is used as a carrier, nickel-containing alumina carrier is impregnated with nickel-containing solution, and the nickel-containing hydrogenation catalyst is prepared by drying and roasting, and the catalyst firstly needs to synthesize nickel-containing pseudo-boehmite, and has relatively complex procedures.
However, the current hydrogenation conditions are related to the catalysts used, noble metal catalysts such as platinum, palladium, rhodium and the like are used, the reaction can be carried out under mild conditions, the hydrogen can pass through once without circulation, the equipment investment and the operation cost are low, and the catalyst price is high. At present, in the hydrogenation process of the superposition products, a non-noble metal nickel-based catalyst is more commonly used, however, when the nickel-based catalyst is used, higher temperature and pressure are required, and meanwhile, the hydrogen consumption is larger and the service life of the catalyst is shorter.
Disclosure of Invention
In view of the problems existing in the prior art, one of the purposes of the invention is to provide a catalyst for hydrogenation of a carbon four-fold product and a preparation method thereof, wherein the specific design of the components improves the activity and selectivity of the catalyst in the hydrogenation process of the carbon four-fold product, reduces the reduction temperature of the catalyst, reduces the energy consumption, has high product purity, can realize large-scale continuous production, and has industrial application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-activity catalyst for hydrogenation of a carbon tetra-stacked product, wherein the catalyst comprises the following components in percentage by mass: 40-80wt% of gamma aluminum oxide, 0.5-40wt% of nickel oxide, 1-10wt% of lanthanum oxide, 0.1-6wt% of magnesium oxide and 0.1-6wt% of titanium dioxide;
wherein, gamma alumina is used as a carrier, magnesium element, titanium element and lanthanum element are used as auxiliary agents, and nickel element is used as an active component.
The catalyst provided by the invention realizes the improvement of the catalyst performance by introducing Ti, mg and La. After Ti is introduced into the modified alumina carrier, the interaction between the surface of the carrier and the metal active component Ni is enhanced, and the dispersion degree is obviously improved; the introduction of Mg reduces olefin polymerization and improves the coking resistance of the catalyst; the lanthanum is added to make nickel crystal grain smaller and contact surface of nickel oxide is increased, crystal grain smaller, lattice defect, dislocation and the like are produced in recombination process, so that the number of nucleation centers is increased, reduction of nickel oxide is promoted, reduction temperature of catalyst (namely, activation temperature of catalyst) is reduced, and meanwhile, improvement of catalyst activity is promoted.
In the invention, gamma alumina is obtained by roasting 1 or at least 2 of pseudo boehmite, gibbsite or amorphous alumina for 3-6 hours at 500-700 ℃ in a non-oxidizing atmosphere. Commercially available gamma alumina may also be used.
In the invention, the sum of the mass percentages of the components in the catalyst is 100%.
In the present invention, the content of gamma alumina in the catalyst is 40 to 80wt%, for example, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt% or 80wt%, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
In the present invention, the nickel oxide content of the catalyst is 0.5 to 40wt%, for example, 0.5wt%, 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%, etc., in terms of mass%, but the nickel oxide content is not limited to the recited values, and other non-recited values within the range are equally applicable.
In the present invention, the lanthanum oxide content of the catalyst is 1 to 10wt%, for example, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 7wt%, 9wt% or 10wt%, etc., but the lanthanum oxide content is not limited to the recited values, and other non-recited values within the range are equally applicable.
In the present invention, the magnesium oxide in the catalyst is 0.1 to 6wt%, for example, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, or 6wt%, etc., in terms of mass%, but the present invention is not limited to the recited values, and other non-recited values in the range are equally applicable.
In the present invention, the titanium dioxide content of the catalyst is 0.1 to 6wt%, for example, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, or 6wt%, etc., in terms of mass%, but the present invention is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the catalyst comprises the following components in percentage by mass: 50-70wt% of gamma aluminum oxide, 5-30wt% of nickel oxide, 2-8wt% of lanthanum oxide, 0.5-5wt% of magnesium oxide and 0.5-5wt% of titanium dioxide.
In a second aspect, the present invention provides a process for the preparation of a catalyst according to the first aspect, the process comprising:
(1) Adding gamma alumina into pretreatment liquid for treatment, then carrying out solid-liquid separation and first roasting to obtain intermediate gamma alumina, mixing the obtained intermediate gamma alumina, an alumina precursor and an auxiliary agent, and then sequentially carrying out molding and second roasting to obtain carrier alumina;
(2) Mixing the carrier alumina obtained in the step (1) with a nickel lanthanum mixed salt solution, then carrying out solid-liquid separation and third roasting to obtain an intermediate catalyst, mixing the intermediate catalyst with the nickel salt solution, and then carrying out solid-liquid separation and fourth roasting to obtain the catalyst.
In the invention, the concentration of metal salt in the solution and the mixed solid-to-liquid ratio are determined according to the content of nickel and lanthanum in the catalyst and the water absorption of the carrier when the first nickel-lanthanum salt solution and the second nickel salt solution are mixed (about the determination of the water absorption of the carrier, weighing 5g of the carrier, putting the carrier into a beaker, adding a proper amount of deionized water into the beaker to ensure that the carrier is soaked by 1-5cm and higher than the carrier, soaking for 0.5-3 hours, sucking excessive water on the surface of the carrier by using water absorption filter paper, weighing the weight of the carrier at the moment, and then, the water absorption of the carrier is (X-5)/5X 100 percent).
In the invention, the nickel salt in the nickel lanthanum mixed salt solution comprises 1 or at least 2 of nickel nitrate, nickel acetate and nickel citrate, and preferably nickel nitrate. The lanthanum salt in the nickel lanthanum mixed salt solution comprises 1 or at least 2 of lanthanum nitrate, lanthanum acetate and lanthanum citrate, and preferably lanthanum nitrate.
As a preferable technical scheme of the invention, the pretreatment liquid is obtained by mixing a magnesium-containing compound, a titanium-containing compound, a water-soluble organic compound and water.
Preferably, the magnesium-containing compound comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate or magnesium chloride.
Preferably, the titanium-containing compound comprises 1 or a combination of at least 2 of isopropyl titanate, titanium sulfate, titanium tetrachloride, tetrabutyl titanate, or titanium isopropoxide.
Preferably, the water-soluble organic matter comprises 1 or a combination of at least 2 of citric acid, lactic acid, sucrose, ethylene glycol or glycerol.
The magnesium-containing compound is preferably added in an amount of 0.1 to 10% by mass of gamma alumina, and may be, for example, 0.1%, 0.2%, 0.5%, 1%, 2%, 4%, 6%, 8% or 10%, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
The amount of the titanium-containing compound added in the mixture is preferably 0.1 to 10% by mass of gamma alumina, and may be, for example, 0.1%, 0.2%, 0.5%, 1%, 2%, 4%, 6%, 8% or 10%, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
In the invention, after the Ti modified alumina carrier is introduced, the interaction between the surface of the carrier and the metal active component Ni is enhanced, and the dispersion degree is obviously more uniform. Probably because Ti and hydroxyl on the surface of alumina form Al-O-Ti bond through a shrinking reaction, the action mode of the carrier and active metal is affected, the basal plane bonding is changed into the side bonding, the steric hindrance of macromolecules is reduced, and the catalytic activity of the hydrogenation catalyst of the superposition product is effectively improved.
The amount of the water-soluble organic compound added in the mixture is preferably 1 to 30% by mass of gamma alumina, and may be, for example, 1%, 5%, 15%, 20%, 25% or 30%, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
In the invention, water-soluble organic matters are added in the preparation process of the carrier and are roasted in a non-oxidizing atmosphere, so that carbon can be remained in the powder by roasting under a non-oxidizing low-temperature condition, on one hand, the carbon can protect the pore channel structure and avoid blocking pores with smaller pore diameters; on the other hand, the carbon can avoid uneven distribution of magnesium caused by the influence of capillary condensation phenomenon, is beneficial to the interaction between the magnesium and the carrier and between the magnesium and the active metal components, and improves the coking resistance in the hydrogenation process of the catalyst.
In a preferred embodiment of the present invention, the solid-to-liquid ratio g/mL of the gamma alumina and the pretreatment liquid in the treatment in the step (1) is (1-1.2): 1, and may be, for example, 1:1, 1.05:1, 1.1:1, 1.15:1, or 1.2:1, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the first firing of step (1) is performed under a protective atmosphere.
Preferably, the protective atmosphere comprises a nitrogen atmosphere and/or an inert atmosphere.
Preferably, the temperature of the first firing in the step (1) is 130 to 320 ℃, for example 130 ℃,150 ℃, 175 ℃, 200 ℃,225 ℃,250 ℃, 275 ℃,300 ℃ or 320 ℃, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the time of the first calcination in step (1) is 2-5h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferred embodiment of the present invention, the alumina precursor in step (1) includes 1 or at least 2 kinds of boehmite, gibbsite, or amorphous alumina.
Preferably, the mass ratio of the alumina precursor to the intermediate gamma alumina in the mixing in step (1) is 1 (0.8-1.8), and may be, for example, 1:0.8, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, or 1:1.8, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the auxiliary agent in the step (1) comprises sesbania powder and nitric acid.
The nitric acid is preferably present in a mass concentration of 1.5 to 8%, for example, 1.5%, 2%, 3%, 4%, 5%, 6%, 7% or 8%, etc., but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the addition amount of sesbania powder in the mixing in the step (1) is 2-5% of the gamma alumina mass, for example, 2%, 3%, 4% or 5%, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
The amount of nitric acid added in the mixture in step (1) is preferably 0.8 to 10% by mass of gamma alumina, and may be, for example, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the second firing in the step (1) is 380 to 600 ℃, and for example, 380 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or the like can be used, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the second calcination in step (1) is performed for a period of time ranging from 4 to 8 hours, for example, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, or 8 hours, etc., but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the third firing in the step (2) is 300 to 500 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the third calcination in step (2) is performed for a period of time ranging from 4 to 6 hours, for example, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, etc., but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the fourth firing in the step (2) is 300 to 500 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the fourth calcination in step (2) is performed for a period of time ranging from 4 to 6 hours, for example, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, etc., but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Adding gamma alumina into pretreatment liquid for treatment, then carrying out solid-liquid separation and first roasting to obtain intermediate gamma alumina, mixing the obtained intermediate gamma alumina, an alumina precursor and an auxiliary agent, and then sequentially carrying out molding and second roasting to obtain carrier alumina;
(2) Mixing the carrier alumina obtained in the step (1) with a first nickel lanthanum salt solution, then carrying out solid-liquid separation and third roasting to obtain an intermediate catalyst, mixing the intermediate catalyst with a second nickel salt solution, and then carrying out solid-liquid separation and fourth roasting to obtain the catalyst;
the pretreatment liquid in the step (1) is obtained by mixing a magnesium-containing compound, a titanium-containing compound, a water-soluble organic compound and water; the magnesium-containing compound comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate or magnesium chloride; the titanium-containing compound comprises 1 or a combination of at least 2 of isopropyl titanate, titanium sulfate, titanium tetrachloride, tetrabutyl titanate or titanium isopropoxide; the water-soluble organic matter comprises 1 or a combination of at least 2 of citric acid, lactic acid, sucrose, ethylene glycol or glycerol; the addition amount of the magnesium-containing compound in the mixture is 0.1-10% of the mass of gamma alumina; the adding amount of the titanium compound in the mixture is 0.1-10% of the mass of gamma alumina; the addition amount of the water-soluble organic matters in the mixture is 1-30% of the mass of gamma alumina; the solid-liquid ratio g/mL of gamma alumina and pretreatment liquid in the treatment is (1-1.2) 1, the temperature of the first roasting is 130-320 ℃, and the time of the first roasting is 2-5h;
the alumina precursor of step (1) comprises 1 or a combination of at least 2 of boehmite, gibbsite, or amorphous alumina; the mass ratio of the alumina precursor to the intermediate gamma alumina in the mixture is 1 (0.8-1.8); the auxiliary agent comprises sesbania powder and nitric acid; the adding amount of sesbania powder in the mixing is 2-5% of the mass of gamma alumina; the addition amount of nitric acid in the mixing is 0.8-10% of the mass of gamma alumina; the method comprises the steps of carrying out a first treatment on the surface of the The temperature of the second roasting is 380-600 ℃, and the time of the second roasting is 4-8h; the temperature of the third roasting in the step (2) is 300-500 ℃, the time of the third roasting is 4-6h, the temperature of the fourth roasting is 300-500 ℃, and the time of the fourth roasting is 4-6h.
In the invention, the reagents selected in the configuration process are all analytically pure reagents.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst provided by the invention realizes the improvement of the catalyst performance by introducing titanium and magnesium, improves the dispersion degree of nickel oxide, and adds water-soluble organic matters in the preparation process, so that magnesium element is uniformly dispersed in the pore channel structure of the catalyst, and further improves the catalyst performance.
(2) The lanthanum element is introduced into the invention, lanthanum oxide and nickel oxide interact, thereby effectively inhibiting the growth and sintering of nickel crystal grains in the supported nickel catalyst, further improving the activity of the catalyst and reducing the reduction temperature of the catalyst. The catalyst used in hydrogenation catalysis of the carbon four-superimposed product has higher activity, obviously improves selectivity, and has high purity of the obtained product, the conversion rate of isooctene is more than or equal to 98.55 percent, the selectivity of isooctane is more than 96.85 percent, and the purity of the obtained isooctane is more than or equal to 94 percent.
Drawings
FIG. 1 is H of the catalysts of example 1 and comparative example 1 of the present invention 2 -TPR profile.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides a high-activity catalyst for hydrogenation of a carbon tetra-stacked product, which comprises the following components in percentage by mass: 67wt% of gamma aluminum oxide, 22.3wt% of nickel oxide, 2.1wt% of lanthanum oxide, 3.8wt% of magnesium oxide and 4.8wt% of titanium dioxide;
wherein, gamma alumina is used as a carrier, magnesium element and titanium element are used as auxiliary agents, nickel element is used as an active component, and lanthanum is used as an auxiliary active component.
The preparation method comprises the following steps:
(1) 35g of Ti (SO) 4 ) 2 、58g Mg(NO 3 ) 2 ·6H 2 O and 10g of citric acid are added into 110mL of deionized water, the mixture is continuously stirred until the solute is completely dissolved, 100g of gamma alumina powder is added, and the mixture is roasted for 3 hours at 225 ℃ under nitrogen atmosphere.
(2) 100g of the calcined mixture, 71.43g of pseudo-boehmite and 6.45g of sesbania powder were weighed into a large container. 6.5mL of analytically pure nitric acid is measured, deionized water is used for constant volume to 142mL, then the analytically pure nitric acid is added into the mixed powder for kneading, extrusion molding is carried out, and the carrier is prepared by roasting for 4 hours at 600 ℃.
(3) 160g of the above-mentioned carrier was weighed into a 200mL beaker, 114.4g of Ni (NO 3 ) 2 ·6H 2 O and 6gLa (NO 3 ) 3 ·6H 2 Adding 120mL of deionized water into O to prepare a solution, impregnating a carrier, and roasting for 3 hours at 350 ℃ to obtain a catalyst precursor; 36.1g of Ni (NO) 3 ) 2 ·6H 2 Adding 56mL of deionized water into O to prepare a solution, saturating and impregnating 100g of catalyst precursor, and roasting for 3 hours at 350 ℃ to obtain the catalyst A1.
H of the resulting catalyst A1 2 The TPR spectrum is shown in FIG. 1. TPR refers to the reduction of the catalyst during the temperature programming process, which can provide information on the interaction between metal oxides or between metal oxides and the support during the reduction of the supported metal catalyst. The H2-TPR spectrogram can effectively see the hydrogen consumption of a supported oxide during reduction and the difficulty during reduction, and provide information such as the interaction between the metal oxide and the carrier, the dispersibility of the metal on the surface of the carrier and the like.
Example 2
The embodiment provides a catalyst for hydrogenation of a carbon four-stacked product, which comprises the following components in percentage by mass: 72wt% of gamma aluminum oxide, 22wt% of nickel oxide, 3wt% of lanthanum oxide, 2wt% of magnesium oxide and 1wt% of titanium dioxide;
wherein, gamma alumina is used as a carrier, magnesium element and titanium element are used as auxiliary agents, and nickel element is used as an active component.
The preparation method comprises the following steps:
(1) 25g of Ti (SO) 4 ) 2 、40g Mg(NO 3 ) 2 ·6H 2 O and 12g of citric acid are added into 100mL of deionized water, the mixture is continuously stirred until the solute is completely dissolved, then 100g of gamma alumina powder is added, and the mixture is roasted for 6 hours at 150 ℃ in nitrogen atmosphere.
(2) 100g of the calcined mixture, 71.43g of pseudo-boehmite and 6g of sesbania powder were weighed into a large container. 10mL of analytically pure nitric acid is measured, deionized water is used for constant volume to 142mL, then the analytically pure nitric acid is added into the mixed powder for kneading, extrusion molding is carried out, and the carrier is prepared by roasting for 7 hours at 400 ℃.
(3) 150g of the above-mentioned carrier was weighed into a 200mL beaker, and 80g of Ni (NO 3 ) 2 ·6H 2 O and 8gLa (NO) 3 ) 3 ·6H 2 Adding 122.64mL deionized water into O to prepare a solution, impregnating a carrier, and roasting at 600 ℃ for 8 hours to obtain a catalyst precursor; 40g Ni (NO) 3 ) 2 ·6H 2 Adding 60mL of deionized water into O to prepare a solution, saturating and impregnating 100g of catalyst precursor, and roasting at 300 ℃ for 5 hours to obtain the catalyst A2.
Example 3
The embodiment provides a catalyst for hydrogenation of a carbon four-stacked product, which comprises the following components in percentage by mass: 65.9wt% of gamma aluminum oxide, 25.4wt% of nickel oxide, 4.2 wt% of lanthanum oxide, 2.4wt% of magnesium oxide and 2.1wt% of titanium dioxide;
wherein, gamma alumina is used as a carrier, magnesium element and titanium element are used as auxiliary agents, and nickel element is used as an active component.
The preparation method comprises the following steps:
(1) 30g of Ti (SO) 4 ) 2 、70g Mg(NO 3 ) 2 ·6H 2 O and 20g of citric acid are added into 240mL of deionized water, the mixture is continuously stirred until the solute is completely dissolved, 200g of gamma alumina powder is added, and the mixture is roasted for 4 hours at 250 ℃ in nitrogen atmosphere.
(2) 100g of the above calcined mixture, 71.43g of pseudo-boehmite and 10g of sesbania powder were weighed into a large container. 15mL of analytically pure nitric acid is measured, deionized water is used for constant volume to 142mL, then the analytically pure nitric acid is added into the mixed powder for kneading, extrusion molding is carried out, and the carrier is prepared by roasting for 3 hours at 800 ℃.
(3) 150g of the above-mentioned carrier was weighed into a 200mL beaker, and 100g of Ni (NO 3 ) 2 ·6H 2 O and 12gLa (NO) 3 ) 3 ·6H 2 Adding 135mL deionized water into O to prepare a solution, impregnating a carrier, and roasting for 5 hours at 200 ℃ to obtain a catalyst precursor; 60g Ni (NO) 3 ) 2 ·6H 2 Adding 65mL of deionized water into O to prepare a solution, saturating and impregnating 100g of catalyst precursor, and roasting at 600 ℃ for 7 hours to obtain the catalyst A3.
Example 4
The embodiment provides a catalyst for hydrogenation of a carbon four-stacked product, which comprises the following components in percentage by mass: 74.4wt% of gamma aluminum oxide, 18.5wt% of nickel oxide, 5.4wt% of lanthanum oxide, 0.9wt% of magnesium oxide and 0.8wt% of titanium dioxide;
wherein, gamma alumina is used as a carrier, magnesium element and titanium element are used as auxiliary agents, and nickel element is used as an active component.
The preparation method comprises the following steps:
(1) 10g of Ti (SO) 4 ) 2 、25g Mg(NO 3 ) 2 ·6H 2 O and 25mL of ethylene glycol are added into 240mL of deionized water, the mixture is continuously stirred until the solute is completely dissolved, 200g of gamma alumina powder is added, and the mixture is roasted for 5 hours at 300 ℃ under nitrogen atmosphere.
(2) 100g of the above calcined mixture, 71.43g of pseudo-boehmite and 6.45g of sesbania powder were weighed into a large container. 8mL of analytically pure nitric acid is measured, deionized water is used for constant volume to 142mL, then the analytically pure nitric acid is added into the mixed powder for kneading, extrusion molding is carried out, and the carrier is prepared by roasting for 5 hours at 550 ℃.
(3) 150g of the above-mentioned carrier was weighed into a 200mL beaker, and 70gNi (NO 3 ) 2 ·6H 2 O and 14gLa (NO) 3 ) 3 ·6H 2 Adding 110mL of deionized water into O to prepare a solution, impregnating a carrier, and roasting at 500 ℃ for 6 hours to obtain a catalyst precursor; 40g Ni (NO) 3 ) 2 ·6H 2 O is added with 50mL deionized water to prepare a solution100g of the catalyst precursor was saturated impregnated and calcined at 400℃for 7 hours to obtain catalyst A4.
Comparative example 1
The difference from example 1 is only that catalysts D1, H are obtained without addition of lanthanum component 2 The TPR profile is shown in figure 1. From the analysis of fig. 1, it is evident that the temperature at which the catalyst undergoes reductive activation is significantly reduced when lanthanum element is added.
Comparative example 2
The difference from example 1 was only that no titanium component was added, resulting in catalyst D2.
Comparative example 3
The only difference from example 1 is that no water-soluble organic solvent was added to give catalyst D3.
Comparative example 4
The difference from example 1 was only that no magnesium component was added, giving catalyst D4.
Comparative example 5
The difference from example 1 was only that the water-soluble organic solvent (citric acid) was replaced with an equal amount of benzene, to obtain catalyst D5.
The catalyst samples obtained in examples 1-4 and comparative examples 1-5 above were each taken 20mL and placed in a fixed bed reactor, pre-reduction was carried out before the reaction at a reduction temperature of 300℃and a hydrogen-to-hydrogen volume ratio of 1000:1 at a pressure of 2MPa for 12 hours, after the completion of the reduction, the reaction temperature was adjusted to 150℃and the reaction pressure was adjusted to 2.0MPa, and the raw materials and hydrogen were introduced under conditions that the raw materials used in the experiment were a mixture of 2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene (volume ratio: 1:1) and the space velocity of the raw materials was 1 hour -1 The hydrogen/liquid volume ratio was 400:1 and the liquid product was analyzed by gas chromatography to evaluate the activity of each catalyst, as detailed in table 1.
Table 1 performance of catalysts in examples and comparative examples
Catalyst D1 of comparative example 1, if the temperature was raised to 400℃during the reduction activation, and then subjected to the same-condition carbon four hydrogenation reaction, gave a slightly lower index than that obtained in the preparation of example 1, with an isooctene conversion of 95%, a selectivity of 92% and a purity of 90%.
As is apparent from the results of the above examples and comparative examples, the improvement of catalyst performance was achieved by introducing Ti, mg and La, so that the catalyst had higher activity, selectivity was also remarkably improved, and purity of the obtained product was high.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (29)
1. A catalyst for hydrogenation of a carbon tetra-stacked product, which is characterized by comprising the following components in percentage by mass: 40-80wt% of gamma aluminum oxide, 0.5-40wt% of nickel oxide, 1-10wt% of lanthanum oxide, 0.1-6wt% of magnesium oxide and 0.1-6wt% of titanium dioxide;
wherein, the gamma aluminum oxide is used as a carrier, magnesium element, titanium element and lanthanum element are used as auxiliary agents, and nickel element is used as an active component;
the conversion rate of isooctene is more than or equal to 98.55%, and the selectivity of isooctane is as high as more than 96.85%.
2. The catalyst according to claim 1, wherein the catalyst comprises, in mass percent: 50-70wt% of gamma aluminum oxide, 5-30wt% of nickel oxide, 2-8wt% of lanthanum oxide, 0.5-5wt% of magnesium oxide and 0.5-5wt% of titanium dioxide.
3. A process for preparing a catalyst for hydrogenation of carbon tetra-stacked products as claimed in claim 1 or 2, comprising:
(1) Adding gamma alumina into pretreatment liquid for treatment, then carrying out solid-liquid separation and first roasting to obtain intermediate gamma alumina, mixing the intermediate gamma alumina, an alumina precursor and an auxiliary agent, and then sequentially carrying out molding and second roasting to obtain carrier alumina;
(2) Mixing the carrier alumina obtained in the step (1) with a nickel lanthanum mixed salt solution, then carrying out solid-liquid separation and third roasting to obtain an intermediate catalyst, mixing the intermediate catalyst with the nickel salt solution, and then carrying out solid-liquid separation and fourth roasting to obtain the catalyst.
4. The method according to claim 3, wherein the pretreatment liquid in the step (1) is obtained by mixing a magnesium-containing compound, a titanium-containing compound, a water-soluble organic compound and water.
5. The method of claim 4, wherein the magnesium-containing compound comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate, or magnesium chloride.
6. The method of claim 4, wherein the titanium-containing compound comprises 1 or a combination of at least 2 of isopropyl titanate, titanium sulfate, titanium tetrachloride, tetrabutyl titanate, or titanium isopropoxide.
7. The method of claim 4, wherein the water-soluble organic material comprises 1 or a combination of at least 2 of citric acid, lactic acid, sucrose, ethylene glycol, or glycerol.
8. The method according to claim 4, wherein the magnesium-containing compound is added in an amount of 0.1 to 10% by mass of gamma alumina.
9. The method according to claim 4, wherein the titanium-containing compound is added in an amount of 0.1 to 10% by mass of gamma alumina.
10. The method according to claim 4, wherein the amount of the water-soluble organic substance added in the mixture is 1 to 30% by mass of gamma alumina.
11. The method according to claim 3, wherein the solid-to-liquid ratio g/mL of the gamma alumina and the pretreatment liquid in the treatment in the step (1) is 1 to 1.2:1.
12. A method of preparing as claimed in claim 3, wherein the first calcination in step (1) is carried out in a protective atmosphere.
13. The method of manufacturing of claim 12, wherein the protective atmosphere comprises a nitrogen atmosphere.
14. The method of manufacturing of claim 12, wherein the protective atmosphere comprises an inert atmosphere.
15. A method according to claim 3, wherein the temperature of the first calcination in step (1) is 130-320 ℃.
16. The method of claim 3, wherein the first firing in step (1) is for a period of 2 to 5 hours.
17. The method of claim 3, wherein the alumina precursor of step (1) comprises 1 or a combination of at least 2 of boehmite, pseudo-boehmite, gibbsite, or amorphous alumina.
18. The method of claim 3, wherein the mass ratio of alumina precursor to intermediate gamma alumina in the mixing in step (1) is 1 (0.8-1.8).
19. A method of preparation as claimed in claim 3 wherein the adjuvant of step (1) comprises sesbania powder and nitric acid.
20. The method of claim 19, wherein the nitric acid has a mass concentration of 1.5-8%.
21. The method according to claim 3, wherein the sesbania powder is added in an amount of 2 to 5% by mass of gamma alumina in the mixing in the step (1).
22. A method according to claim 3, wherein the nitric acid is added in the amount of 0.8 to 10% by mass of gamma alumina in the mixing in step (1).
23. A method according to claim 3, wherein the second calcination in step (1) is carried out at a temperature of 380 to 600 ℃.
24. The method of claim 3, wherein the second firing in step (1) is for a period of 4 to 8 hours.
25. The method of claim 3, wherein the temperature of the third firing in step (2) is 300-500 ℃.
26. The method of claim 3, wherein the third firing in step (2) is for a period of 4 to 6 hours.
27. The method of claim 3, wherein the fourth firing in step (2) is performed at a temperature of 300-500 ℃.
28. The method of claim 3, wherein the fourth firing in step (2) is for a period of 4 to 6 hours.
29. The method of any one of claims 3-28, wherein the method of preparation comprises:
(1) Adding gamma alumina into pretreatment liquid for treatment, then carrying out solid-liquid separation and first roasting to obtain intermediate gamma alumina, mixing the obtained intermediate gamma alumina, an alumina precursor and an auxiliary agent, and then sequentially carrying out molding and second roasting to obtain carrier alumina;
(2) Mixing the carrier alumina obtained in the step (1) with a first nickel and lanthanum salt solution, then carrying out solid-liquid separation and third roasting to obtain an intermediate catalyst, mixing the intermediate catalyst with a second nickel salt solution, and then carrying out solid-liquid separation and fourth roasting to obtain the catalyst;
the pretreatment liquid in the step (1) is obtained by mixing a magnesium-containing compound, a titanium-containing compound, a water-soluble organic compound and water; the magnesium-containing compound comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate or magnesium chloride; the titanium-containing compound comprises 1 or a combination of at least 2 of isopropyl titanate, titanium sulfate, titanium tetrachloride, tetrabutyl titanate or titanium isopropoxide; the water-soluble organic matter comprises 1 or a combination of at least 2 of citric acid, lactic acid, sucrose, ethylene glycol or glycerol; the addition amount of the magnesium-containing compound in the mixture is 0.1-10% of the mass of gamma alumina; the adding amount of the titanium compound in the mixture is 0.1-10% of the mass of gamma alumina; the addition amount of the water-soluble organic matters in the mixture is 1-30% of the mass of gamma alumina; the solid-liquid ratio g/mL of gamma alumina and pretreatment liquid in the treatment is (1-1.2) 1, the temperature of the first roasting is 130-320 ℃, and the time of the first roasting is 2-5h;
the alumina precursor of step (1) comprises 1 or a combination of at least 2 of boehmite, gibbsite, or amorphous alumina; the mass ratio of the alumina precursor to the intermediate gamma alumina in the mixture is 1 (0.8-1.8); the auxiliary agent comprises sesbania powder and nitric acid; the adding amount of sesbania powder in the mixing is 2-5% of the mass of gamma alumina; the addition amount of nitric acid in the mixing is 0.8-10% of the mass of gamma alumina; the temperature of the second roasting is 380-600 ℃, and the time of the second roasting is 4-8h; the temperature of the third roasting in the step (2) is 300-500 ℃, the time of the third roasting is 4-6h, the temperature of the fourth roasting is 300-500 ℃, and the time of the fourth roasting is 4-6h.
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