CN109468141B - C4Process for the saturation hydrogenation of distillates - Google Patents
C4Process for the saturation hydrogenation of distillates Download PDFInfo
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- CN109468141B CN109468141B CN201811285969.2A CN201811285969A CN109468141B CN 109468141 B CN109468141 B CN 109468141B CN 201811285969 A CN201811285969 A CN 201811285969A CN 109468141 B CN109468141 B CN 109468141B
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- 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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
Abstract
The invention relates to a compound C4Method for saturated hydrogenation of distillate by fixingA bed reactor; the catalyst is nickel hydrogenation catalyst, which comprises main active components of molybdenum, nickel, cobalt, potassium and silicon oxide-aluminum oxide composition. The hydrogenation process conditions are as follows: the inlet temperature of the reactor is 30-60 ℃, the reaction pressure is 1.5-6.0 MPa, and the liquid volume space velocity is 1.0-6.0 h‑1The volume ratio of hydrogen to oil is 100-400. C of the invention4The saturated hydrogenation method of fraction uses nickel-based saturated hydrogenation catalyst which has higher hydrogenation activity, can carry out hydrogenation reaction at lower temperature and has the characteristics of good sulfur resistance, water resistance and colloid resistance.
Description
Technical Field
The invention relates to a compound C4Fraction saturation hydrogenation method, C4The alkyne and diene in the fraction are hydrogenated into corresponding alkane.
Background
C4Unsaturated hydrocarbon contains more alkadiene, and the alkadiene can be polymerized with other hydrocarbons at a certain reaction temperature to generate coking precursors such as colloid and the like. Moreover, olefins are easily polymerized, and mono-olefins are easily hydrogenated and saturated. The diolefin in the raw oil is removed by hydrogenation, and simultaneously, the olefin polymerization reaction is avoided or reduced.
Steam cracking for preparing ethylene and a large amount of C as by-product of refinery4、C5The fractions, the yields and the compositions of which vary depending on the type of cracking raw material, the cracking depth and the cracking process. Wherein C is4、C5After the diolefin separated from the hydrocarbons is used as a chemical raw material, the rest of the diolefin is used in the fields of alkylate oil, petroleum resin and the like, and the surplus diolefin can only be used as fuel, so that the added value of the product is low. To surplus C of drawing4And C5The fraction is saturated and hydrogenated to obtain high-quality cracking material, solvent, foaming agent and other chemical products with increased C content4And C5The additional value of the fraction relieves the problem of shortage of the ethylene raw material. But the process conditions of various manufacturers are different, so that the raffinate C is generated4And C5The composition of the fraction varied considerably, some C4And C5The residual diene and alkyne content in the fraction is high, and C is simultaneously4The fraction often contains part of water, so that the catalyst is easy to be poisoned and coked. For C4、C5The distillate is usually produced by two-stage hydrogenation process, wherein diene and alkyne are removed by one-stage hydrogenation, and then saturated alkane is produced by two-stage hydrogenation. If a one-stage saturated hydrogenation process is adopted, a saturated hydrogenation catalyst with high hydrogenation activity and good hydrogenation depth is needed.
Due to C4High water content in the distillate, C5The diolefin content of the fraction is high and it is therefore desirable to use it in C4Fraction, C5The catalyst for saturated hydrogenation of the fraction has high hydrogenation activity, good sulfur, water and other impurity resistance, good thermal stability and high-temperature reduction and regeneration treatment resistance. If the catalyst is a catalystThe thermal stability is not good, the first high-temperature reduction can cause the reduction of the utilization rate of the active components of the catalyst, and the frequent high-temperature regeneration treatment can cause the reduction of the unrecoverable activity of the catalyst, so that the replacement of the catalyst can cause the increase of the production cost of manufacturers.
1.3-butadiene is an important raw material for synthesizing rubber, the waste gas of a rubber factory contains about 40 v% of 1.3-butadiene and about 10 v% of alkyne, and at present, most of the catalysts for removing diene and alkyne in the hydrocarbon fraction are palladium-platinum-silver/alpha-alumina by adopting a selective hydrogenation method, and then the catalysts are non-noble metal catalysts represented by copper-nickel. CN1295880A, CN85100761A, CN85106117A, CN1236333A, and CN1084222C describe a catalyst for selective hydrogenation of dienes and alkynes, palladium is an active component, and a carrier is alpha-alumina. The catalyst can promote acid catalytic reactions such as polymerization, isomerization and the like, and influence the selectivity of the catalyst. In particular, various polymers produced by the polymerization reaction adhere to the surface of the catalyst, and the reactivity of the catalyst is lowered. CN200510047499.2 discloses a preparation method of a catalyst for selective hydrogenation of unsaturated hydrocarbons. The hydrogenation catalyst changes the competitive adsorption state in the dipping process by using active carbon as a carrier and palladium as an active component and adding hydrogen peroxide and nitric acid into a dipping solution in advance, effectively controls the direct reduction of noble metal by the carrier during the adsorption, enables the metal palladium to be uniformly distributed on the surface of the carrier, and improves the utilization rate of the palladium. The catalyst obtained by the method is particularly suitable for the selective hydrogenation process of high-content highly unsaturated compounds in the hydrocarbon fraction of carbon four, can effectively inhibit the polymerization reaction of the highly unsaturated hydrocarbons on the surface of the catalyst, and obviously prolongs the service life of the catalyst. Especially, when the content of the conjugated diolefin (1, 3-butadiene) is high, polymerization reaction is easy to occur, and a sticky polymer (commonly called green oil) is generated, so that the catalyst is deactivated in a short time, and thus the catalyst must be regenerated frequently.
Compared with noble metal catalysts, non-noble metal catalysts which take nickel as a main active component are not sensitive to impurities due to the structural characteristics of the catalysts, and have more advantages in terms of catalyst cost and hydrogenation effect. At present, there are mainly supported and nickel-based catalysts prepared by coprecipitation method, but oneHigher nickel levels are generally required to ensure catalyst activity. CN95111774.2 discloses a method for saturated hydrogenation of raffinate oil with a byproduct of carbon five in the process of preparing ethylene by naphtha cracking, which is characterized in that a coprecipitation method is adopted to prepare a Ni-Cu/kieselguhr catalyst, the atomic ratio of nickel to copper is 9, the total amount of nickel and copper accounts for 40% of the catalyst, the single olefin in the raw material is 90%, the alkane is 8.5%, the diolefin is 1.5%, the temperature is 130 ℃, the pressure is 0.6MPa, the molar ratio of hydrogen to oil is 7, and the liquid hourly space velocity is 0.3h-1The mono-olefin conversion rate was 87%, and the pentane yield was 90%. The catalyst has high use temperature and low space velocity.
ZL200610064904.6 discloses a nickel series hydrogenation catalyst, which is prepared by taking alumina or silicon oxide as a carrier and adopting a coprecipitation method, mainly contains an active component Ni, and is characterized in that the catalyst is prepared from active components Ni, La and an auxiliary agent X1And vector X2O, and the weight percentage of the catalyst composition is as follows: contains NiO 40-70% and La2O3 2～5％， X1O 2～5％，X2O20-50%, wherein X1One or more selected from Cu, Mg and Zr, X2Selected from Al or and Si; the specific surface area is 80-200 m2The specific pore volume is 0.4-0.8 ml/g. The catalyst is suitable for mono-olefin hydrogenation, especially for cracking C9The hydrogenation of the fraction has certain sulfur poisoning resistance and colloid resistance, can meet the requirement of hydrogenation of raw materials with colloid of 500mg/100ml, and has high hydrogenation activity and good stability.
US 49563228 researches the mixed aqueous solution of nickel, aluminum and zirconium salts, and the catalyst prepared by coprecipitation with an alkaline compound is suitable for hydrogenation of aromatic hydrocarbon, nitrogen-containing hydrocarbon and olefin under the conditions that the temperature is higher than 60 ℃ and the pH value is 7-10, and the activity of the catalyst is poor. US5258346 discloses an aromatics hydrogenation catalyst using reduced nickel as an active component, which can be applied to the hydrogenation and dearomatization of various oil products, especially heavier hydrocarbon oils. The catalyst is prepared by a coprecipitation method, the content of nickel oxide is 10-90%, and the catalyst also contains alkali metal oxide, alkaline earth metal oxide or rare earth metal oxide or a mixture of the alkali metal oxide, the alkaline earth metal oxide and the rare earth metal oxide. The catalyst of the patent has limited anti-sulfuration capability and has certain difficulty in industrial application. CN02104336.1 discloses a method for producing olefinsThe catalyst for controllably reducing olefin content in gasoline by superposition and the process method using the catalyst are characterized in that mesoporous and macroporous gamma-alumina are doped with a certain amount of silicon dioxide as a carrier, nickel is selected as an active component, the activity and selectivity of olefin superposition/oligomerization are improved by changing the types of loading capacity and auxiliaries, the olefin content of the obtained superposed gasoline is reduced by 10-50%, and the yield of the superposed diesel oil is 10-50%. The adoption of the catalyst requires that the content of impurities in the raw materials is limited as follows: water is less than 100 mug/g, sulfur is less than 5 mug/g, and diene is less than 0.1%; the reaction temperature is above 60 ℃. CN200710176670.9 discloses a selective nickel hydrogenation catalyst and a preparation method thereof, wherein alumina is used as a carrier, and the catalyst is characterized by comprising 14-20% of nickel oxide, 2-8% of lanthanum oxide and/or cerium oxide and 1-8% of VIB oxide auxiliary agent, 2-8% of silicon dioxide and 1-8% of alkaline earth metal oxide by taking the weight of the catalyst as 100%, and the specific surface area of the catalyst is 60-150 m2The pore volume is 0.4-0.6 ml/g. The catalyst is suitable for the selective hydrogenation of diene of medium and low distillate oil, and has the capability of resisting impurities and colloid. ZL200610064905.0 discloses a hydrofining catalyst preparation method and application, the catalyst takes molybdenum, cobalt and nickel as active components, an auxiliary agent is added, alumina is taken as a carrier, the total weight of the catalyst is 100%, the catalyst contains 14-20% of molybdenum oxide, 1-6% of cobalt oxide, 1-4% of nickel oxide, 1-3% of auxiliary agent alkali metal oxide, 1-5% of auxiliary agent P or/and Sb oxide and 2-6% of Si or/and tin oxide; the pore volume of the catalyst is 0.45-0.65 cm3A specific surface area of 150 to 280 m/g2(ii) in terms of/g. The catalyst can be used for hydrofining of medium and low distillate oil, can hydrogenate saturated monoolefine to the maximum extent while hydrodesulfurizing, can adapt to the requirements of oil products with variable sulfur content and high space velocity, and does not have hydrogenation selectivity to alkadiene.
Therefore, it is necessary to develop a high-activity and high-stability saturated hydrogenation catalyst and process, and the catalyst has the characteristics of good sulfur resistance, water resistance, colloid resistance, coking resistance and olefin polymerization inhibition, so as to adapt to the hydrogenation of alkyne and diene in unsaturated hydrocarbon raw materials into corresponding alkane.
Disclosure of Invention
The invention provides a compound C4A method for saturated hydrogenation of distillate, which comprises using a nickel-based catalyst comprising Ni, Co, Mo and other metal oxide components4The alkyne and diene in the fraction are hydrogenated into corresponding alkane. The catalyst has the characteristics of high activity, sulfur resistance, water resistance, strong glue energy resistance and good stability.
C4A saturated hydrogenation method of distillate, which adopts a fixed bed reactor; the catalyst is a nickel hydrogenation catalyst, and comprises main active components of molybdenum, nickel, cobalt, potassium and silicon oxide-aluminum oxide compositions, wherein the main active components comprise, by weight, 26-36 wt% of nickel oxide, 0.05-2.5 wt% of molybdenum oxide, 0.1-2.5 wt% of cobalt oxide, 2.5-7.5 wt% of potassium oxide and 0-2.2 wt% of one or two auxiliary agents selected from oxides of strontium and manganese; the content of the silica-alumina composition is 35-70 wt%, and the silica-alumina composition comprises 0.1-16 wt% of silica, 0.5-15 wt% of nickel-containing lanthanum magnesium aluminate and 60-86.0 wt% of alumina; the hydrogenation process conditions are as follows: the inlet temperature of the reactor is 30-60 ℃, the reaction pressure is 1.5-6.0 MPa, and the liquid volume space velocity is 1.0-6.0 h-1The volume ratio of hydrogen to oil is 100-400.
Preferably, the hydrogenation process conditions are: the inlet temperature of the reactor is 30-50 ℃, the reaction pressure is 1.5-4.5 MPa, and the liquid volume space velocity is 1.0-4.0 h-1The volume ratio of hydrogen to oil is 100-350.
Preferably, the catalyst comprises 26-35 wt% of nickel oxide and 0.01-2.2 wt% of one or two of strontium and manganese oxides.
The nickel-based catalyst has a high alumina content, and is easy to form nickel aluminate spinel under a high temperature condition, and the formation of the nickel aluminate spinel can reduce the reaction activity of the catalyst, so that the stability of the catalyst is poor. The nickel-containing magnesium lanthanum aluminate is introduced into the silicon oxide-aluminum oxide composition, so that the formation of nickel aluminate spinel in the catalyst is effectively inhibited, the activity stability of the nickel catalyst is improved, and the nickel catalyst can bear reduction treatment and regeneration under the high-temperature condition.
The invention also provides a preparation method of the nickel-based saturated hydrogenation catalyst, which comprises the following specific steps:
dissolving soluble salts of active components and auxiliaries in water, adding sodium carbonate or potassium carbonate and polyacrylic acid or sodium polyacrylate, controlling the temperature to be 40-100 ℃, and adjusting the pH to be 8.0-9.5 under the stirring condition to obtain an active component precursor; adding polyacrylic acid or sodium polyacrylate into dilute nitric acid, uniformly mixing with silicon oxide-aluminum oxide composition powder according to the volume ratio of 1.1-2.1: 1, then adding an active component precursor, adjusting the pH value to 8.0-9.0 by using ammonia water, carrying out stirring reaction for 0.5-2.0 h, filtering for 1-5 times, washing, forming, drying, and roasting at 400-600 ℃ for 3-8 h to obtain the catalyst. The catalyst nickel prepared by the method is not easy to agglomerate and has good dispersibility.
The preparation method of the silica-alumina composition comprises the following steps: uniformly mixing 55-75% of an aluminum source with sesbania powder, adding an acid solution and a pore-expanding agent 1, wherein the addition amount of the pore-expanding agent 1 accounts for 15-30% of the mass of the added alumina, uniformly kneading, adding nickel-containing lanthanum magnesium aluminate, and uniformly mixing to obtain a mixture (1) containing aluminum and nickel-containing lanthanum magnesium aluminate; uniformly mixing a silicon source and 25-45% of an aluminum source, adding a binder and a pore-expanding agent 2, wherein the adding amount of the pore-expanding agent 2 accounts for 0.1-8% of the mass of the added aluminum oxide and silicon oxide, and obtaining a silicon-aluminum mixture (2); uniformly mixing a mixture (1) containing aluminum and nickel-containing magnesium lanthanum aluminate with a silicon-aluminum mixture (2), extruding, drying, roasting at 400-650 ℃ for 3-12 h, crushing and grinding to obtain the silicon oxide-aluminum oxide composition. The silicon source is one or two of silica gel, sodium silicate or silica micropowder and diatomite. The aluminum source is one or more of aluminum oxide, pseudo-boehmite and aluminum sulfate. The aluminum source can also be selected from one or more of montmorillonite, kaolin, perlite and rectorite. The binder is clay containing silicon and aluminum, alumina sol or silica sol, and the silica-alumina composition is controlled to contain 0.1-16 wt% of silica, 0.5-15 wt% of nickel-containing lanthanum magnesium aluminate and 60-86.0 wt% of alumina.
In the preparation process of the silicon oxide-aluminum oxide composition, the pore-expanding agent 1 is one or more of polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene glycol and polyacrylate. The pore-expanding agent 2 is one or more of methylcellulose, polymethacrylic acid, ammonium acrylate, glucose, chitosan and the like.
Preferably, the content of the nickel-containing lanthanum magnesium aluminate in the silica-alumina composition is 0.5 to 10 wt%, and the mass content of nickel in the nickel-containing lanthanum magnesium aluminate is 0.1 to 12%.
Adding deionized water into the nickel-containing magnesium lanthanum aluminate powder, stirring at a high speed or oscillating by ultrasonic waves to obtain highly dispersed nickel-containing magnesium lanthanum aluminate slurry, and then adding the highly dispersed nickel-containing magnesium lanthanum aluminate slurry into the mixture (1). One or more of clay containing silicon and aluminum, alumina sol, silica sol and the like can be introduced into the nickel-containing magnesium lanthanum aluminate slurry, and the using amount of the one or more of clay, alumina sol, silica sol and the like accounts for 0.1-18% of the total mass of the nickel-containing magnesium lanthanum aluminate slurry. The silica-alumina composition comprises 0.1-16 wt% of silica, 0.5-15 wt% of nickel-containing lanthanum magnesium aluminate, and 60-86.0 wt% of alumina.
Preparation of nickel-containing lanthanum magnesium aluminate LaMgAl11O19The process of (2) is as follows: basic magnesium carbonate, lanthanum carbonate and aluminium hydroxide according to LaMgAl11O19The nickel-containing magnesium lanthanum aluminate powder is obtained by uniformly mixing the stoichiometric coefficient ratio, adding the mixture into deionized water, uniformly stirring, adding nickel nitrate, uniformly mixing, spray-drying, roasting at 1200-1400 ℃ for 2-10 hours under the condition of introducing air, crushing and ball-milling.
Steam cracking for preparing ethylene and a large amount of C as by-product of refinery4、C5The fractions, the yields and the compositions of which vary depending on the type of cracking raw material, the cracking depth and the cracking process. C4、C5The fraction contains more diolefins, and at a certain reaction temperature, the diolefins can be polymerized and reacted with other hydrocarbons to generate coke precursors such as colloid and the like. Olefin polymerization is avoided or reduced while removing diolefins in the feed oil by hydrogenation. Due to C4High water content in the distillate C5The diolefin content of the fraction is high and it is therefore desirable to use it in C4Fraction, C5The catalyst for saturated hydrogenation of fraction has high hydrogenation activity, good sulfur resistance,The material has the advantages of colloid resistance, water resistance and other impurity performances, good thermal stability, and capability of bearing high-temperature reduction and regeneration treatment. If the catalyst is not good in thermal stability, the first high-temperature reduction can cause the reduction of the utilization rate of the active components of the catalyst, and the frequent high-temperature regeneration treatment can cause the unrecoverable activity reduction of the catalyst, so that the catalyst is replaced, and the production cost of manufacturers is increased.
According to the high-content nickel-based hydrogenation catalyst containing the silica-alumina composition prepared by the coprecipitation method, nickel-containing magnesium lanthanum aluminate is added in the preparation process of the silica-alumina composition, so that the formation of nickel aluminate spinel under a high-temperature condition of the catalyst can be inhibited, the reaction activity of the catalyst is further reduced, and the stability of the catalyst is poor. In the preparation process of the silicon oxide-aluminum oxide composition, aluminum oxide is added in two parts and is respectively mixed with nickel-containing magnesium lanthanum aluminate and silicon oxide, different pore-expanding agents are introduced into the mixture, the content of the pore-expanding agents is different, and the mass content of the pore-expanding agents in the mixture (1) of the aluminum oxide and the nickel-containing magnesium lanthanum aluminate is higher than that of the pore-expanding agents in the mixture (2) of the aluminum oxide and the silicon oxide. The catalyst prepared by the method can inhibit olefin polymerization to synthesize rubber, reduces the generation amount of rubber, improves the rubber resistance of the catalyst, reduces the surface coking process of the catalyst and has high hydrogenation selectivity of diene and alkyne. The device is beneficial to long-period operation; but also promotes the synergistic effect of the silicon oxide-aluminum oxide composition and active components such as nickel, molybdenum, cobalt and the like, and improves the hydrogenation activity of the nickel catalyst.
The catalyst of the invention is not limited in shape, and the catalyst is preferably in the shape of a cylinder with phi of 1.5-3 multiplied by 1-10 mm and can be obtained by extruding strips.
Invention C4The saturated hydrogenation method of fraction uses nickel-based saturated hydrogenation catalyst which has higher hydrogenation activity, can carry out hydrogenation reaction at lower temperature, and has the characteristics of good sulfur resistance, water resistance and colloid resistance, low coking rate and good stability. C is to be4The alkyne and diene in the fraction are hydrogenated into corresponding alkane.
Detailed Description
All starting materials for the present invention are commercially available.
Example 1
(1) Preparation of silica-alumina composition 1
1. Preparation of nickel-containing lanthanum magnesium aluminate LaMgAl11O19The process of (2) is as follows:
taking 7.8 g of basic magnesium carbonate, 25 g of lanthanum carbonate and 70.5 g of aluminum hydroxide, uniformly mixing, adding into deionized water to form a highly dispersed suspension, adding 8g of nickel nitrate, performing spray drying, drying at 140 ℃ for 5 hours, placing in an air atmosphere, roasting at 1300 ℃ for 4 hours, and then performing ball milling for 18 hours to obtain the nickel-containing magnesium lanthanum aluminate powder. Adding water into the nickel-containing magnesium lanthanum aluminate powder, and performing ultrasonic oscillation to obtain the high-dispersion nickel-containing magnesium lanthanum aluminate slurry.
2. Preparation of silica-alumina composition
Uniformly mixing 150g of pseudo-boehmite with 24g of sesbania powder, adding dilute nitric acid, adding 26g of polyacrylic acid sodium nitrate solution, uniformly mixing, adding nickel-containing magnesium lanthanum aluminate slurry, and uniformly mixing to obtain a mixture (1) containing aluminum and nickel-containing magnesium lanthanum aluminate; uniformly mixing 18g of silicon micropowder and 65g of pseudo-boehmite, adding 7.5g of water-soluble chitosan, and then adding silica sol to obtain a silicon-aluminum mixture (2); uniformly mixing a mixture (1) containing aluminum and nickel-containing magnesium lanthanum aluminate with a silicon-aluminum mixture (2), extruding, drying, roasting at 580 ℃ for 5 hours, crushing and grinding to obtain the silica-alumina composition.
(2) Preparation of the catalyst
Preparing nickel nitrate, cobalt nitrate, potassium nitrate and ammonium molybdate solutions, uniformly mixing, adding sodium polyacrylate and sodium carbonate solutions, and adjusting the pH value to 8.5 to obtain an active component precursor; adding sodium polyacrylate into dilute nitric acid, mixing with the silicon oxide-aluminum oxide composition powder at a volume ratio of 1.2:1, adding active component precursor, adjusting pH to 8.6 with ammonia water, and stirring for 0.5 h. After filtration, washing, drying, extrusion into cylindrical shape of phi 3X 6mm, roasting at 480 ℃ for 5h to obtain catalyst 1, the composition of which is shown in Table 1.
Example 2
(1) Preparation of silica-alumina composition 2
The preparation of nickel-containing magnesium lanthanum aluminate is the same as that of example 1, the preparation of the silica-alumina composition is the same as that of example 1, 68% of pseudo-boehmite is uniformly mixed with sesbania powder, the addition amount of sodium polyacrylate of the pore-expanding agent 1 accounts for 19% of the mass of the added alumina, and the addition amount of chitosan of the pore-expanding agent 2 accounts for 4% of the mass of the added alumina and silica. The silica-alumina composition contained 6.1 wt% silica, 5.8 wt% nickel-containing lanthanum magnesium aluminate.
(2) Preparation of the catalyst
The preparation method of the catalyst is the same as that of example 1, the polyacrylic acid solution and the silica-alumina composition powder are uniformly mixed according to the volume ratio of 1.8:1, and the composition of the catalyst is shown in table 1.
Example 3
(1) Preparation of silica-alumina composition 3
The preparation of nickel-containing magnesium lanthanum aluminate is the same as that of example 1, the preparation of the silica-alumina composition is the same as that of example 1, 72 percent of pseudo-boehmite is uniformly mixed with sesbania powder, the addition amount of polyacrylate of the pore-expanding agent 1 accounts for 21 percent of the mass of the added alumina, and the addition amount of methyl cellulose of the pore-expanding agent 2 accounts for 2.6 percent of the mass of the added alumina and the added silica. The silica-alumina composition contained 4.3 wt% silica, 5.9 wt% nickel-containing lanthanum magnesium aluminate.
(2) Preparation of the catalyst
The preparation method of catalyst 3 was the same as example 1, sodium polyacrylate was added to dilute nitric acid and mixed uniformly with silica-alumina composition powder in a volume ratio of 1.5:1, and the composition of the catalyst is shown in table 1.
Example 4
(1) Preparation of silica-alumina composition 4
The preparation of nickel-containing magnesium lanthanum aluminate is the same as that of example 1, the preparation of the silica-alumina composition is the same as that of example 1, 61% of pseudo-boehmite is uniformly mixed with sesbania powder, the addition amount of the sodium polyacrylate of the pore-expanding agent 1 accounts for 19% of the mass of the added alumina, and the addition amount of the glucose of the pore-expanding agent 2 accounts for 3.1% of the mass of the added alumina and the added silica. The silica-alumina composition contained 8.1 wt% silica, 3.1 wt% nickel-containing lanthanum magnesium aluminate.
(2) Preparation of the catalyst
The preparation method of catalyst 4 was the same as example 1, sodium polyacrylate was added to dilute nitric acid and mixed uniformly with silica-alumina composition powder in a volume ratio of 2.0:1, and the composition of the catalyst is shown in table 1.
Comparative example 1
(1) Preparation of comparative example silica-alumina composition 1
The procedure for preparing silica-alumina composition 1 was as follows:
uniformly mixing 140g of pseudo-boehmite with 22g of sesbania powder, adding dilute nitric acid, adding 20g of polyacrylic acid sodium nitrate solution, and uniformly mixing to obtain an aluminum-containing mixture (1); uniformly mixing 16g of silicon micropowder and 60g of pseudo-boehmite, adding 7g of chitosan, and then adding silica sol to obtain a silicon-aluminum mixture (2); uniformly mixing the aluminum-containing mixture (1) and the silicon-aluminum mixture (2), extruding, drying, roasting at 550 ℃ for 5 hours, crushing and grinding to obtain the silicon oxide-aluminum oxide composition.
(2) Preparation of comparative catalyst 1
Preparing nickel nitrate, cobalt nitrate, potassium nitrate and ammonium molybdate solutions, uniformly mixing, adding sodium polyacrylate and sodium carbonate solutions, and adjusting the pH value to 8.5 to obtain an active component precursor; adding sodium polyacrylate into dilute nitric acid, mixing with the silicon oxide-aluminum oxide composition powder at a volume ratio of 1.2:1, adding active component precursor, adjusting pH to 8.6 with ammonia water, and stirring for 0.5 h. After filtration, washing, drying, extrusion into a cylindrical shape of phi 3X 6mm, roasting at 480 ℃ for 5h, comparative catalyst 1 was obtained, the composition of which is shown in Table 1.
Comparative example 2
(1) Preparation of comparative example silica-alumina composition 2
Preparation of nickel-containing lanthanum magnesium aluminate as in example 1, the silica-alumina composition was prepared as follows:
the preparation method comprises the steps of uniformly mixing 200g of pseudo-boehmite and 22g of sesbania powder, adding dilute nitric acid, adding 20g of polyacrylic acid sodium nitrate solution, uniformly mixing, adding nickel-containing magnesium lanthanum aluminate slurry and 16g of silicon micropowder, uniformly mixing, extruding, drying, roasting at 550 ℃ for 5 hours, crushing and grinding to obtain the silicon oxide-aluminum oxide composition.
(2) Preparation of comparative catalyst 2
Preparing nickel nitrate, cobalt nitrate, potassium nitrate and ammonium molybdate solutions, uniformly mixing, adding sodium polyacrylate and sodium carbonate solutions, and adjusting the pH value to 8.5 to obtain an active component precursor; adding sodium polyacrylate into dilute nitric acid, mixing with the silicon oxide-aluminum oxide composition powder at a volume ratio of 1.2:1, adding active component precursor, adjusting pH to 8.6 with ammonia water, and stirring for 0.5 h. After filtration, washing, drying, extrusion into a cylindrical shape of phi 3X 6mm, roasting at 480 ℃ for 5h, comparative catalyst 2 was obtained, the composition of which is shown in Table 1.
Table 1 example/comparative catalyst composition/wt%
C4And (3) fraction saturation hydrogenation reaction:
the catalyst and the comparative catalyst were each reduced at 360 ℃ for 24h under a hydrogen atmosphere on a 100ml adiabatic bed hydrogenation apparatus. Cooling to 90 deg.C, introducing nitrogen gas, and cooling to 30 deg.C. Reduced catalyst and comparative catalyst used mixture C4Fraction evaluation, C4The fraction contained 83mg of gum per 100ml of oil, 65ppm of sulfur and 1431ppm of water; the inlet temperature of the reactor is 30 ℃, the reaction pressure is 3.0MPa, and the liquid volume space velocity is 4h-1The volume ratio of hydrogen to oil is 380: 1. The composition analysis of the starting materials and the catalyst and the comparative catalyst after 800h of reaction is shown in Table 2. As can be seen from Table 2, the catalyst has high hydrogenation saturation activity and low carbon deposition rate, and the comparative catalyst has weak capability of further hydrogenating high-content dienes and alkynes into alkanes, insufficient olefin saturation hydrogenation depth, incomplete hydrogenation of partial olefins and high carbon deposition rate. The catalyst silicon oxide-aluminum oxide composition contains nickel-containing magnesium lanthanum aluminate, which is beneficial to inhibiting polymerization reaction of unsaturated components such as diene and the like, reducing hydrogen consumption and reducing the generation amount of green oil; catalyst and process for preparing sameThe catalyst is insensitive to water, colloid and other impurities, and has good colloid resistance and water resistance, strong sulfur resistance and stable catalytic performance.
TABLE 2 analysis of raw materials and product composition (omega%)
| Diene + alkyne | Mono-olefins | Carbon deposition of catalyst | |
| Raw materials | 19.3 | 42.6 | / |
| Catalyst 1 | 0 | 39.4 | 2％ |
| Catalyst 2 | 0 | 38.7 | 3％ |
| Catalyst 3 | 0 | 39.0 | 3％ |
| Catalyst 4 | 0 | 38.1 | 3％ |
| Comparative agent 1 | 7.4 | 24.3 | 11％ |
| Contrast agent 2 | 9.7 | 29.1 | 8％ |
Regenerating the catalysts 1 and 3 after 800h operation, reducing the temperature of the reactor to 90 ℃, reducing the pressure to 0.5MPa and controlling the pressure to 55m3Introducing hydrogen for 6 hours; the reactor inlet temperature was raised to 240 ℃ at 25 ℃/h and held for 7 h; the reactor temperature was again reduced to 30 ℃ and then the mixing C was resumed4And (5) fraction hydrogenation reaction. The inlet temperature of the reactor is 30 ℃, the reaction pressure is 3.0MPa, and the liquid volume space velocity is 4h-1The volume ratio of hydrogen to oil is 380: 1. The product performance analysis after 300h of operation is shown in table 3:
TABLE 3 analysis of the product compositions of catalysts 1 and 3 (. omega.%)
| Diene + alkyne | Mono-olefins | Carbon deposition of catalyst | |
| Raw materials | 19.3 | 42.6 | / |
| Catalyst 1 | 0 | 39.9 | 2％ |
| Catalyst 3 | 0 | 38.6 | 3％ |
After high-temperature regeneration treatment, the hydrogenation performance of the catalyst can be recovered to the level of a fresh catalyst, the catalyst can effectively inhibit the generation of nickel aluminate spinel, the activity stability of the nickel catalyst is improved, the reduction and regeneration can be carried out under the high-temperature condition, and the catalyst has better thermal stability.
Claims (8)
1. C4The saturated hydrogenation method of the fraction is characterized in that a fixed bed reactor is adopted; the catalyst is a nickel hydrogenation catalyst, and comprises main active components of molybdenum, nickel, cobalt, potassium and silicon oxide-aluminum oxide compositions, wherein the main active components comprise, by weight, 26-36 wt% of nickel oxide, 0.05-2.5 wt% of molybdenum oxide, 0.1-2.5 wt% of cobalt oxide, 2.5-7.5 wt% of potassium oxide and 0-2.2 wt% of one or two auxiliary agents selected from oxides of strontium and manganese; the content of the silica-alumina composition is 35-70 wt%, and the silica-alumina composition comprises 0.1-16 wt% of silica, 3.1-15 wt% of nickel-containing lanthanum magnesium aluminate and 60-86.0 wt% of alumina; the preparation method of the nickel-based hydrogenation catalyst comprises the following stepsThe method comprises the following steps: dissolving soluble salts of active components and auxiliaries in water, adding sodium carbonate or potassium carbonate and polyacrylic acid or sodium polyacrylate, controlling the temperature to be 40-100 ℃, and adjusting the pH to be 8.0-9.5 under the stirring condition to obtain an active component precursor; adding polyacrylic acid or sodium polyacrylate into dilute nitric acid, uniformly mixing with silicon oxide-aluminum oxide composition powder according to the volume ratio of 1.1-2.1: 1, then adding an active component precursor, adjusting the pH value to 8.0-9.0 by using ammonia water, carrying out stirring reaction for 0.5-2.0 h, filtering for 1-5 times, washing, forming, drying, and roasting at 400-600 ℃ for 3-8 h to obtain a catalyst; the preparation method of the silica-alumina composition comprises the following steps: uniformly mixing 55-75% of an aluminum source with sesbania powder, adding an acid solution and a pore-expanding agent 1, wherein the addition amount of the pore-expanding agent 1 accounts for 15-30% of the mass of the added alumina, uniformly kneading, adding nickel-containing lanthanum magnesium aluminate, and uniformly mixing to obtain a mixture (1) containing aluminum and nickel-containing lanthanum magnesium aluminate; uniformly mixing a silicon source and 25-45% of an aluminum source, adding a binder and a pore-expanding agent 2, wherein the adding amount of the pore-expanding agent 2 accounts for 0.1-8% of the mass of the added aluminum oxide and silicon oxide, and obtaining a silicon-aluminum mixture (2); uniformly mixing a mixture (1) containing aluminum and nickel-containing magnesium lanthanum aluminate with a silicon-aluminum mixture (2), extruding, drying, roasting at 400-650 ℃ for 3-12 h, crushing and grinding to obtain a silicon oxide-aluminum oxide composition; the hydrogenation process conditions are as follows: the inlet temperature of the reactor is 30-60 ℃, the reaction pressure is 1.5-6.0 MPa, and the liquid volume space velocity is 1.0-6.0 h-1The volume ratio of hydrogen to oil is 100-400.
2. C according to claim 14The saturated hydrogenation method of the fraction is characterized in that the hydrogenation process conditions are as follows: the inlet temperature of the reactor is 30-50 ℃, and the reaction pressure is 1.5-4.5 MPa.
3. C according to claim 14The saturated hydrogenation method of the fraction is characterized in that the hydrogenation process conditions are as follows: the liquid volume airspeed is 1.0-4.0 h-1The volume ratio of hydrogen to oil is 100-350.
4. C according to claim 14Saturation of the distillateThe hydrogenation method is characterized in that the silicon source is one or more of silica gel, sodium silicate or silica micropowder.
5. C according to claim 14The method for saturated hydrogenation of the distillate is characterized in that the catalyst comprises 26-35 wt% of nickel oxide and 0.01-2.2 wt% of one or two auxiliary agents selected from oxides of strontium and manganese in percentage by weight.
6. C according to claim 14A method for the saturated hydrogenation of distillate, characterized in that the preparation method of the nickel-containing lanthanum magnesium aluminate in the silica-alumina composition is as follows: basic magnesium carbonate, lanthanum carbonate and aluminium hydroxide according to LaMgAl11O19The nickel-containing magnesium aluminate lanthanum powder is prepared by uniformly mixing the stoichiometric ratio, adding the mixture into deionized water, uniformly stirring, adding nickel nitrate, uniformly mixing, spray-drying, roasting at 1200-1400 ℃ for 2-10 hours under the condition of introducing air, crushing and ball-milling.
7. C according to claim 14The saturated hydrogenation method of the fraction is characterized in that the pore-enlarging agent 1 is one or more of polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene glycol and polyacrylate; the pore-expanding agent 2 is one or more of methylcellulose, polymethacrylic acid, ammonium acrylate, glucose and chitosan.
8. C according to claim 14The saturated hydrogenation method of the distillate is characterized in that the binder is one of clay containing silicon and aluminum, aluminum sol or silica sol.
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| CN1676580A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Fractional oil selective hydro-de-diene method |
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