CN109364929B - Method for selective hydrogenation of pyrolysis gasoline - Google Patents

Method for selective hydrogenation of pyrolysis gasoline Download PDF

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CN109364929B
CN109364929B CN201811182798.0A CN201811182798A CN109364929B CN 109364929 B CN109364929 B CN 109364929B CN 201811182798 A CN201811182798 A CN 201811182798A CN 109364929 B CN109364929 B CN 109364929B
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carrier
catalyst
nickel
pyrolysis gasoline
alumina
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CN109364929A (en
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陈雅菁
陈新忠
陈明海
施清彩
庄旭森
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Chen Yajing
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a selective hydrogenation method for pyrolysis gasoline, wherein a catalyst comprises a silicon oxide-alumina carrier and a metal active component palladium loaded on the carrier, and the content of the palladiumBased on the total weight of the catalyst, the catalyst is 0.15-0.45 wt%, the silicon oxide-aluminum oxide carrier comprises 0.1-12 wt% of silicon oxide, 0.1-10 wt% of nickel-doped lanthanum ferrite and 0.05-7.8 wt% of magnesium, and the hydrogenation process conditions are as follows: the temperature of a reaction inlet is less than or equal to 45 ℃, the reaction pressure is 2.5-4.5MPa, and the volume ratio of hydrogen to oil is 60-450; liquid volume space velocity of 3.0-5.5h‑1. The catalyst has good colloid resistance, strong arsenic resistance, sulfur resistance and water resistance.

Description

Method for selective hydrogenation of pyrolysis gasoline
Technical Field
The invention relates to a method for one-stage selective hydrogenation of pyrolysis gasoline.
Background
The pyrolysis gasoline is an important byproduct of ethylene and propylene produced by steam cracking industry and comprises C5-C10 fractions. The pyrolysis gasoline has complex composition, mainly comprises benzene, toluene, xylene, monoolefin, diolefin, straight-chain alkane, cycloparaffin, nitrogen, sulfur, oxygen, chlorine and heavy metal organic compounds, and the like, and has more than 200 components, wherein the benzene, the toluene and the xylene (generally called BTX) are about 50-90%, and the unsaturated hydrocarbon is 25-30%. According to the characteristic that pyrolysis gasoline contains a large amount of aromatic hydrocarbon, the application of the pyrolysis gasoline is wide, and the pyrolysis gasoline can be used as a blending component of gasoline to produce gasoline with high octane number, and can also be used for producing aromatic hydrocarbon and the like through separation.
Because the pyrolysis gasoline has complex composition and poor thermal stability, usually, the diolefin and the styrene are removed by first-stage selective hydrogenation, and the pyrolysis gasoline is mainly used for extracting the aromatic hydrocarbon after second-stage hydrodesulfurization. At present, the catalyst for selective hydrogenation of pyrolysis gasoline in industry is mainly Pd-series or Ni-series catalyst, and middle distillate (C)6～C8Hydrocarbon compound fraction) hydrogenation or whole fraction (C)5Hydrocarbon-hydrocarbon compound fraction having a dry point of 204 deg.c). Due to the difference between the pyrolysis raw materials and the pyrolysis conditions of all ethylene units, the composition of the pyrolysis gasoline raw materials of all the ethylene units has larger difference, and particularly, the contents of diene, colloid (high molecular polymer generated by polymerization reaction of unsaturated components such As diene, styrene and the like) As well As As and heavy metal of the pyrolysis gasoline have larger difference; some crude pyrolysis gasoline has high diene and colloid content, some crude pyrolysis gasoline has high colloid content, As, heavy metal and other toxic matter content, and some crude pyrolysis gasoline has diene, colloid content, As, heavy metal and other toxic matter contentThe amounts are all high.
Diolefins and alkynes in the pyrolysis gasoline are easy to polymerize into colloid at high temperature, deposit on the surface of the catalyst, easily cause the deactivation of the catalyst, and need to be frequently activated and regenerated. The first-stage hydrogenation catalyst for pyrolysis gasoline mainly comprises Pd/Al2O3And Ni/Al2O3Two catalysts. The Pd catalyst has the advantages of low initial temperature, high hydrogenation activity, high adaptive airspeed, long service life and the like, and the existing catalyst for industrial application comprises Pd-Cr/Al2O3，Pd/Al2O3。
Generally, the pyrolysis gasoline hydrogenation catalyst adopts a solution of metal salt or organic metal compound of an active component to impregnate the carrier, then the active component oxide is loaded on the surface of the carrier through the working procedures of drying, roasting and the like, and the catalyst can be used for the pyrolysis gasoline hydrogenation reaction after being reduced by introducing hydrogen before use. The pore diameter of the common alumina carrier is too small, and when the content of colloid, arsenic and sulfur in the raw material exceeds the standard, pores on the catalyst are easy to coke and block, so that the activity and the hydrogenation stability of the catalyst are influenced.
CN201310379189.5 discloses a pyrolysis gasoline selective hydrogenation catalyst, which comprises a carrier and a metal active component loaded on the carrier, wherein the active component is prepared in a microemulsion method system containing a high molecular polymer water phase and no auxiliary surfactant; the carrier is selected from at least one of alumina, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolin and cordierite; the active component comprises a main active component and an auxiliary active component, wherein the main active component is palladium, the content of the palladium is 0.01-1.0 wt% of the total weight of the carrier, and the high molecular polymer is a water-soluble high molecular polymer. The catalyst has higher activity, better selectivity and better gel-holding capacity in the reaction, the preparation process is simple and convenient, and the particle shape of the catalyst can be well controlled. CN201110089806.9 relates to a palladium-silver/alumina-titania catalyst for selective hydrogenation of pyrolysis gasoline or fractions thereof, which comprises an alumina-titania composite as a carrier, and active components Pd and Ag supported on the carrier, wherein the content of Pd is based on the catalystThe total weight of the catalyst is 0.15-0.5 wt%, and the content of Ag is 0.8-4.5 wt% based on the total weight of the catalyst. Compared with the similar catalyst, the catalyst of the invention can be used for hydrogenation of pyrolysis gasoline or fractions thereof, and has the advantages of high low-temperature hydrogenation selectivity, strong As impurity resistance, large gel capacity and stable activity. CN200610029962.5 relates to a method for selective hydrogenation of full-range pyrolysis gasoline, which mainly solves the technical problem that the full-range pyrolysis gasoline with high content of colloid and free water is difficult to be selectively hydrogenated in the prior art. The invention adopts C5Cracking gasoline of hydrocarbon compound fraction with a hydrocarbon-dry point of 204 ℃ and hydrogen are used as raw materials, the reaction temperature is 30-80 ℃, the reaction pressure is 2.0-3.0 MPa, and the space velocity of fresh oil is 2.5-5.0 hours－1Under the condition that the volume ratio of hydrogen to oil is 60-120: 1, the raw material is contacted with a catalyst for reaction to convert diolefin and olefin-based aromatic hydrocarbon components in the raw material into mono-olefin and alkyl aromatic hydrocarbon, wherein the catalyst comprises an alumina carrier, an active component of metallic palladium or an oxide thereof, at least one element selected from IA or IIA in a periodic table of elements or an oxide thereof, and at least one element selected from IVA or VA in the periodic table of elements or an oxide thereof, the specific surface area of the carrier is 40-160 m2The catalyst has the advantages that the catalyst can be used for the selective hydrogenation of full fraction pyrolysis gasoline, the total pore volume is 0.3-1.2 ml/g, and the carrier has the technical scheme of composite pore distribution, so that the problem is solved well, and the catalyst can be used for the industrial production of the selective hydrogenation of the full fraction pyrolysis gasoline. The preparation method of the catalyst is the same as the impregnation technology of the common shell layer catalyst: the method comprises the steps of pre-soaking a carrier in a liquid capable of being mutually soluble with an impregnation solution, then impregnating the carrier in a salt solution containing palladium, washing, drying and roasting the impregnated carrier in air at 300-600 ℃ to obtain the finished product of the oxidative catalyst. The finished catalyst can be used only by introducing hydrogen into a reactor for reduction. The catalyst adopted by the invention has a composite pore structure, a larger pore diameter and rich mesopores. The catalyst of the invention has good low-temperature activity, selectivity and stability when being used for selective hydrogenation of full-fraction pyrolysis gasoline, and has good anti-interference performance, high colloid resistance and high free water content. At the inlet temperature of 40 ℃, the reaction pressure of 2.7Mpa and the volume ratio of hydrogen to oil of 801, fresh oil space velocity of 3.8 hours-1Under the conditions, the whole fraction (C) having a gum content of 150 mg/100 g of oil and a free water content of 1000ppm was subjected5Hydrocarbon-to-dry point 204 deg.c) pyrolysis gasoline, the average value of the diene at the outlet is 0.0 g iodine/100 g oil, and the diene hydrogenation rate is 100%, so as to obtain good technological effect. The preparation method of the carrier comprises the steps of mixing alumina, a modifier, a peptizing agent and water according to required amounts, extruding and forming, drying at 50-120 ℃ for 1-24 hours, and then roasting at 800-1150 ℃ for 1-10 hours to obtain the alumina carrier.
The prior art mainly changes the chemical composition and type of a carrier and adds a promoter to improve the performance of a catalyst. As the contents of impurities such As As, S, O, N and the like and colloid in the pyrolysis gasoline are high, the catalyst is easy to inactivate, so that the pyrolysis gasoline catalyst is required to have the characteristics of good colloid resistance and water resistance, and strong arsenic resistance and sulfur resistance.
Disclosure of Invention
The invention provides a one-stage selective hydrogenation method for pyrolysis gasoline, which is particularly suitable for pyrolysis gasoline C6-C8And (4) selectively hydrogenating the distillate. The process method adopts a supported palladium catalyst, the carrier is a silicon oxide-aluminum oxide carrier containing nickel-doped lanthanum ferrite, the adaptability to pyrolysis gasoline raw materials with different arsenic contents, sulfur contents, water contents and colloid contents is strong, and the catalyst has higher low-temperature activity and better selectivity in the reaction.
A one-stage selective hydrogenation method for pyrolysis gasoline comprises a silicon oxide-alumina carrier and a metal active component palladium loaded on the carrier, wherein the content of palladium is 0.15-0.45 wt% based on the total weight of the catalyst, the silicon oxide-alumina carrier comprises 0.1-12 wt% of silicon oxide, 0.1-10 wt% of nickel-doped lanthanum ferrite and 0.05-7.8 wt% of magnesium, mesoporous pores of the carrier account for 3-75% of total pores, and macroporous pores account for 1.5-60% of the total pores. The micropores, mesopores and macropores in the carrier are not uniformly distributed. The hydrogenation process conditions are as follows: the temperature of a reaction inlet is less than or equal to 45 ℃, the reaction pressure is 2.5-4.5MPa, and the volume ratio of hydrogen to oil is 60-450; the liquid volume space velocity is 3.0-5.5 h-1.
Preference is given toThe hydrogenation process conditions are as follows: liquid volume space velocity of 3.0-4.5h-1The temperature of a reaction inlet is less than or equal to 40 ℃, the reaction pressure is 2.5-4.0MPa, and the volume ratio of hydrogen to oil is 60-300.
The palladium content in the above catalyst is preferably 0.20 to 0.35% by weight. Preferably, the mesopores account for 3-65% of the total pores, and the macropores account for 3-45% of the total pores.
The preparation method of the silica-alumina carrier comprises the following steps: adding pseudo-boehmite and sesbania powder into a kneading machine, uniformly mixing, adding an inorganic acid solution and an organic polymer, uniformly kneading, then adding nickel-doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor for later use; adding a silicon source and pseudo-boehmite into acid liquor of an organic polymer, and uniformly mixing to obtain a silicon source-pseudo-boehmite-organic polymer mixture, wherein the content of the organic polymer in the unit content of an alumina precursor is more than 2 times higher than that of the organic polymer in the silicon source-pseudo-boehmite-organic polymer mixture (abbreviated as silicon-aluminum-organic matter mixture), then mixing the silicon source-pseudo-boehmite-organic polymer mixture with the alumina precursor, adding a magnesium source, extruding, forming, drying and roasting to obtain the silica-alumina carrier. The silicon source is silica gel, sodium silicate or silica micropowder. The alumina in the silicon-aluminum-organic matter mixture accounts for 1-35 wt% of the alumina in the carrier.
In the preparation process of the silicon oxide-alumina carrier, the organic polymer is one or more of polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene glycol and polyacrylate.
Preferably, the nickel-doped lanthanum ferrite in the silica-alumina carrier is 0.1-12 wt%, more preferably 0.2-8 wt%, and the nickel in the nickel-doped lanthanum ferrite accounts for 0.1-8 wt% of the lanthanum ferrite.
The preparation method of the nickel-doped lanthanum ferrite comprises the following steps: dissolving citric acid in deionized water, stirring and dissolving, then adding lanthanum nitrate and ferric nitrate into the citric acid, stirring and dissolving, and adding sodium polyacrylate, polyacrylate or polyacrylic acid, wherein the adding amount of the sodium polyacrylate, the polyacrylate or the polyacrylic acid is 0.1-10 wt% of the nickel-doped lanthanum ferrite, and preferably 0.1-8.0 wt%. Adding nickel-containing compound, stirring, drying, roasting and grinding to obtain the finished product. The nickel-containing compound includes nickel nitrate, nickel acetate, and the like.
The preparation method of the catalyst can adopt methods such as dipping, spraying and the like, the active component palladium is dipped and sprayed on the silicon oxide-carrier, and then the catalyst is dried and roasted to obtain the catalyst. The catalyst can be prepared, for example, by the following steps: preparing a palladium-containing solution to dip a silicon oxide-alumina carrier, drying the carrier for 3 to 9 hours at the temperature of 110 to 160 ℃, and roasting the carrier for 4 to 9 hours at the temperature of 400 to 650 ℃ to finally obtain a catalyst product.
In the preparation method of the catalyst of the present invention, the palladium compound used may be any one of the palladium compounds disclosed in the prior art as being suitable for preparing a palladium catalyst, such as palladium chloride, palladium nitrate, palladium sulfate, aluminum tetrachloropalladate, aluminum tetracyanopalladate, sodium tetranitropalladate, salts of organic acids of palladium such as palladium oxalate, etc. The solvent used for preparing the palladium compound solution is not particularly limited as long as it can dissolve the palladium compound used. Preferred solvents are, for example, water, dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, or a mixture thereof.
The nickel-doped lanthanum ferrite is added into the silicon oxide-alumina carrier, so that the arsenic resistance, the sulfur resistance and the water resistance are effectively improved, and the alkyne or diene hydrogenation selectivity is improved. In the preparation process of the silicon oxide-aluminum oxide carrier, the content of organic polymers in unit content in the aluminum oxide precursor is more than 2 times higher than that of organic polymers in a silicon-aluminum-organic matter mixture, so that the pore structure of the carrier can be improved, the micropores, mesopores and macropores of the carrier are not uniformly distributed, the anti-colloid capacity of the catalyst is improved, the stability and the service life of the catalyst are improved, and the long-period operation of a device is facilitated; and the surface of the carrier is promoted to generate more active site loading centers, and the hydrogenation activity of the palladium catalyst is improved.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
The main raw material sources for preparing the catalyst are as follows: the raw material reagents used in the invention are all commercial products.
Example 1
1. Preparation of nickel-doped lanthanum ferrite
Dissolving 2.51mol of lanthanum nitrate in 120mL of water under the condition of stirring, adding citric acid, and stirring for dissolving; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, then adding the water solution containing 42g of nickel nitrate, continuously stirring for 30min, and obtaining the nickel-doped lanthanum ferrite through drying, roasting and grinding.
2. Preparation of silica-alumina Carrier
4.5g of nickel-doped lanthanum ferrite is added with citric acid for standby. Adding 300g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.2g of sodium polyacrylate nitric acid solution, uniformly mixing, adding nickel-doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor. 5g of sodium polyacrylate is dissolved in nitric acid, 38g of silica powder and 50g of pseudo-boehmite powder are added and stirred uniformly to obtain a silica powder-pseudo-boehmite-sodium polyacrylate mixture (abbreviated as silica-alumina-organic matter mixture). 1/8 silicon-aluminum-organic matter mixture is taken, the alumina precursor and 4.2g magnesium nitrate are added, the mixture is evenly kneaded, and the mixture is kneaded and extruded to form clover shape. Drying at 120 ℃ for 8 hours, and roasting at 650 ℃ for 6 hours to obtain the nickel-doped lanthanum ferrite-containing silica-alumina carrier 1. The mesopores of the carrier account for 55.4 percent of the total pores, and the macropores account for 28.6 percent of the total pores.
3. Preparation of the catalyst
The carrier 1 is impregnated with a palladium solution, dried at 140 ℃ for 6 hours and calcined at 560 ℃ for 5 hours to obtain the catalyst 1. The palladium content of catalyst 1 was 0.29 wt%.
Example 2
The nickel-doped lanthanum ferrite is prepared as in example 1, except that 260g of sodium polyacrylate is added, and the silica-alumina carrier is prepared as in example 1, wherein the silica-alumina carrier contains 4.4 wt% of silica, 5.7 wt% of nickel-doped lanthanum ferrite and 1.2 wt% of magnesium, the mesopores of the carrier account for 64.2% of the total pores, and the macropores account for 25.6% of the total pores. The unit content of sodium polyacrylate in the alumina precursor is 3 times higher than that of sodium polyacrylate in the silicon source-organic polymer mixture. Catalyst 2 was prepared in the same manner as in example 1, except that the amount of palladium was 0.35% by weight.
Example 3
The nickel-doped lanthanum ferrite is prepared as in example 1, except that 220g of polyacrylic acid is added, and the silica-alumina carrier is prepared as in example 1, wherein the silica-alumina carrier contains 8.4 wt% of silica, 2.6 wt% of nickel-doped lanthanum ferrite and 2.1 wt% of magnesium, mesoporous pores of the carrier account for 54.6% of total pores, and macroporous pores account for 33.5% of total pores. The unit content of polyacrylic acid in the alumina precursor is 3.3 times higher than that of polyacrylic acid in the silicon source-organic polymer mixture. Catalyst 3 was prepared in the same manner as in example 1, except that the amount of palladium was 0.21% by weight.
Example 4
Nickel-doped lanthanum ferrite was prepared as in example 1 except that 280g of sodium polyacrylate was added, and a silica-alumina carrier was prepared as in example 1, the silica-alumina carrier contained 8.4 wt% of silica, 2.6 wt% of nickel-doped lanthanum ferrite, and 2.8 wt% of magnesium, with the carrier mesopores accounting for 49.3% of the total pores and the macropores accounting for 39.4% of the total pores. The polyacrylate content per unit content in the alumina precursor was 3.3 times higher than the polyacrylate content in the silicon source-organic polymer mixture. Catalyst 3 was prepared in the same manner as in example 1, except that the amount of palladium was 0.26% by weight.
Comparative example 1
1. Preparation of lanthanum ferrite
Dissolving 2.51mol of lanthanum nitrate in 120mL of water under the condition of stirring, adding citric acid, and stirring for dissolving; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, stirring for 30min, drying, roasting and grinding to obtain the nickel-doped lanthanum ferrite.
2. Preparation of silica-alumina Carrier
5g of sodium polyacrylate is dissolved in nitric acid, 38g of silica powder and 50g of pseudo-boehmite powder are added and uniformly stirred to obtain a silica powder-pseudo-boehmite-sodium polyacrylate mixture (abbreviated as a silica-alumina-organic matter mixture), 1/8 is taken for later use, and 4.5g of lanthanum ferrite is added with citric acid for later use. Adding 300g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.2g of sodium polyacrylate nitric acid solution, uniformly mixing, adding the silicon micropowder-sodium polyacrylate mixture, uniformly kneading, adding lanthanum ferrite and 4.2g of magnesium nitrate, uniformly mixing, and kneading and extruding to form the clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 6 hr to obtain the carrier 1-1 of silicon oxide-aluminium oxide containing lanthanum ferrite.
3. Preparation of comparative catalyst 1
Preparing a palladium solution to impregnate a carrier 1-1, drying at 140 ℃ for 6 hours, and roasting at 560 ℃ for 5 hours to obtain the catalyst 1. The palladium content of comparative catalyst 1 was 0.29 wt%.
Comparative example 2
1. Preparation of nickel-doped lanthanum ferrite
Dissolving 2.51mol of lanthanum nitrate in 120mL of water under the condition of stirring, adding citric acid, and stirring for dissolving; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, then adding the water solution containing 42g of nickel nitrate, continuously stirring for 30min, and obtaining the nickel-doped lanthanum ferrite through drying, roasting and grinding.
2. Preparation of silica-alumina Carrier
Adding citric acid into 4.5g of nickel-doped lanthanum ferrite for later use, adding 350g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.7g of sodium polyacrylate nitric acid solution, uniformly mixing, adding 4.8g of silicon micropowder, uniformly kneading, adding nickel-doped lanthanum ferrite and 4.2g of magnesium nitrate, uniformly mixing, and kneading and extruding to form the clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 6 hr to obtain the carrier 1-2 containing nickel-doped lanthanum ferrite silica-alumina.
3. Preparation of comparative catalyst 2
A palladium solution was prepared to impregnate the support 1-2, dried at 140 ℃ for 6 hours and calcined at 560 ℃ for 5 hours to give comparative catalyst 2. The palladium content of comparative catalyst 2 was 0.29 wt%.
Catalysts 1-4 and comparative catalysts 1 and 2 were each charged to a 100ml adiabatic bed reactor at a temperature of 130 ℃, a hydrogen to catalyst volume ratio of 220: reducing for 7 hours under the condition of 1, cooling to 40 ℃, and then adding the raw oil and the pyrolysis gasoline C6-C8Fraction with a diene content of 19.51g iodine/100 g oil, a bromine number of 26.76g bromine/100 g oil, a gum content of 41mg/100ml oil, a free water content of1123ppm, a sulfur content of 156ppm and an arsenic content of 151 ppb; the reaction process conditions are as follows: the inlet temperature is 45 ℃, the volume ratio of hydrogen to oil is 300: 1, the reaction pressure is 3.5MPa, and the space velocity of fresh oil is 3.5h-1(ii) a The average diene of the hydrogenation product of the catalyst 1 in 220h running is 0.38 g of iodine/100 g of oil, the bromine number is 15.68 g of bromine/100 g, and the diene hydrogenation rate is 98.7%. The average diene of the hydrogenation product of the catalyst 2 is 0.33 g of iodine/100 g of oil, the bromine number is 14.56 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.8 percent; the average diene of the hydrogenation product of the catalyst 3 is 0.42 g of iodine/100 g of oil, the bromine number is 16.54 g of bromine/100 g, and the hydrogenation rate of the diene is 98.2 percent. The average diene of the hydrogenated product of the catalyst 4 is 0.40 g of iodine/100 g of oil, the bromine number is 15.29 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.3 percent. The catalyst has higher activity, better selectivity, better colloid resistance and water resistance, and strong arsenic resistance and sulfur resistance.
After the catalyst 1-2 is operated for 500 hours, the average diene of the hydrogenation product of the catalyst 1 is 0.40 g of iodine/100 g of oil, the bromine number is 20.25 g of bromine/100 g of oil, and the diene hydrogenation rate is 98.5 percent; the average diene of the hydrogenation product of the catalyst 2 is 0.45 g of iodine/100 g of oil, the bromine number is 20.48 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.7 percent. The catalyst carrier contains nickel-doped lanthanum ferrite, which is beneficial to inhibiting polymerization reaction of unsaturated components such as alkadiene, styrene and the like; the catalyst is not sensitive to impurities such as water, colloid and the like, and has good colloid resistance and water resistance, strong arsenic resistance and sulfur resistance and stable catalytic performance. The catalyst carrier has unevenly distributed micropores, mesopores and macropores, and the palladium catalyst has good activity, good stability and long service life and is beneficial to long-period operation of the device.
Catalysts 1-2 were each charged to a 100ml adiabatic bed reactor at a temperature of 125 ℃, a hydrogen to catalyst volume ratio of 250: reducing for 8 hours under the condition of 1, cooling to 40 ℃, and then adding the raw oil and the pyrolysis gasoline C6-C8A fraction having a diene content of 23.32g iodine/100 g oil, a bromine number of 24.35g bromine/100 g oil, a gum content of 104mg/100ml oil, a free water content of 1045ppm, a sulfur content of 87ppm and an arsenic content of 96 ppb; the reaction process conditions are as follows: the inlet temperature is 41 ℃, the volume ratio of hydrogen to oil is 260: 1, the reaction pressure is 3.0MPa, and the space velocity of fresh oil is 3.0h-1(ii) a Catalyst 1 hydrogenation product running for 200hThe average diene of (1) was 0.45 g of iodine per 100g of oil, the bromine number was 16.12 g of bromine per 100g of oil, and the diene hydrogenation rate was 98.5%. The average diene of the hydrogenation product of the catalyst 2 is 0.37 g of iodine/100 g of oil, the bromine number is 15.13 g of bromine/100 g of oil, and the diene hydrogenation rate is 98.7 percent; the catalyst has strong adaptability to oil with different sulfur content, free water content, arsenic content and colloid content.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (8)

1. The selective hydrogenation method for the pyrolysis gasoline is characterized in that a catalyst comprises a silicon oxide-aluminum oxide carrier and a metal active component palladium loaded on the carrier, wherein the content of the palladium is 0.15-0.45 wt% based on the total weight of the catalyst, the silicon oxide-aluminum oxide carrier comprises 0.1-12 wt% of silicon oxide, 0.1-10 wt% of nickel-doped lanthanum ferrite and 0.05-7.8 wt% of magnesium, nickel in the nickel-doped lanthanum ferrite accounts for 0.1-8 wt% of the lanthanum ferrite, carrier mesopores account for 3-75% of the total pores, macropores account for 1.5-60% of the total pores, and micropores, mesopores and macropores in the carrier are unevenly distributed; the hydrogenation process conditions are as follows: the temperature of a reaction inlet is less than or equal to 45 ℃, the reaction pressure is 2.5-4.5MPa, and the volume ratio of hydrogen to oil is 60-450; liquid volume space velocity of 3.0-5.5h-1(ii) a The preparation method of the silica-alumina carrier comprises the following steps: adding pseudo-boehmite and sesbania powder into a kneading machine, uniformly mixing, adding an inorganic acid solution and an organic polymer, uniformly kneading, then adding nickel-doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor for later use; adding a silicon source and pseudo-boehmite into acid liquor of an organic polymer, uniformly mixing to obtain a silicon source-pseudo-boehmite-organic polymer mixture, wherein the content of the organic polymer in the unit content of an alumina precursor is more than 2 times higher than that of the organic polymer in the silicon source-pseudo-boehmite-organic polymer mixture, mixing the silicon source-pseudo-boehmite-organic polymer mixture with the alumina precursor, adding a magnesium source, extruding, forming, drying and roasting to obtain oxidized aluminumA silica-alumina support; the preparation method of the catalyst comprises the following steps: preparing a palladium-containing solution to dip a silicon oxide-alumina carrier, drying the carrier for 3 to 9 hours at the temperature of 110 to 160 ℃, and roasting the carrier for 4 to 9 hours at the temperature of 400 to 650 ℃ to finally obtain a catalyst product.
2. The selective hydrogenation process for pyrolysis gasoline according to claim 1, wherein the hydrogenation process conditions are: liquid volume space velocity of 3.0-4.5h-1The temperature of a reaction inlet is less than or equal to 40 ℃, the reaction pressure is 2.5-4.0MPa, and the volume ratio of hydrogen to oil is 60-300.
3. The selective hydrogenation method for pyrolysis gasoline according to claim 1, wherein the mesopores of the carrier account for 3-65% of the total pores, and the macropores account for 3-45% of the total pores.
4. The selective hydrogenation process for pyrolysis gasoline of claim 1 wherein the catalyst palladium content is 0.20-0.35 wt%.
5. The selective hydrogenation method for pyrolysis gasoline according to claim 1, wherein the silicon source is silica gel, sodium silicate or silica micropowder, and the alumina in the silicon source-pseudo-boehmite-organic polymer mixture accounts for 1-35 wt% of the alumina in the carrier.
6. The selective hydrogenation method for pyrolysis gasoline according to claim 1, wherein the organic polymer is one or more of polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene glycol and polyacrylate.
7. The selective hydrogenation method for pyrolysis gasoline of claim 1, wherein the nickel-doped lanthanum ferrite in the silica-alumina carrier is 0.2-8 wt%.
8. The selective hydrogenation method for pyrolysis gasoline according to any one of claims 1 to 7, wherein the preparation method for nickel-doped lanthanum ferrite comprises the following steps: dissolving citric acid in deionized water, stirring and dissolving, then adding lanthanum nitrate and ferric nitrate into the citric acid, stirring and dissolving, adding sodium polyacrylate, polyacrylate or polyacrylic acid, wherein the adding amount of the sodium polyacrylate, the polyacrylate or the polyacrylic acid is 0.1-10 wt% of that of the nickel-doped lanthanum ferrite, then adding a nickel-containing compound, stirring, drying, roasting and grinding to obtain a finished product.
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