CN109289868B - Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof - Google Patents

Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof Download PDF

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CN109289868B
CN109289868B CN201811183029.2A CN201811183029A CN109289868B CN 109289868 B CN109289868 B CN 109289868B CN 201811183029 A CN201811183029 A CN 201811183029A CN 109289868 B CN109289868 B CN 109289868B
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catalyst
carrier
nickel
pyrolysis gasoline
alumina
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CN109289868A (en
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施清彩
陈新忠
陈明海
庄旭森
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YANTAI BAICHUAN HUITONG TECHNOLOGY Co.,Ltd.
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Yantai Baichuan Huitong Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • C10G45/10—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 platinum group metals 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a selective hydrogenation catalyst for pyrolysis gasoline, which 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 contains 0.1-12 wt% of silicon oxide, 0.1-10 wt% of nickel-doped lanthanum ferrite and 0.05-6.8 wt% of potassium, mesoporous pores of the carrier account for 3-75% of total pores, and macropores account for 1.5-60% of the total pores. The catalyst has good colloid resistance, strong arsenic resistance, sulfur resistance and water resistance, and is particularly suitable for cracking gasoline first-stage C6‑C8And C8And (4) selectively hydrogenating the distillate.

Description

Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst for selective hydrogenation of pyrolysis gasoline and a preparation method thereof.
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 cracking raw material and the cracking condition of each ethylene unit, the composition of the cracking gasoline raw material of each unit has larger difference, in particular to diene and colloid (diene) of the cracking gasolineAnd high molecular polymer generated by polymerization reaction of unsaturated components such As styrene) and the contents of As and heavy metal are greatly different; some crude pyrolysis gasoline has high diene and colloid content, while some crude pyrolysis gasoline has high colloid content, high As content, high heavy metal content and other toxic materials, and some crude pyrolysis gasoline has high diene, colloid content, high As content, high heavy metal content and other toxic materials.
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.
CN201010622227.1 relates to a catalyst for selective hydrogenation of pyrolysis gasoline, which comprises magnesia-titania-alumina composite oxide as a carrier, and metallic palladium active component and group IIA and/or group IIIB metal promoter metal loaded on the composite oxide carrier, wherein the metallic palladium content is 0.25-0.35 wt%, the promoter metal content is 0.2-3 wt%, and the magnesia content and titania content in the carrier based on alumina are 0.1-3 wt%. The catalyst can be used for selective hydrogenation of pyrolysis gasoline, and has the advantages of high low-temperature activity, high selectivity, strong As, S, O and N impurity resistance, large gel capacity and stable activity under long-period operation. Furthermore, the invention relates to the preparation of said catalystAnd application in the selection of hydrocracked gasoline. Finally, the invention also relates to a method for preparing the composite oxide carrier by adopting a parallel-flow coprecipitation method. 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, comprising an alumina-titania composite as a carrier, and active components Pd and Ag supported on the carrier, wherein the content of Pd is 0.15-0.5 wt% based on the total weight of the catalyst, 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 to react, so that the components of diolefin and alkenyl aromatic hydrocarbon in the raw material are converted into mono-olefin and alkyl aromatic hydrocarbon, wherein the catalyst comprisesAn alumina carrier, active component metallic palladium or oxide thereof, at least one element selected from IA or IIA in the periodic table of elements or oxide thereof, at least one element selected from IVA or VA in the periodic table of elements or oxide thereof, and 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, the hydrogen/oil volume ratio of 80: 1 and the fresh oil airspeed 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 aims to provide a selective hydrogenation catalyst for pyrolysis gasoline, which has higher activity and better selectivity in reaction and has strong colloid resistance, arsenic resistance, water resistance and sulfur resistance. The carrier of the catalyst is a silicon oxide-aluminum oxide carrier, the carrier contains nickel-doped lanthanum ferrite, and the catalyst is particularly suitable for cracking gasoline in a first section C6-C8And C8And (4) selectively hydrogenating the distillate.
The invention provides a selective hydrogenation catalyst for pyrolysis gasoline, which 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 contains 0.1-12 wt% of silicon oxide, 0.1-10 wt% of nickel-doped lanthanum ferrite and 0.05-6.8 wt% of potassium, mesoporous pores of the carrier account for 3-75% of total pores, and macropores account for 1.5-60% of the total pores. The micropores, mesopores and macropores in the carrier are not uniformly distributed.
The palladium content in the above catalyst is preferably 0.20 to 0.3% 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 potassium 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 with 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, and the organic polymers are not simply expanded, but the micropores, mesopores and macropores of the carrier are not uniformly distributed, so that the pore structure of the carrier can be improved, the micropores, mesopores and macropores of the carrier are not uniformly distributed, the colloid resistance of the catalyst is improved, the stability and the service life of the catalyst are improved, and the long-period operation of the device is facilitated; and the surface of the carrier is promoted to generate more active site loading centers, the hydrogenation activity of the palladium catalyst is improved, and the method is suitable for one-stage selective hydrogenation of pyrolysis gasoline.
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, then the alumina precursor and 2.5g potassium nitrate are added, evenly mixed and 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 comprises 4.4 wt% of silica, 5.7 wt% of nickel-doped lanthanum ferrite and 1.6 wt% of potassium, mesoporous pores of the carrier account for 64.2% of total pores, and macroporous pores account for 25.6% of 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 comprises 8.4 wt% of silica, 2.6 wt% of nickel-doped lanthanum ferrite and 0.8 wt% of potassium, 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 3.5 wt% of potassium, 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 2.5g of potassium 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 2.5g of potassium 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 loaded separately into 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 C8The diene content of the distillate was 17.24g iodine/100 g oil, the gum content was 197mg/100ml oil, the bromine number was 36.34g bromine/100 g oil, the sulfur content was 95ppm, the free water content was 967ppm and the arsenic content was 156 ppb; the reaction process conditions are as follows: the inlet temperature is 40 ℃, the volume ratio of hydrogen to oil is 120: 1, the reaction pressure is 2.5MPa, and the space velocity of fresh oil is 5.5h-1(ii) a The average diene of the hydrogenation product of the catalyst 1 is 0.45 g of iodine/100 g of oil after running for 200h, the bromine number is 19.45 g of bromine/100 g of oil, and the diene hydrogenation rate is 98.7 percent; the average diene of the hydrogenation product of the catalyst 2 in 200 hours of running is 0.39 g of iodine/100 g of oil, the bromine number is 20.41 g of bromine/100 g of oil, and the diene hydrogenation rate is 98.4%. The average diene of the hydrogenation product of the catalyst 3 is 0.34 g of iodine/100 g of oil, the bromine number is 20.33 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.1 percent. The average diene of the hydrogenated product of the catalyst 4 is 0.37 g of iodine/100 g of oil, the bromine number is 19.32 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.9 percent; compared with the catalyst 1, the average diene of the hydrogenated product is 2.18 g of iodine/100 g of oil, the bromine number is 27.45 g of bromine/100 g of oil, and the diene hydrogenation rate is 78.3 percent; compared with the catalyst 1, the performances of arsenic resistance, sulfur resistance and water resistance are poor, and the hydrogenation selectivity of diene is low; compared with catalyst 2, the average diene of the hydrogenated product is 1.46 g iodine/100 g oil, the bromine number is 25.23 g bromine/100 g oil, and the diene hydrogenation rate is 84.6%; the comparative catalyst 2 has poor colloid resistance and low activity.
Under the conditions that the diene content of raw oil is 17.24g of iodine/100 g of oil, the colloid content is 197mg/100ml of oil, the sulfur content is 95ppm, the free water content is 967ppm and the arsenic content is 156ppb, the diene hydrogenation rate is over 98.1 percent, the average diene is 0.34-0.45 g of iodine/100 g of oil, the catalyst activity is higher, the selectivity is better, the colloid resistance and water resistance are better, and the arsenic resistance and sulfur resistance are strong.
After the catalyst 1-4 is operated for 500 hours, the average diene of the hydrogenation product of the catalyst 1 is 0.49 g of iodine/100 g of oil, the bromine number is 19.89 g of bromine/100 g of oil, and the diene hydrogenation rate is 98.6 percent; the average diene of the hydrogenation product of the catalyst 2 is 0.42 g of iodine/100 g of oil, the bromine number is 20.53 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.5 percent. The average diene of the hydrogenation product of the catalyst 3 is 0.36 g of iodine/100 g of oil, the bromine number is 20.73 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 97.8 percent. The average diene of the hydrogenated product of the catalyst 4 is 0.35 g of iodine/100 g of oil, the bromine number is 19.38 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.8 percent. The catalyst carrier contains nickel-doped lanthanum ferrite, which is beneficial to inhibiting polymerization reaction of unsaturated components such as diene, 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.
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 catalyst for the pyrolysis gasoline is characterized by comprising 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 contains 0.1-12 wt% of silicon oxide and 0.1-10 wt% of nickel-doped lanthanum ferrite, nickel in the nickel-doped lanthanum ferrite accounts for 0.1-8 wt% of the lanthanum ferrite and 0.05-6.8 wt% of potassium, mesoporous pores of the carrier account for 3-75% of the total pores, macroporous pores account for 1.5-60% of the total pores, and micropores, mesoporous pores and macropores in the carrier are unevenly distributed; 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, then mixing the silicon source-pseudo-boehmite-organic polymer mixture with the alumina precursor, adding a potassium source, extruding, forming, drying and roasting to obtain a silica-alumina carrier; the preparation method of the catalyst comprises the following steps: the active component palladium is dipped and sprayed on the carrier, and then the catalyst is dried and roasted to obtain the catalyst.
2. The pyrolysis gasoline selective hydrogenation catalyst of claim 1, wherein the catalyst palladium content is 0.20-0.3 wt%.
3. The selective hydrogenation catalyst 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 catalyst for pyrolysis gasoline according to claim 1, wherein the silicon source is silica gel, sodium silicate or silica micropowder, and the alumina in the mixture of the silicon source, pseudo-boehmite and organic polymer accounts for 1-35 wt% of the alumina in the carrier.
5. The selective hydrogenation catalyst 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.
6. The selective hydrogenation catalyst for pyrolysis gasoline of claim 1, wherein the nickel-doped lanthanum ferrite in the silica-alumina carrier is 0.2-8 wt%.
7. The pyrolysis gasoline selective hydrogenation catalyst of any one of claims 1 to 6, wherein 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, 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.
8. The pyrolysis gasoline selective hydrogenation catalyst of claim 1, wherein the catalyst is prepared by the following process: preparing a palladium-containing solution to dip the macroporous alumina carrier, drying the alumina carrier for 3 to 9 hours at the temperature of 110 to 160 ℃, and roasting the alumina carrier for 4 to 9 hours at the temperature of 400 to 650 ℃ to finally obtain a catalyst product.
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