CN107754845A - High life reformate olefine lowering catalyst - Google Patents

High life reformate olefine lowering catalyst Download PDF

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Publication number
CN107754845A
CN107754845A CN201610707681.4A CN201610707681A CN107754845A CN 107754845 A CN107754845 A CN 107754845A CN 201610707681 A CN201610707681 A CN 201610707681A CN 107754845 A CN107754845 A CN 107754845A
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catalyst
reformate
aromatic hydrocarbons
olefin
high life
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CN107754845B (en
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李为
王月梅
孔德金
龚燕芳
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/106—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • C10G2300/70—Catalyst aspects

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

Abstract

The present invention relates to a kind of high life reformate olefine lowering catalyst, mainly solves current techniques and the problem of service life is short, and catalyst switching is frequent be present.The reformate olefin-reducing catalyst for aromatic hydrocarbons of high life of the present invention a kind of, is formed with catalyst and counted, including following component：0.02~70 part of solid super-strong acid, 0.01~8 part of one or more of element for being selected from first, second main group, 30~85 parts of USY type molecular sieves, binding agent is selected from salic, silica one or more, preferably solves the problem, it is active good, the advantages of long lifespan, it can be used in the industrial production of aromatic hydrocarbons Olefin decrease.

Description

High life reformate olefine lowering catalyst
Technical field
The invention belongs to a kind of reformate olefin-reducing catalyst for aromatic hydrocarbons, and in particular to NEW TYPE OF COMPOSITE reforms oil-off olefin catalysis Agent.
Background technology
The present invention relates to a kind of reformate olefin-reducing catalyst for aromatic hydrocarbons, the new catalyst of specific extra long life.
Aromatic hydrocarbons is to mostly come from aromatic hydrocarbons to reform combined unit.In reformate aromatic product after catalytic reforming reaction Contain a certain amount of olefin impurity.Alkene chemistry property is active, and not only easily polymerization forms macromolecular colloid debris, but also easily Reacted with other aromatic components, generate other components outside triphen, so as to influence the quality of aromatic hydrocarbon product and triphen yield, drop The benefit of low device.
Aromatic hydrocarbons subsequent production technique such as dimethylbenzene adsorption separation process is to alkene caused by reformate or other drippolenes It is especially sensitive, even if the content of olefin impurity is a small amount of, can also very detrimental effect be produced to technical process.It is qualified in order to obtain Subsequent production needed for industrial chemicals and ensure the stable operation of subsequent technique, have removing trace amounts of olefin impurity unit.
Due to refining step all in most Aromatic Hydrocarbon United Plants using carclazyte as refining agent, as low pressure is reformed Popularization, gum level increase in reformate, the puzzlement that carclazyte is brought will be more serious, substitute the efficient deolefination of industrial carclazyte Catalyst and application technology are into trend.
Clay-filtered is to contact reformate with carclazyte, reaches removing alkene using the suction-operated and catalytic action of carclazyte Impurity.Carclazyte has acid centre, under the conditions of high pressure liquid phase, 150~200 DEG C, has certain catalytic polymerization ability and hole Road adsorption capacity, the trace amounts of olefin that can make to contain in reformate occur the reaction such as hydrocarbonylation, polymerization, generate higher-boiling compound, so Afterwards by bleaching earth adsorption, or removed in later separation flow.Typical catalyst CN102091648A, CN1232862, It is described in the patents such as CN102658196A.Although carclazyte have removing alkene ability, due to its specific surface area compared with Small, pore passage structure is simple, therefore inactivates comparatively fast, and the life-span is shorter, and because the carclazyte high temperature regeneration pore structure after inactivation substantially contracts It is small, cause deolefination ability to decline very fast, regenerability is poor, causes carclazyte frequently to change, and the carclazyte after inactivation can only By buried processing, environmental pollution is caused.
It is using noble metal platinum or palladium catalyst after petroleum reforming technique, to aromatic hydrocarbons original to have deolefination technique hydrofinishing Material carry out " back end hydrogenation process ", make alkene saturation and remove olefin impurity, typical catalyst CN85100760A, In the patents such as CN85100215A, CN1448474A, CN101260320A.But for simultaneously containing benzene, toluene and dimethylbenzene For the wide component of aromatic hydrocarbons, hydrogenation reaction depth is difficult to take into account comprehensively, and low boiling is formed after C9 aromatic and the hydrogenation of the above when special The aromatic hydrocarbons such as point toluene, make the loss of aromatic hydrocarbon product larger.Hydrogen circulation and the separation of hydrogen and oil product be present in hydrofinishing route For problem, it is necessary to set up the equipment such as compressor, gas-liquid separator and stripper, technique is complex, and energy consumption and material consumption are high, used to urge Agent is mostly noble metal catalyst, expensive.
Relatively reasonable removes olefin process using molecular sieve.Molecular sieve is that artificial synthesized have spacious multidimensional structure Alumionsilicate crystalline body.Compared with carclazyte, molecular sieve specific surface area is high, has higher appearance charcoal ability, lasts a long time；Molecular sieve Acidity is produced by the unsaturated coordination of skeletal atom, therefore acidity is basically unchanged after high temperature regeneration, and reproducibility is preferable, therefore point Sub- sieve catalyst has preferable stability and longer life-span.In view of the above-mentioned advantage of molecular sieve catalyst, it has been disclosed that permitted More achievements in research and the olefinic hydrocarbon expelling catalyzer prepared using molecular sieve as key component.EP0895977A1 is disclosed with 80% molecule It is main body to sieve as active component and 20% aluminum oxide, mediates extrusion by binding agent of acid Alusil, is ground into after drying and roasting The particle of 20-40 mesh is finished catalyst.It is active component to be described in WO 01/30942A1 using mesoporous molecular sieve MCM-22 Catalyst removal alkene is prepared with clay carrier shaping, the extrusion rate of alkene is higher than 95%.CN1618932A、CN 103495435A is described under conditions of non-hydrogen, uses molecular sieve as active component, and aluminum oxide or kaolin are that carrier preparation is urged The method of agent, catalyst have renewable recycling.One kind is described in CN102008976A by high silica alumina ratio ReUSY to be divided Son sieve is main active component, and using mordenite molecular sieve as the second active component, aluminum oxide is binder component, is added inorganic Acid or organic acid carry out kneading extrusion, and drying roasting obtains catalyst.But in above-mentioned invention disclosed patent, it is urged The acidity of agent is mainly supplied by molecular sieve, and this is weaker for trace amounts of olefin in reformate is removed by alkylated reaction , need higher reaction temperature to can be only achieved the purpose for thoroughly removing alkene during use, do not only result in energy consumption increase, The generation of the side reactions such as coking carbon distribution, the reaction of aromatic hydrocarbons dealkylation, aromatic hydrocarbons cracking is caused, causes the loss of aromatic hydrocarbons.
Chinese patent CN1618932 describes one kind catalytic refining reforming aromatic oil catalyst under conditions of non-hydrogen.Should Catalyst is non-loading type solid acid catalyst, using the catalyst treatment reforming aromatic oil, in 100~300 DEG C of reaction temperature, 0.5~3.0MPa of reaction pressure, during air speed 0.5~40-1Under the conditions of, the trace amounts of olefin in energy Arene removal, but although this is urged Agent can regenerate reuse, but its single pass life is still too short, when air speed is 15-1Under the conditions of check and rate 18 hours after, Its activity is just reduced to 50%, thus commercial Application is very limited.
The invention aims to overcome the problem of reformation oil-off olefin molecular sieve catalyst life-span is low in the past, using super Strong acid is combined the method prepared with molecular sieve, obtains the catalyst purpose of high life.
The content of the invention
One of technical problems to be solved by the invention are that mainly to solve the conventional catalyst for removing olefins from reforming oil life-span relatively low The problem of.By the compound method for preparing catalyst of super acids and molecular sieve, preferably solves problem, catalyst has the life-span The advantages of long.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of reformate virtue of high life Hydrocarbon drops
Alkene catalyst, in terms of catalyst proportion of composing, containing following component：
E) 0.02~70 part of solid super-strong acid；
F) 0.01~8 part of one or more of element for being selected from first, second main group；
G) 30~85 parts of Y type molecular sieve；
H) wherein binding agent is selected from salic, silica one or more.
For in above-mentioned offer technical scheme：
Solid super-strong acid as the catalytic activity component in catalyst, catalyst is mesoporous and macropore duct on contact alkene And other reactants, so as to remove olefin impurity.For the process because duct is larger, diffusion rate is more much faster than micro porous molecular sieve. By weight percentage, solid super-strong acid weight content 0.02-70%, the solid super-strong acid weight content 15-50% of optimization.
In above-mentioned technical proposal, solid super-strong acid SO4 2-/MxOyOne or more, wherein M is Zr, Ti, Fe.Or Solid super-strong acid is WO3/ZrO2、MoO3/ZrO2One or more.Both the above can also have.
A part as catalysts is by adjusting the alkylation activity present invention using a certain amount of acid side of addition Method.In above-mentioned technical proposal, by weight percentage, contained in terms of the oxide of Li, Na, K, Rb, Cs one or more of elements Have 0.01~8%.By weight percentage, contained in terms of the oxide of one or more of elements in Be, Mg, Ca, Sr, Ba 0.01~8%.The oxide containing 0.5~3% one or more of elements in Na, K, Mg, Ca, Sr, Ba of optimization.Institute The element stated before the forming, shaping in, shaping after simultaneously or it is different when in introduce.
Y molecular sieve is that have to adjust pore passage structure and acidity in a big way, as chain carrier supplier and carrier, By weight percentage, containing 30~80% Y type molecular sieve.Catalyst is 30~85%, and optimization is accounted for percentage by weight Meter, contains 50~85% USY type molecular sieves.General industry, which is produced as USY, can also add a part of NaY or HY.
It is salic in catalyst, silica is one or more of in above-mentioned technical proposal.
Molecular sieve after silica or alumina binder shaping and roasting with obtaining the molecular sieve catalyst containing a certain amount of pore volume. Silica or account for 15~60% or so of weight with aluminum oxide knot in the catalyst.Preferable scope silica or and oxidation Aluminium accounts for overall catalyst weight 15~40%.
Olefinic hydrocarbon expelling catalyzer by super acids and molecular sieve it is kneaded and formed then roasting etc. means prepare.Kneading process uses In addition to material containing catalyst activity component, a certain amount of lubricant, carrier, perforating agent etc. are chosen, carries out kneaded and formed and then roasting Burning obtains catalyst.It can be modified in preparation by the first main group, the second main group or rare earth element, adjust catalyst Acidity.Can also then it be molded first to super acids or molecular sieve modified.Row element can also be entered in forming process to add Add.It is modified in shaping and roasting rear catalyst, is combined with acid centre, obtains the catalyst of better performance.
Catalyst is prepared according to the technical program, the described reformate Olefin decrease reaction condition that is used for is in temperature 130~260 DEG C, 0.3~5.0MPa of pressure, 0.1~10h of weight space velocity-1。
In aromatic hydrocarbons reforms oil-off olefin molecular sieve catalyst, molecular sieve is employed as catalyst activity component, when Using the acid activated centre of molecular sieve, and duct is more, but causes a problem and can not solve, due to for liquid phase reactor, Reaction product is polycyclic aromatic hydrocarbon, and the diffusion rate of aromatic hydrocarbons is relatively low, therefore reaction is diffused into mesoporous or macropore duct from molecular sieve, It is diffused into again from above-mentioned duct outside outer catalyst, its is less efficient, easily causes secondary response again, forms colloid or coke, causes The loss of catalyst inactivation and raw material.And the method for using solid super-strong acid, react, go on the mesoporous duct with macropore Except alkene, it can at once spread and depart from activated centre, so as to avoid secondary response again, so as to obtain preferable catalyst.While by Larger in duct, diffusion is very fast, therefore catalyst activity greatly improves, and catalyst amount is less.Catalyst prepared by the present invention Method by providing novel active center, solve the problems, such as that the life-span of conventional catalyst is shorter.
By using example below, the invention will be further elaborated：
【Embodiment 1】
Containing 1.0wt%Na2O USY (SiO2/Al2O3Than 6.5) 60.0g, SO4 2-/ZrO2(sulphur weight content in super acids 4.0%) 20.0g and aluminum oxide 20.0g, add sesbania powder 4.0g and mediate extruded moulding.After dry 550 DEG C of roastings 3 hours, obtain To catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination in fixed bed reactors, raw material is reformation Oil, bromine index are 1238 milligrams of Br/100 grams of oil (reaction raw materials evaluation that all examples below uses).Activity calculates public Formula is as follows：
Reaction pressure：2.0MPa, temperature：160 DEG C, air speed：10.0h-1, Activity Results 2 hours 95%, 100 hours 93.5%, 200 hours 90.0%.
【Embodiment 2】
USY (SiO containing 2.0wt%MgO2/Al2O3Than 18.0) 70.0g, SO4 2-/TiO2(sulphur weight content 3.0%) 16.0g and aluminum oxide 15.0g, add sesbania powder 5.0g and mediate extruded moulding.After dry 560 DEG C of roastings 2 hours, it is catalyzed Agent.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 5.0MPa, temperature：180 DEG C, air speed：8.0h-1, Activity Results 2 hours 94.0%, 100 hours 93.0%, 200 hours 90.0%.
【Embodiment 3】
Containing 0.01wt%Na2O USY (SiO2/Al2O3Than 18.0) 85.0g, SO4 2-/Fe2O3(sulphur weight content 2.0%) 10.0g and aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.After dry 560 DEG C of roastings 2 hours, it is catalyzed Agent.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：170 DEG C, air speed：5.0h-1, Activity Results 2 hours 95.0%, 100 hours 92.0%, 200 hours 90.0%.
【Embodiment 4】
Containing 0.01wt%K2O USY (SiO2/Al2O3Than 12.0) 85.0g, SO4 2-/ZrO2(sulphur weight content 1.0%) 0.02g and aluminum oxide 15.0g, add sesbania powder 5.0g and mediate extruded moulding.After dry 560 DEG C of roastings 2 hours, then, 35.0g the solution ((NO containing Sr3)22.0%) incipient impregnation, dry, then 500 DEG C are calcined 3 hours.Obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：260 DEG C, air speed：8.0h-1, Activity Results 2 hours 96.0%, 100 hours 95.0%, 200 hours 93.0%.
【Embodiment 5】
USY (SiO containing 1.0wt%BaO2/Al2O3Than 6.0) 30.0g, SO4 2-/ZrO2(sulphur weight content 1.0%) 70.0g, add sesbania powder 5.0g and mediate extruded moulding.560 DEG C of roastings are dried, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：260 DEG C, air speed：2.0h-1, Activity Results 2 hours 95.0%.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 0.3MPa, temperature：130 DEG C, air speed：6.0h-1, Activity Results 2 hours 90.0%, 100 hours 90.1%, 200 hours 88.9%.
【Embodiment 6】
Containing 0.8wt%MgO, 1.0%Na2O (amount of addition is year-on-year) USY (SiO2/Al2O3Than 5.0) 50.0g, SO4 2-/ZrO2(sulphur weight content 1.0%) 35.0g, 2.0g barium nitrates and silica 1 5.0g, add the g of sesbania powder 5.0 and pinch Close extruded moulding.560 DEG C of roastings are dried, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：180 DEG C, air speed：2.0h-1, Activity Results 2 hours 96.0%.
【Embodiment 7】
Containing 1.2wt%MgO, 1.0%Na2O USY (SiO2/Al2O3Than 9.0) 60.0g, WO3/ZrO2(tungsten weight content 30.0%) 35.0g, 2.0gBa (NO3)2And aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.Dry 560 DEG C of roastings Burn, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：130 DEG C, air speed：0.1h-1, Activity Results 2 hours 98.0%.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：160 DEG C, air speed：1.7h-1, Activity Results 2 hours 97.6%.
【Embodiment 8】
Containing 1.0wt%MgO, 1.0%Na2O USY (SiO2/Al2O3Than 10) 45.0g, MoO3/ZrO2(tungsten weight content 30.0%) 45.0g and silica 5.0g and aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.Dry 560 DEG C Roasting, obtains catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 2.0MPa, temperature：180 DEG C, air speed：1.0h-1, Activity Results 2 hours 98.0%, 200 hours 97.0%.
【Embodiment 9】
Containing 1.0%Na2O USY (SiO2/Al2O3Than 10) 45.0g (containing NaHY10.0g), MoO3/ZrO2(MoO3Weight contains Measure 30.0%) 25.0g, WO3/ZrO2-SiO2(WO3Weight content 20.0%) 20.0g and silica 5.0g and aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.600 DEG C of roastings are dried, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 2.0MPa, temperature：180 DEG C, air speed：1.5h-1, Activity Results 2 hours 97.0%, 200 hours 96.9%.
【Embodiment 10】
Containing 1.3%Na2O USY (SiO2/Al2O3Than 10) 45.0g (containing NaY10.0g), MoO3/ZrO2(tungsten weight content 30.0%) 25.0g, S2O8 2-/ZrO2-La2O3(S weight contents 6.0%) 20.0g and silica 5.0g and aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.600 DEG C of roastings are dried, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 1.8MPa, temperature：170 DEG C, air speed：10.0h-1, Activity Results 2 hours 95.0%, 200 hours 94.0%, 400 hours 90.2%, 600 hours 80.0%.
【Embodiment 11】
Containing 1.3%Na2O USY (SiO2/Al2O3Than 10) 45.0g (containing NaY10.0g), MoO3/ZrO2(tungsten weight content 30.0%) 25.0g, S2O8 2-/ZrO2-La2O3(S weight contents 6.0%) 20.0g and silica 5.0g and aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.600 DEG C of roastings are dried, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 2.0MPa, temperature：180 DEG C, air speed：10.0h-1, Activity Results 2 hours 96.0%, 200 hours 95.5%, 400 hours 90.0%, 600 hours 81.0%.
【Embodiment 12】
Containing 1.0wt%BeO, 1.0%Li2O USY (SiO2/Al2O3Than 9.0) 60.0g, WO3/ZrO2(tungsten weight content 30.0%) 35.0g, 2.0gRbNO3And aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.Dry 560 DEG C of roastings Burn, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：160 DEG C, air speed：10h-1, Activity Results 2 hours 95.6%, 200 hours 95.0%, 400 hours 93.0%, 600 hours 89.0%.
【Embodiment 13】
Containing 1.0wt%MgO, 1.0%Cs2O USY (SiO2/Al2O3Than 8.0) 60.0g, WO3/ZrO2(tungsten weight content 30.0%) 35.0g, 1.8gB (NO3)2And aluminum oxide 5.0g, add sesbania powder 5.0g and mediate extruded moulding.Dry 560 DEG C of roastings Burn, obtain catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 3.0MPa, temperature：160 DEG C, air speed：1.7h-1, Activity Results 2 hours 95.0%, 200 hours 94.5%, 400 hours 94.0%, 600 hours 89.2%.
【Comparative example 1】
Take and contain 1.0wt%Na2O USY (SiO2/Al2O3Than 6.5) 3.0g catalyst, reaction pressure：2.0MPa, temperature： 160 DEG C, air speed：10.0h-1, Activity Results 2 hours 94%, 100 hours 90%, 200 hours 75%.
【Comparative example 2】
Take and contain 0.5wt%Na2O USY (SiO2/Al2O3Than 9.0) (weight 60%), WO3/ZrO2(WO3Weight content 30.0%) (super acids weight 35.0%), the catalyst 3.0g of aluminum oxide (containing 5.0%), reaction pressure：2.0MPa, temperature： 160 DEG C, air speed：10h-1, Activity Results 2 hours 96.6%, 200 hours 85.0%, 400 hours 70.0%.
【Comparative example 3】
Containing 0.3wt%Na2O USY (SiO2/Al2O3Than 6.5), the catalyst of 1.0wt%CaO and 15% aluminum oxide 60.0g, 3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors： 1.8MPa, temperature：170 DEG C, air speed：10.0h-1, Activity Results 2 hours 96.0%, 200 hours 89.0%, 400 hours 70%.

Claims (9)

  1. A kind of 1. high life reformate olefin-reducing catalyst for aromatic hydrocarbons, in terms of catalyst proportion of composing, containing following component：
    A) 0.02~70 part of solid super-strong acid；
    B) 0.01~8 part of one or more of element for being selected from first, second main group；
    C) 30~85 parts of Y type molecular sieve；
    D) wherein binding agent is selected from salic, silica one or more.
  2. 2. high life reformate olefin-reducing catalyst for aromatic hydrocarbons according to claim 1, it is characterised in that with percentage by weight Meter, solid super-strong acid weight content 0.02-70%.
  3. 3. high life reformate olefin-reducing catalyst for aromatic hydrocarbons according to claim 1, solid super-strong acid SO4 2-/MxOy's One or more, wherein M are Zr, Ti, Fe.
  4. 4. high life reformate olefin-reducing catalyst for aromatic hydrocarbons according to claim 1, it is characterised in that solid super-strong acid is WO3/ZrO2、MoO3/ZrO2One or more.
  5. 5. high life reformate olefin-reducing catalyst for aromatic hydrocarbons according to claim 1, it is characterised in that the first major element The oxide of one or more of elements selected from Li, Na, K, Rb, Cs, by weight percentage containing 0.01~8%.
  6. 6. high life reformate olefin-reducing catalyst for aromatic hydrocarbons according to claim 1, it is characterised in that the second major element The oxide of one or more of elements in Be, Mg, Ca, Sr, Ba, by weight percentage containing 0.01~8%.
  7. 7. high life reformate olefin-reducing catalyst for aromatic hydrocarbons according to claim 1, it is characterised in that with percentage by weight Meter, contains 30~80% Y type molecular sieve.
  8. 8. high life reformate olefin-reducing catalyst for aromatic hydrocarbons according to claim 7, Y type molecular sieve includes NaY, HY, USY It is one or more of.
  9. A kind of 9. method of reformate aromatic hydrocarbons Olefin decrease, using any one catalyst in claim 1~8, it is characterised in that It is 130~260 DEG C, 0.3~5.0MPa of reaction pressure, 0.1~10h of weight space velocity of reaction temperature that reaction process, which adjusts part,-1。
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CN108636399A (en) * 2018-04-27 2018-10-12 中国科学院山西煤炭化学研究所 The non-precious metal catalyst and its preparation method of reformed oil selective hydrogenation and olefin hydrocarbon removal and application
CN109433250A (en) * 2018-10-16 2019-03-08 江苏华伦化工有限公司 Reduce the catalyst of high boiling aromatic hydrocarbon solvent bromine index
CN111054426A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation and application thereof
CN111054429A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation and application thereof
CN112657544A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof
CN112657549A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Regenerated catalyst and preparation method and application thereof
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CN108636399A (en) * 2018-04-27 2018-10-12 中国科学院山西煤炭化学研究所 The non-precious metal catalyst and its preparation method of reformed oil selective hydrogenation and olefin hydrocarbon removal and application
CN109433250A (en) * 2018-10-16 2019-03-08 江苏华伦化工有限公司 Reduce the catalyst of high boiling aromatic hydrocarbon solvent bromine index
CN111054426A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation and application thereof
CN111054429A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation and application thereof
CN112657544A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof
CN112657549A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Regenerated catalyst and preparation method and application thereof
CN112657544B (en) * 2019-10-15 2023-09-29 中国石油化工股份有限公司 Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof
CN114425401A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Solid super acidic catalyst and preparation method and application thereof
CN114425401B (en) * 2020-10-15 2024-02-02 中国石油化工股份有限公司 Solid super acidic catalyst and preparation method and application thereof

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